A Literature Review on Co-processing of Alternative Fuels and Raw Materials and Hazardous Wastes in Cement Kilns Kåre Helge Karstensen 6 September 2007 Page 3 of 420 Table of content Table of content ........................................................................................................................... 3 Acronyms and abbreviations........................................................................................................ 8 Conversion of mass and mass divided by volume .................................................................... 13 Conversion of energy .................................................................................................................. 15 Glossary ......................................................................................................................... 17 1. Introduction ......................................................................................................................... 18 1.1 Policy and strategy ......................................................................................................... 19 1.2 Outline and content of this report................................................................................... 21 2. Thermal destruction of hazardous chemicals – an introduction..................................... 22 3. Cement production and the use of AFRs and hazardous waste...................................... 24 3.1 Fuels and materials used and possible replacements ..................................................... 26 3.2 Replacement practise ..................................................................................................... 31 3.3 Ability to destroy hazardous chemicals - inherent features ........................................... 33 3.3.1 Types of hazardous waste used by the cement industry ................................. 37 3.3.2 Fossil fuel versus hazardous waste fuel .......................................................... 39 3.4 Resource consumption in cement production ................................................................ 40 3.5 Benefits of burning hazardous waste in cement kilns.................................................... 43 3.5.1 Recovery of energy value from hazardous waste ........................................... 43 3.5.2 Conservation of nonrenewable fossil fuels ..................................................... 44 3.5.3 Reduction in production costs......................................................................... 44 3.5.4 Use of existing technology to treat large volumes of hazardous waste .......... 45 4. Environmental significance of cement production ........................................................... 46 4.1 Dust ......................................................................................................................... 46 4.2 Gaseous atmospheric emissions..................................................................................... 47 4.2.1 Carbon dioxide................................................................................................ 48 4.2.2 Nitrogen oxides ............................................................................................... 48 4.2.3 Sulfur oxides ................................................................................................... 49 4.2.4 Organic compounds ........................................................................................ 51 4.3 PCDD/PCDF emissions ................................................................................................. 51 4.3.1 Trace elements ................................................................................................ 54 4.4 Other emissions.............................................................................................................. 55 4.5 Normal emission levels from rotary kilns...................................................................... 56 4.6 Pollution reduction ......................................................................................................... 56 4.6.1 Water pollution and dust recovery .................................................................. 58 4.6.2 Health and safety............................................................................................. 58 4.6.3 Impacts on land use......................................................................................... 59 4.6.4 Communication............................................................................................... 60 4.7 Air pollution control in cement production.................................................................... 60 4.7.1 Inherent "scrubbing" of exit gases in preheater kiln ....................................... 65 5. Regulation of co-processing in the cement industry......................................................... 67 5.1 Waste definition ............................................................................................................. 68 5.2 Introduction to co-processing of hazardous waste in the US......................................... 69 Kåre Helge Karstensen [email protected] Page 4 of 420 5.2.1 Hazardous waste in the US ............................................................................. 69 5.3 Hazardous waste incineration in the EU ........................................................................ 72 5.3.1 Hazardous waste definition............................................................................. 74 5.3.2 Hazardous constitutents .................................................................................. 76 5.4 Emissions of dioxins - regulatory framework in the European Union........................... 80 5.4.1 PCDD/F emission limit values for cement kilns............................................. 82 5.4.2 Sampling and analysis..................................................................................... 84 5.4.3 Development and validation of the EN-1948 ................................................. 85 5.4.4 Analysis and recovery..................................................................................... 87 5.4.5 Detection/quantification limits and interferences ........................................... 87 5.4.6 HCB and PCBs................................................................................................ 88 5.5 Dioxin emission standards in the US ............................................................................. 88 5.6 The main emission regulation in the US ........................................................................ 89 5.7 The main emission regulation in the EU........................................................................ 93 5.8 Waste input control ........................................................................................................ 95 5.8.1 GTZ-Holcim Guidelines ................................................................................. 95 5.8.2 The Swiss Agency for the Environment, Forests and Landscape (1998) ....... 99 5.8.3 The Stockholm Convention .......................................................................... 101 5.9 Test burn....................................................................................................................... 101 6. Co-processing of hazardous wastes – fate of contaminants ........................................... 104 6.1.1 Fate of the constituents in the hazardous waste fuel..................................... 104 6.1.2 Organic constituents...................................................................................... 105 6.2 Metals ....................................................................................................................... 106 6.2.1 General behavior of metals in the cement kiln ............................................. 106 6.2.2 Emissions ...................................................................................................... 108 6.3 Results from trial burns................................................................................................ 112 6.3.1 Results from trial burns conducted in the 1980s........................................... 112 6.3.2 Results from trial burns conducted in the 1990s........................................... 113 6.3.3 Results from newer trial burns ...................................................................... 114 6.3.4 Results from trial burns that focused on PCBs ............................................. 114 6.3.5 Trial burns – a summary ............................................................................... 115 7. Formation, relase and control of PCDD/PCDFs............................................................. 116 7.1 Formation of PCDD/PCDFs in thermal processes....................................................... 116 7.2 Factors influencing formation of PCDD/PCDFs in cement production ...................... 118 7.3 Products of incomplete combustion - from the fuel..................................................... 119 7.3.1 Products of incomplete combustion - DRE of hazardous wastes ................. 120 7.3.2 Products of incomplete combustion - formation in the preheater................. 121 7.4 Feeding of hazardous wastes........................................................................................ 122 7.5 Feeding of non-hazardous wastes ................................................................................ 125 7.6 PCDD/PCDFs in solid materials.................................................................................. 131 7.7 Organics in the raw material (raw meal)...................................................................... 133 7.8 Chlorine ....................................................................................................................... 135 7.9 Catalysts ....................................................................................................................... 136 7.10 Particulates ................................................................................................................... 137 7.11 Temperature and operating conditions......................................................................... 138 7.12 Inhibitors ...................................................................................................................... 139 7.13 Factors influencing formation of PCDD/PCDFs in cement production - a summary 141 7.14 Controlling emissions of PCDD/PCDFs...................................................................... 143 7.15 UNEP Standardized Toolkit default emission factors for cement production.......... 147 7.16 Dioxin emission inventories and release contribution of the cement industry ............ 150 Kåre Helge Karstensen [email protected] Page 5 of 420 8. Potential risks to human health........................................................................................ 152 8.1 Introductory risk assessment in planning AFR activities............................................. 152 8.2 Cement operations........................................................................................................ 154 8.2.1 Cement plant emissions ................................................................................ 157 8.2.2 Fugitive emissions......................................................................................... 159 8.2.3 Regulated risks to human health ................................................................... 159 8.2.4 Health assessments of burning hazardous waste and conventional fuel....... 161 8.2.5 “Acceptable” risk .......................................................................................... 163 9. BAT/BEP for co-processing hazardous wastes in cement kilns .................................... 164 9.1 General measures for management .............................................................................. 164 9.2 Specific measures......................................................................................................... 166 9.3 Performance requirements based on best available techniques ................................... 171 10. Conclusion ....................................................................................................................... 173 11. References and bibliography ............................................................................................ 174 Annex 1 A review of the literature – general co-processing of AFR .................................... 217 Using alternative fuels and the advantages of process modeling in cement manufacturing217 Use of alternative fuels in the Polish cement industry ........................................................ 217 Research on alternative fuels for the cement industry......................................................... 218 Waste management and environmental protection by the use of alternative fuels in the cement production - experience from Germany -................................................................ 219 Efficiency of destruction of waste used in the co-incineration in the rotary kilns .............. 219 Waste incineration in cement plants: constraints and development opportunities (a French-German comparison) ............................................................................................... 220 The economics of tire remanufacturing............................................................................... 220 Thermal residue disposal in cement works – comparison with other methods of waste treatment ....................................................................................................................... 221 Experience with specialized control techniques when using secondary materials.............. 222 Burning of solid waste in cement kilns................................................................................ 222 Waste-derived fuel as a supplementary energy source at the Woodstock Cement Plant .... 223 The reuse of petroleum and petrochemical waste in cement kilns ...................................... 224 Replace coal by using refuse derived fuel, and reduce the fuel cost ................................... 224 The use of industrial sludges as raw materials in the cement industry................................ 227 Portland cement: constitution and processing. Part 1: cement manufacture ..................... 228 How to install a waste system.............................................................................................. 228 Best available technology for environmental protection in the cement industry ................ 230 Current knowledge of use of waste fuel in cement kilns..................................................... 230 Annex 2 A review of the literature –co-processing of hazardous wastes ............................. 232 Clean – up of persistent organic pollutants in the industrialized world .............................. 232 Environmentally Sound Destruction of Obsolete Pesticides in Developing Countries using Cement Kilns.............................................................................................................. 244 Implementation of using solid and hazardous wastes as supplementary fuel in Australia.. 244 Information support for the incineration of chemical waste in cement kilns ...................... 245 Destruction of chlorofluorocarbons in a cement kiln .......................................................... 245 Information support for toxic waste management ............................................................... 246 Incineration of waste liquid fuel review of the literature .................................................... 247 Metal spikes for incinerator and BIF compliance test and trial burn .................................. 248 Staying under the limit......................................................................................................... 248 Fuel substitution in cement kilns: an overview in the context of the proposed EU directive on the incineration of hazardous waste................................................................. 249 Kåre Helge Karstensen [email protected] Page 6 of 420 The use of monochlorobenzene as a principal organic hazardous constituent for destruction efficiency determinations in cement kilns ........................................................ 251 Hazardous waste fuels and the cement kiln......................................................................... 252 Types of risks associated with the combustion of hazardous waste in cement kiln ............ 253 Incineration of hazardous waste in cement kilns ................................................................. 253 Trial burns: methods perspective......................................................................................... 253 Waste solvent combustion sampling at kiln 1 for St. Lawrence Cement ............................ 254 Trial burns for hazardous waste incineration permits.......................................................... 256 Performance audit results for volatile POCH measurements during RCRA trial burn tests256 Safety arrangements for the auxiliary combustion of waste oils containing PCB in rotary cement kilns ....................................................................................................................... 257 RCRA trial burn considerations........................................................................................... 257 Hazardous waste combustion in industrial processes: cement and lime kilns..................... 258 Evaluation of hazardous waste incineration in a dry process cement kiln .......................... 258 Trial burn verification program for hazardous waste incineration ...................................... 259 Determination of the thermal stability of selected hazardous organic compounds ............. 260 Destruction of PCB’s in cement kilns ................................................................................. 260 Treatment of hazardous waste in cement kiln within a decentralized scheme: the Norwegian experience ......................................................................................................... 262 Knowledge of the potential problems as well as the opportunities by burning hazardous waste in cement kilns........................................................................................................... 262 Burning chemichal wastes as fuel in cement kilns .............................................................. 264 Destruction of chlorinated hydrocarbons in a cement kiln.................................................. 265 Burning waste chlorinated hydrocarbons in a cement kiln at the St. Lawrence Cement Co., Mississauga, Ontario.................................................................................................... 265 Annex 3 A review of the literature – environmental and health effects............................... 267 Formation, release and control of dioxins in cement kilns -a review.................................. 267 Pollutants emitted by a cement plant: health risks for the population living in the neighbourhood ..................................................................................................................... 268 Collecting air samplings for analyzing; to set a risk level for carcinogenic benchmark concentrations ...................................................................................................................... 269 Effect of burning supplementary waste fuels on the pollutant emissions by cement plants: a statistical analysis of process data..................................................................................... 269 Cement manufacture and the environment, part I ............................................................... 270 Cement manufacture and the environment, part II .............................................................. 271 PCDD/F and metal concentrations in soil and herbage samples collected in the vicinity of a cement plant ...................................................................................................................... 272 Field testing of particulate matter continuous emission monitors at the DOE Oak Ridge TSCA incinerator................................................................................................................. 272 Carbon dioxide emissions from the global cement industry ............................................... 273 Letter to the editor: comments on “The health effects of living near cement kilns; a symptom survey in Midlothian, Texas”............................................................................... 274 Mass balance of toxic metals in cement and aggregate kilns co-fired with fossil and hazardous waste-derived fuels............................................................................................. 274 The health effects of living near cement kilns; a symptom survey in Midlothian, Texas ... 275 Heavy metal outputs from a cement kiln co-fired with hazardous waste fuels ................... 276 Environmental challenges.................................................................................................... 276 Determining controls on element concentrations in cement kiln dust leachate................... 277 Environmental relevance of the use of secondary constituents in cement production ........ 278 Health effects from hazardous waste incineration facilities: five case studies.................... 278 Kåre Helge Karstensen [email protected] Page 7 of 420 Possibilities to reduce dioxin/furan and PCB emissions when using alternative combustibles in the cement industry.................................................................................... 279 A study of emissions, offsite concentrations, and health effects by burning hazardous waste in cement kilns........................................................................................................... 280 Sampling of trace constituents in the clean gas from rotary cement kilns .......................... 281 Experiences regarding pollution control problems in connection with the production of cement ....................................................................................................................... 282 Detecting waste combustion emissions ............................................................................... 282 Annex 4 A review of the literature – guidelines...................................................................... 284 The GTZ-Holcim Guidelines on Co-Processing Waste Materials in Cement Production .. 284 Waste to recovered fuel - cost-benefit analysis ................................................................... 287 Development of CCME National emission guidelines for cement kilns............................. 291 Cement manufacturing. Pollution prevention and abatement Handbook 1998 : Toward cleaner production ............................................................................................................... 291 Development of national guidelines for the use of hazardous and non-hazardous wastes in cement kilns in Canada.................................................................................................... 296 Comparison of criteria pollutants for cement kilns burning coal and hazardous waste fuels ....................................................................................................................... 297 Annex 5 A review of the literature – objections to co-processing of wastes in cement kilns ....................................................................................................................... 298 Annex 6 Council Directive of 12 December 1991 on hazardous waste (91/689/EEC)......... 317 Annex 7 Directive 2000/76/EC of the European Parliament and of the council of 4 December 2000 on the incineration of waste .......................................................................... 334 Annex 8 The example of Brevik, Norway, HeidelbergCement Group................................. 384 Annex 9 Permit for NORCEM cement plant, Brevik, Norway (1998)................................. 391 Annex 10 Swiss Guidelines (1998) ...................................................................................... 405 Kåre Helge Karstensen [email protected] Page 8 of 420 Acronyms and abbreviations AFR Alternative fuel and raw material APCD Air pollution control device ATSDR Agency for Toxic Substances and Disease Registry AWFCO Automatic waste feed cut-off BAT Best available techniques BEP Best environmental practise BHF Bag house filter BIF Boiler and industrial furnace Btu British thermal unit (One Btu was originally defined as the quantity of heat required to raise the temperature of 1 lb (0.45 kg) of water from 59.5° F (15.3° C) to 60.5° F (15.8° C) at constant pressure of 1 atmosphere; for very accurate scientific or engineering measurements, however, this value was not precise enough. The Btu has now been redefined in terms of the joule as equal to 1055 joules; in engineering, a Btu is equivalent to approximately 0.293 watt-hour. o C CAA Degree Celsius Clean Air Act CEMBUREAU European Cement Association CEMS Continuous emissions monitoring system CEN European Standardisation Organisation CFR Code of Federal Regulations CKD Cement kiln dust Cl2 Molecular chlorine CSI Cement Sustainability Initiative DL Detection limit CO Carbon monoxide CO2 Carbon dioxide DE Destruction efficiency Dioxins A term/abbreviation for polychlorinated dibenzodioxins and polychlorinated dibenzofurans (see also PCDD/Fs) DRE Destruction and removal efficiency Dscm Dry standard cubic meter Kåre Helge Karstensen [email protected] Page 9 of 420 EC European Commission EF Emission factor e.g. For example EPA Environmental Protection Agency EPER European Pollutant Emission Register ESP Electro static precipitator EU European Union 0 Celsius and Fahrenheit temperatures can be interconverted as follows: C = (F - F 32) × 100/180; F = (C × 180/100) + 32. FF Fabric filter g Gram GC-ECD Gas chromatography with electron capture detector GC-MS Gas chromatography with mass spectrometry HAPs Hazardous air pollutants HCB Hexachlorobenzene HCI Hydrogen chloride HF Hydrofluoric acid i.e. That is IPPC Integrated Pollution Prevention and Control I-TEF International Toxicity Equivalency Factor I-TEQ International Toxic Equivalent IUPAC International Union of Pure and Applied Chemistry J Joules 0 (Degree) Kelvin. Celsius and Kelvin can be interconverted as follows: C = (K K - 273.15); K = (C + 273.15) kcal Kilocalorie (1 kcal = 4.19 kJ) kg Kilogramme (1 kg = 1000 g) kJ Kilojoules (1 kJ = 0.24 kcal) kPa Kilo Pascal (= one thousand Pascal) L Litre lb Pound LCA Life cycle analysis LOD Limit of detection LOl Loss of ignition Kåre Helge Karstensen [email protected] Page 10 of 420 LOQ Limits of quantification m3 Cubic meter (typically under operating conditions without normalization to, e.g., temperature, pressure, humidity) MACT Maximum Achievable Control Technology MJ Mega joule (l MJ= 1000 kJ) mg/kg Milligrams per kilogram MS Mass spectrometry mol Mole (Unit of Substance) Na Sodium NA Not applicable NAAQS National Ambient Air Quality Standards NATO North Atlantic Treaty Organisation ND Not determined/no data (in other words: so far, no measurements available) NESHAP National Emission Standards for Hazardous Air Pollutants ng Nanogram (1 ng = 10-9 gram) Nm3 Normal cubic metre (101.3 kPa, 273 K) NH3 Ammonia NOx Nitrogen oxides (NO+NO2) NR Not reported N-TEQ Toxic equivalent using the Nordic scheme (commonly used in the Scandinavian countries) OECD Organisation for Economic Co-operation and Development O2 Oxygen PAH Polycyclic aromatic hydrocarbons PCA Portland Cement Association (USA) PCB Polychlorinated biphenyls PCDDs Polychlorinated dibenzodioxins PCDFs Polychlorinated dibenzofurans PCDD/Fs Informal term used in this document for PCDDs and PCDFs PIC Product of incomplete combustion pg Picogram (1 pg = 10-12 gram) PM Particulate matter POHC Principal organic hazardous constituent POM Polycyclic organic matter Kåre Helge Karstensen [email protected] Page 11 of 420 POP Persistent organic pollutants ppb Parts per billion ppm Parts per million ppmv Parts per million (volume basis) ppq Parts per quadrillion ppt Parts per trillion ppt/v Parts per trillion (volume basis) ppm Parts per million Pound imperial unit (abbreviation lb) of mass; the avoirdupois pound or imperial standard pound = 0.45 kg/7,000 grains, while the pound troy (used for weighing precious metals) = 0.37 kg/5,760 grains. QA/QC Quality assurance/quality control QL Quantification limit RACT Reasonably Available Control Technology RCRA Resource Conservation and Recovery Act RDF Refuse derived fuel RT Residence time sec Second SINTEF Foundation for Industrial and Scientific Research of Norway SNCR Selective non catalytic reduction SiO2 Silicon dioxide SCR Selective catalytic reduction SO2 Sulfur dioxide SO3 Sulfur trioxide SOx Sulfur oxides SQL Sample quantification limit SRE System removal efficiency t Tonne (metric) TCDD Abbreviation for 2,3,7,8-tetrachlorobidenzo-p-dioxin TCDF Abbreviation for 2,3,7,8-tetrachlorobidenzofuran TEF Toxicity Equivalency Factor TEQ Toxic Equivalent (I-TEQ, N-TEQ or WHO-TEQ) TEQ/yr Toxic Equivalents per year THC Total hydrocarbons Kåre Helge Karstensen [email protected] Page 12 of 420 TOC Total organic carbon tpa Tonnes per annum (year) TRI Toxics Release Inventory TSCA Toxics Substances Control Act UK United Kingdom US United States of America US EPA United States Environmental Protection Agency VDZ Verein Deutsche Zementwerke VOC Volatile organic compounds VSK Vertical shaft kilns WBCSD World Business Council for Sustainable Development WHO World Health Organization y Year % v/v Percentage by volume µg/m3 Micrograms per cubic meter µg Microgram Kåre Helge Karstensen [email protected] Page 13 of 420 Conversion of mass and mass divided by volume (http://physics.nist.gov/Pubs/SP811/appenB9.html#MASSinertia) To convert from to Multiply by carat, metric kilogram (kg) 2.0 E-04 carat, metric gram (g) 2.0 E-01 6.479 891 grain (gr) kilogram (kg) grain (gr) milligram (mg) 6.479 891 E+01 hundredweight (long, 112 lb) kilogram (kg) 5.080 235 E+01 hundredweight (short, 100 lb) kilogram (kg) 4.535 924 E+01 · s2/m) kilogram (kg) 9.806 65 E+00 ounce (avoirdupois) (oz) kilogram (kg) 2.834 952 E-02 ounce (avoirdupois) (oz) gram (g) 2.834 952 E+01 ounce (troy or apothecary) (oz) kilogram (kg) 3.110 348 E-02 ounce (troy or apothecary) (oz) gram (g) 3.110 348 E+01 pennyweight (dwt) kilogram (kg) 1.555 174 E-03 pennyweight (dwt) gram (g) 1.555 174 E+00 pound (avoirdupois) (lb) 23 kilogram (kg) 4.535 924 E-01 pound (troy or apothecary) (lb) kilogram (kg) 3.732 417 E-01 E-05 kilogram-force second squared per meter (kgf kilogram meter squared (kg · 2 pound foot squared (lb · ft ) m2) 4.214 011 E-02 kilogram meter squared (kg · 2 pound inch squared (lb · in ) m2) 2.926 397 E-04 slug (slug) kilogram (kg) 1.459 390 E+01 ton, assay (AT) kilogram (kg) 2.916 667 E-02 ton, assay (AT) gram (g) 2.916 667 E+01 ton, long (2240 lb) kilogram (kg) 1.016 047 E+03 Kåre Helge Karstensen [email protected] Page 14 of 420 ton, metric (t) kilogram (kg) 1.0 E+03 tonne (called "metric ton" in U.S.) (t) kilogram (kg) 1.0 E+03 ton, short (2000 lb) kilogram (kg) 9.071 847 E+02 To convert from to grain per gallon (U.S.) (gr/gal) Multiply by kilogram per cubic meter 1.711 (kg/m3) 806 grain per gallon (U.S.) (gr/gal) milligram per liter (mg/L) 1.711 806 3 gram per cubic centimeter (g/cm ) kilogram per cubic meter 1.0 (kg/m3) ounce (avoirdupois) per cubic inch (oz/in3) kilogram per cubic meter 1.729 (kg/m3) 994 ounce (avoirdupois) per gallon [Canadian and U.K. kilogram per cubic meter 6.236 (Imperial)] (oz/gal) (kg/m3) 023 ounce (avoirdupois) per gallon [Canadian and U.K. gram per liter (g/L) 6.236 (Imperial)] (oz/gal) 023 ounce (avoirdupois) per gallon (U.S.) (oz/gal) kilogram per cubic meter 7.489 (kg/m3) 152 ounce (avoirdupois) per gallon (U.S.) (oz/gal) gram per liter (g/L) 7.489 152 3 pound per cubic foot (lb/ft ) kilogram per cubic meter 1.601 (kg/m3) 846 3 kilogram per cubic meter 2.767 pound per cubic inch (lb/in ) 990 (kg/m3) 3 pound per cubic yard (lb/yd ) kilogram per cubic meter 5.932 (kg/m3) 764 pound per gallon [Canadian and U.K. (Imperial)] kilogram per cubic meter 9.977 637 (lb/gal) (kg/m3) pound per gallon [Canadian and U.K. (Imperial)] kilogram per liter (kg/L) 9.977 (lb/gal) 637 pound per gallon (U.S.) (lb/gal) kilogram per cubic meter 1.198 (kg/m3) 264 pound per gallon (U.S.) (lb/gal) kilogram per liter (kg/L) 1.198 264 3 slug per cubic foot (slug/ft ) kilogram per cubic meter 5.153 (kg/m3) 788 ton, long, per cubic yard kilogram per cubic meter 1.328 (kg/m3) 939 ton, short, per cubic yard kilogram per cubic meter 1.186 (kg/m3) 553 Kåre Helge Karstensen [email protected] E-02 E+01 E+03 E+03 E+00 E+00 E+00 E+00 E+01 E+04 E-01 E+01 E-02 E+02 E-01 E+02 E+03 E+03 Page 15 of 420 Conversion of energy (http://physics.nist.gov/Pubs/SP811/appenB9.html#MASSinertia) To convert from to Multiply by British thermal unitIT (BtuIT) 11 joule (J) 1.055 056 E+03 British thermal unitth (Btuth) 11 joule (J) 1.054 350 E+03 British thermal unit (mean) (Btu) joule (J) 1.055 87 E+03 British thermal unit (39 °F) (Btu) joule (J) 1.059 67 E+03 British thermal unit (59 °F) (Btu) joule (J) 1.054 80 E+03 British thermal unit (60 °F) (Btu) joule (J) 1.054 68 E+03 calorieIT (calIT) 11 joule (J) 4.1868 E+00 calorieth (calth) 11 joule (J) 4.184 E+00 calorie (mean) (cal) joule (J) 4.190 02 E+00 calorie (15 °C) (cal15) joule (J) 4.185 80 E+00 calorie (20 °C) (cal20) joule (J) 4.181 90 E+00 calorieIT, kilogram (nutrition) 12 joule (J) 4.1868 E+03 calorieth, kilogram (nutrition) 12 joule (J) 4.184 E+03 calorie (mean), kilogram (nutrition) 12 joule (J) 4.190 02 E+03 electronvolt (eV) joule (J) 1.602 177 E-19 erg (erg) joule (J) 1.0 foot poundal joule (J) 4.214 011 E-02 foot pound-force (ft · lbf) joule (J) 1.355 818 E+00 kilocalorieIT (kcalIT) joule (J) 4.1868 E+03 kilocalorieth (kcalth) joule (J) 4.184 E+03 kilocalorie (mean) (kcal) joule (J) 4.190 02 E+03 kilowatt hour (kW · h) joule (J) 3.6 E+06 kilowatt hour (kW · h) megajoule (MJ) 3.6 E+00 quad (1015 BtuIT) 11 joule (J) 1.055 056 E+18 therm (EC) 25 joule (J) 1.055 06 Kåre Helge Karstensen [email protected] E-07 E+08 Page 16 of 420 therm (U.S.) 25 joule (J) 1.054 804 E+08 ton of TNT (energy equivalent) 26 joule (J) 4.184 E+09 watt hour (W · h) joule (J) 3.6 E+03 watt second (W · s) joule (J) 1.0 E+00 Kåre Helge Karstensen [email protected] Page 17 of 420 Glossary AFR Alternative fuel and raw materials, often wastes or secondary products from other industries, used to substitute conventional fossil fuel and conventional raw materials. Cementitious Materials behaving like cement, i.e. reactive in the presence of water; also compatible with cement. Co-processing Utilisation of alternative fuel and raw materials in the purpose of energy and resource recovery. Dioxins Together with PCDD/PCDFs used as term/abbreviation for Polychlorinated dibenzodioxins and Polychlorinated dibenzofurans t DRE/DE Destruction and Removal Efficiency/Destruction Efficiency. The efficiency of organic compounds destruction under Combustion in the kiln. Kiln inlet/outlet Were the raw meal enters the kiln system and the clinker leaves the kiln system. Pozzolana Pozzolanas are materials that, though not cementitious in themselves, contain silica (and alumina) in a reactive form able to combine with lime in the presence of water to form compounds with cementitious properties. Natural pozzolana is composed mainly of a fine, reddish volcanic earth. An artificial pozzolana has been developed that combines a fly ash and water-quenched boiler slag. Kåre Helge Karstensen [email protected] Page 18 of 420 1. Introduction The development of a proper hazardous waste management infrastructure in emerging economies is not only required to protect human health and the environment but it is also necessary to sustain further development of their economies. The degree to which emerging economies have proper rules and regulations in place varies widely from country to country and even when regulations are in place, enforcement of such regulations can be weak. Many emerging economies do not have a proper hazardous waste management infrastructure in place. They often lack proper options for collection, transportation, storage and treatment often due to unclear standards and lack of enforcement, creating uncertainties regarding the prospects of the treatment and disposal facility business for private investors. Only easily recyclable hazardous wastes are processed while more difficult materials are often dumped. Some generators export their hazardous wastes to developed countries for treatment and disposal. Often the industries generating substantial quantities of hazardous wastes have limited options available to dispose of such wastes in a cost-effective and an environmental sound manner. They are reluctant to discuss waste generation and disposal practices and often report unusually low quantities of wastes generated. Liquid organic hazardous wastes including oily wastes frequently find their way into small furnaces and boilers. In most emerging economies, the rapid growth of industrial activity leads to increased levels of hazardous waste generation, long time before proper disposal means are available. Sometimes, temporary solutions are implemented, such as on-site storage or temporary landfilling. Emerging economies are therefore faced, not only with the management of current waste production, but also with the management of stockpiles of stored wastes. As these countries continue with their development, their environmental authorities are elaborating waste management regulations on a national level. In parallel, the cement industry in these countries has followed an economic boom, since concrete is a basic construction and development element, and invested in new plants in emerging markets. Thus large cement plants, producing millions of tonnes per year, have begun to spring up. Kåre Helge Karstensen [email protected] Page 19 of 420 The global cement industry is more and more dominated by the bigger international players, which is first of all expanding in emerging markets. When new plants are built today in any country, with no exception the best available techniques (BAT) applies. With rising energy costs, this is the only economic feasible option, which contributes to raise the performance and to phase out older, polluting technologies. The joining of the cement industry to the hazardous waste management system, can if well controlled provide a viable, economical and environmentally sound option for treating many hazardous and non-hazardous industrial wastes. As compared to other disposal processes, co-processing in cement kiln requires no major investments and creates no liquid or solid residues, and they are already in place with proper infrastructure. Cement kiln coprocessing can therefore be extremely attractive under proper guidance, regulation and control in emerging economies. A co-processing practise needs however to be anchored in a national policy. 1.1 Policy and strategy Co-processing of alternative fuels and raw materials (AFRs) and hazardous wastes in cement kilns will usually constitute one tool in a complete toolbox, complementary with other treatment options, usually consisting of physical/chemical treatment, various incineration options and landfill. A national policy on hazardous waste management should be the fundament to ensure that the development, implementation of strategies, legislation, guidelines, plans, treatment options and other elements of hazardous waste management will be exercised in accordance with the following guiding principles: • Hazardous wastes are a major environmental problem and priority should be given to prevention of dangerous impacts on human, the environment and the ecosystem; Kåre Helge Karstensen [email protected] Page 20 of 420 • The prevention and reduction of hazardous waste generation is the most beneficial approach to hazardous waste management and should be given priority; • Choice of waste management options should be based on the following hierarchy/priority: 1. Avoidance, prevention and minimisation; 2. Reuse and recycling; 3. Recovery of energy and resources; 4. Treatment and destruction; 5. Final sound and safe environmental disposal; • A hazardous waste minimisation strategy comprising waste prevention, cleaner production, reuse and recovery of materials and energy should be established; • The cost of preventing pollution and of treating waste should be borne by the individual or the organisation responsible for the pollution or by those who has produced the waste; • Control of hazardous waste should be based on the "cradle to grave principle"; • Hazardous waste treatment and disposal facilities for all categories of hazardous wastes comprising physical/chemical treatment, incineration and landfill should be safe, environmentally sound and cost efficient; • Proper management of hazardous waste requires the active involvement and cooperation of a wide range of stakeholders, including government, industry other waste generators, NGOs and the general public; • Enforcement of the hazardous waste management regulations should be based on qualified national and provincial capacity; Kåre Helge Karstensen [email protected] Page 21 of 420 • Development and operation of hazardous waste treatment and disposal facilities often requires involvement of the private sector. 1.2 Outline and content of this report This report focuses on co-processing of AFR and hazardous wastes in the cement industry; a comparative technology assessment will focus on features of cement production. This report is based on the collection and compilation of hundreds of documents published the last thirty years. The information sources used in this review is taken from reports published by international organisations, regulatory agencies as well as the cement industry, as well as articles in scientific peer reviewed and other professional journals. Some information is also from the internet, especially documents published by NGOs. It has not been possible to check the content of all material used. This literature review on co-processing of AFRs and hazardous wastes in the cement industry describes briefly the state of the state of the art when it comes to cement production and the environmental significance and the resource consumption in cement production. The report also gives an introduction to various regulatory approaches, mainly the European Union (EU) and the United States of America (USA/US), it goes through the fate of the contaminants in the waste when it is co-processed, it provides an comprehensive discussion of dioxin formation and control in cement kilns, potential risks to human health when coprocessing as well as the best available techniques (BAT) and best environmental practise (BEP) for co-processing hazardous wastes in cement kilns recommended by the Stockholm Convention. The annexes provides an comprehensive overview of literature available on the subject of co-processing in the cement industry, divided on general co-processing, hazardous wastes, environmental and health effects as well as guidelines. The annex also provides an collection of the views of various NGOs on this subject, as well as some relevant regulations and permits. Kåre Helge Karstensen [email protected] Page 22 of 420 2. Thermal destruction of hazardous chemicals – an introduction Combustion and other forms of thermal treatment have, over the years, been adopted as proven and the best available techniques to dispose of hazardous waste, municipal solid waste, and medical waste as regulated under the Resource Conservation and Recovery Act RCRA and toxic substances under the Toxic Substances Control Act TSCA in the United States (US) (Lee et al., 2000; Dempsey and Oppelt, 1993). Both dedicated incinerators and cement kilns can fulfil the combustion requirements with respect to safe and sound destruction of hazardous wastes, but cement kilns usually have higher temperatures and longer residence times than hazardous waste incinerators (Brunner 1993; Dempsey and Oppelt 1993; Niessen 1995). Combustion is a combination of pyrolysis and oxidation. Pyrolysis is a chemical change resulting from heat alone and involves the breaking of stable chemical bonds, often resulting in molecular rearrangement. Oxidation is the gross reaction of an organic species with oxygen and requires relatively low activation energies (Niessen, 1995). For efficient combustion, oxidation should be the dominant process, with pyrolysis occurring either incidentally to the oxidation or to put a material into a better physical form for oxidation. To combust hazardous wastes effectively, pyrolysis must be efficient and complete before oxidation of the molecular chemical by-products can occur. To achieve a complete thermal destruction, sufficient temperature, oxygen supply, residence time and mixing conditions are needed (Brunner 1993; Dempsey and Oppelt, 1993). Both dedicated hazardous waste incinerators and cement kilns can achieve a complete thermal destruction of mixed hazardous wastes, but normally cement kilns have higher temperature and longer residence times than incinerators (Freeman, 1997). This is why cement kilns are ideal; flame and kiln gas temperatures up to 2,000oC and long residence times up to 8 seconds ensures complete pyrolysis and surplus oxygen ensures complete oxidation (Freeman, 1997). Combustion temperature and residence time needed for mixed hazardous wastes cannot be readily calculated and are often determined empirically. Some common solvents such as alcohols and toluene can easily be combusted at lower temperatures, while other more Kåre Helge Karstensen [email protected] Page 23 of 420 complex organic halogens require more stringent conditions such as the United States Environmental Protection Agency (US EPA) Toxic Substances Control Act (TSCA) PCB incineration criteria of 2 seconds residence time at 1,200oC and 3% excess oxygen in the stack gas (Federal Register, 1999) or the European Council Directive 2000/76/EC on the Incineration of Waste criteria of 1100°C for at least two seconds if more than 1 % of halogenated organic substances are incinerated (Council Directive, 2000). Combustion and other forms of thermal treatment have, over the years, been adopted as proven technologies to dispose of hazardous waste, municipal solid waste, and medical waste regulated under the Resource Conservation and Recovery Act RCRA and toxic substances under the Toxic Substances Control Act TSCA (Lee et al., 2000; Dempsey and Oppelt, 1993). Pesticides constitute a considerable part of the compounds regulated under the TSCA (Ferguson and Wilkinson, 1984). The Stockholm Convention has mandated the Basel Convention (2006) to develop technical guidelines for environmentally sound management of wastes consisting of or contaminated with POPs. An important criterion for environmentally sound destruction and irreversible transformation is to achieve a sufficient destruction efficiency (DE) or destruction and removal efficiency (DRE). A DRE value greater than 99.9999 % is required for POPs in the United States (US) (Federal Register, 1999). The DRE consider emissions to air only while the more comprehensive DE is also taking into account all other out-streams, i.e. products and liquid and solid residues. The Basel Convention technical guidelines consider ten technologies to be suitable for environmentally sound destruction/disposal of POPs (Basel Convention, 2006). The most common among these are hazardous waste incineration and cement kilns, which also constitute the largest disposal capacity. The remaining eight technologies have comparatively low capacities (some are still at laboratory scale), are technically sophisticated and currently not affordable by many developing countries (UNEP, 2004). A thorough and objective comparison between all of these technologies on aspects like sustainability, suitability, destruction performance, robustness, cost-efficiency, patent restrictions (availability), competence requirements and capacities is not aviable. Kåre Helge Karstensen [email protected] Page 24 of 420 3. Cement production and the use of AFRs and hazardous waste Predecessors of current inorganic cements have been known ever since mankind first began to build with stone and brick, i.e. the lime-based materials used by the Greeks and Romans six centuries B.C. To-days Portland cement, however, was invented in the late 18th century and is manufactured in high temperature kilns (Roy, 1985). The cement industry is today widely distributed throughout the world and produced in 2003 approximately 1,940 million tons of cement (Cembureau, 2004). In short, Portland cement is made by heating a mixture of calcareous and argillaceous materials to a temperature of about 1450oC. In this process, partial fusion occurs and nodules of so-called clinker are formed. The cooled clinker is mixed with a few percent of gypsum, and sometimes other cementitious materials, and ground into a fine meal – cement (Duda, 1985). In the clinker burning process, which is primarily done in rotary kilns, it is essential to maintain kiln charge temperatures of approximately 1450°C and gas temperatures of about 2000°C. Also, the clinker needs to be burned under oxidising conditions (Duda, 1985; IPPC, 2001). The rotary kiln consists of a steel tube with a length to diameter ratio of between 10:1 and 38:1. The tube is supported by two to seven support stations, has an inclination of 2.5 to 4.5% and a drive rotates the kiln about its axis at 0.5 to 4.5 revolutions per minute. The raw mix is fed to the upper cool end of the kiln and the combination of the tube’s slope and rotation causes material to be transported slowly along it. In order to withstand the very high peak temperatures the entire rotary kiln is lined with heat resistant bricks (refractories). Modern short dry kiln systems with 5 cyclone multi stage preheating and precalcination are considered best available technology for ordinary new plants today and such a configuration will use 2,900-3,300 MJ of energy per ton of clinker (Environment Agency, 2001; IPPC, 2001). Cement kilns are equipped with either electro static precipitator (ESP’s) or fabric filters, or both, for particulate matter control. Acid gas pollution control devices are not used at cement kilns (except for SO2 in some instances) since the raw materials are highly alkaline and provide acid gas control. Kåre Helge Karstensen [email protected] Page 25 of 420 The emissions of CO2 is estimated to be 900 to 1,000 kg per ton clinker, related to a specific heat demand of approximately 3,000 to 5,000 MJ per ton clinker, but also depending on fuel type (Oss and Padovani, 2003; Worrell et al., 2001). Approximately 60% of the CO2 originates in calcination of limestone and the remaining 40% is related to fossil fuel combustion. The CO2 resulting from the combustion of the carbon content of the fuel is directly proportional to the specific heat demand as well as the ratio of carbon content to the calorific value of the fuel. For example, a specific heat demand of 3,000 MJ/ton of clinker and the use of hard coal with a calorific value of 30 MJ/kg and a carbon content of 88% results in a CO2 emission of 0.32 ton per ton of clinker, when regarding the fossil fuel only. This energy-intensive industry annually consumes the equivalent of approximately 200-300 million tons of coal and contributes to about 5% of the global anthropogenic CO2 emissions (Oss and Padovani, 2003; WBCSD, 2002; Worrell et al., 2001). Half of this is a result of the chemical process involved in the transformation of limestone into clinker; 40% is a result of burning the fuel. The remaining 10% is split between electricity use and transport. There are three main techniques available to the industry in reducing net total and per tonne CO2 emissions: Maximize the efficiency of the manufacturing process and associated equipment to use fuels and materials as efficiently as possible; Reduce the amount of fossil fuel used in the process by replacing it with biomass and wastes that would otherwise have been burned without energy recovery, and other materials having lower carbon content; Replace a proportion of the clinker in cement with alternative materials (which do not require thermal processing), reducing the CO2 emissions per tonne of cement produced. One of the main routes towards sustainability in the cement industry is to reduce the use of non-renewable fossil fuels and raw materials and replace by recovery of waste materials. The bigger international companies have realised their challenges with regards to Kåre Helge Karstensen [email protected] Page 26 of 420 sustainability and created the Cement Sustainability Initiative (CSI), which is a project spearheaded by 16 of the world’s largest cement producers in association with the World Business Council for Sustainable Development (WBCSD, 2005). 3.1 Fuels and materials used and possible replacements A cement plant consumes 3,000 to 6,500 MJ of fuel per tonne of clinker produced, depending on the raw materials and the process used (WBCSD, 2005). Most cement kilns today use coal and petroleum coke as primary fuels, and to a lesser extent natural gas and fuel oil. As well as providing energy, some of these fuels burn to leave fuel ash containing silica and alumina compounds (and other trace elements). These combine with the raw materials in the kiln contributing to the structure of the clinker and form part of the final product. Energy use typically accounts for 30-40% of the production costs. The main components of cement are oxides of calcium, silica, aluminum, and iron. These are formed by the transformation of minerals and materials in the kiln. Calcium is provided mainly by raw materials such as limestone, marl, or chalk. Silica, aluminum, and iron components, as well as other elements, are provided by clay, shale, and other materials. The different kinds of raw materials needed to achieve the required cement composition are ground and mixed to produce a homogeneous blend processed in the kiln. Natural limestone contains calcium carbonate and a complex mixture of minerals that varies from place to place. The composition of the raw materials is tested on a regular basis. A variety of other constituents can be used with clinker to create different kinds of cement with different uses. These other raw materials may have cementitious properties in their own right. In Ordinary Portland Cement, the proportion of gypsum (required to control the setting time of cement) to clinker is around 5%. For blended cements, a variety of materials can be added in varying proportions, in addition to clinker and gypsum. These include pozzolana and limestone. The properties and proportions of clinker, gypsum, and other constituents must be managed carefully to provide a product that meets the desired performance criteria or set of standards. Kåre Helge Karstensen [email protected] Page 27 of 420 None of the natural materials (fuels, marls, and limestone) used in cement production are pure substances as extracted from the ground; all are complex mixtures and all contain trace mineral elements, including heavy metals. The chemical compositions of typical materials compare to the clinker and to Portland cement can be found in the report of WBCSD (2005). The cement industry has many opportunities to replace a portion of the virgin natural resources it uses with waste and by-products from other processes. These may be used as fuels, raw materials, or as constituents of cement, depending on their properties. Alternative fuels and raw materials must meet quality specifications in the same way as conventional fuels and raw materials. Selected waste and by-products with recoverable calorific value can be used as fuels in a cement kiln, replacing a portion of conventional fossil fuels, like coal, if they meet strict specifications (WBCSD, 2005). Sometimes they can only be used after pre-processing to provide ‘tailor-made’ fuels for the cement process. At other times they can be just used as they are delivered without further processing. In nearly all cases, fuel components are blended prior to use to ensure a homogenous mixture with near constant thermal properties. When the Prestige, a large tanker carrying heavy oil, broke up off the coast of Spain in 2004, much of its oil cargo reached the shoreline, contaminating local beaches. As there is no effective cleaning method to restore the sand, it ultimately had to be removed. At the request of local governments, it was burned in a cement kiln, where the oil residue contributed thermal energy, and the sand provided the silica dioxide necessary to make cement (WBCSD, 2005). When mad-cow disease was linked to contaminated animal feed in 2000, several governments requested and received special assistance to burn the remaining feed in cement kilns where it was completely destroyed (WBCSD, 2005). Selected waste and by-products containing useful minerals such as calcium, silica, alumina, and iron can be used as raw materials in the kiln, replacing raw materials such as clay, shale, and limestone. Because some materials have both useful mineral content and recoverable calorific value, the distinction between alternative fuels and raw materials is not Kåre Helge Karstensen [email protected] Page 28 of 420 always clear. For example, sewage sludge has a low but significant calorific value, and burns to give ash containing minerals useful in the clinker matrix Cement kilns have several features that make them particularly appropriate and efficient for the recovery of minerals and energy from waste fuels and raw materials (WBCSD, 2005). Kilns have high temperatures, which the process requires: 2,000°C in the flame of the main burner, 1,450°C in the material to make clinker, and 1,000 to 1,200°C in the precalciner. The typical residence time of combustion gases in the kiln is more than five seconds at a temperature higher than 1,000°C. By constrast, gas residence time in a typical incinerator is only two seconds. Residence time for solid materials varies from tens of minutes to an hour depending on the cement process. The process takes place under oxidizing conditions. The stable nature of these conditions in a well-operated kiln guarantees the complete destruction of the organic components of the waste, provided that the waste is introduced in the hot part of the process. Waste materials in the kiln are in contact with a large flow of alkaline (basic) materials that remove potential acid off-gases from combustion. Any inorganic mineral residues from combustion – including most heavy metals – are trapped in the complex matrix of the clinker and cement. (Some volatile heavy metals are not completely immobilized; so their content in raw and/or waste materials must be assessed and controlled). Complete combustion and the trapping of mineral residues mean that in most cases there is no ash residue from the process. Excess in chlorine or alkali which may be in Kåre Helge Karstensen [email protected] Page 29 of 420 some virgin materials may produce cement kiln dust or bypass dust which must be removed, recycled or disposed of responsibly. Given the differences in temperature between different parts of the process, it is important that waste materials are introduced at the correct point in the process to ensure complete combustion or incorporation and to avoid unwanted emissions. For example, raw materials with volatile organic components may be introduced in the cement kiln at the main burner, in mid-kiln, in the riser duct, or at the precalciner. They should not be introduced with other raw materials except where tests demonstrate that this will have no effect on the off-gases. Controlling emissions to the atmosphere from cement manufacture requires precise control of the process, whether using conventional or alternative fuels and raw materials. Particular attention is paid to the specification of the fuel, (specifically its homogeneity, particle size, and flammability) and to the use of best combustion practices, including proper metering, feeding, and burner technology to maintain smooth kiln operating conditions (WBCSD, 2005). In some countries, the cement industry provides a public or industrial service by disposing of wastes even those with little or no useful energy or mineral content. This may be done at the request of national governments or in response to local demand. It can be done because a cement kiln provides high temperatures, long residence time, and a carefully controlled facility capable of high destruction efficiency. However, this activity is not part of the fuel or raw material substitution process. Cement kilns have been used in this way for many years in countries such as Japan, Norway, and Switzerland, where there is little space for landfill sites. In Norway, PCBs have been disposed of in this way for more than ten years (WBCSD, 2005). More recently, modern kilns have been used for waste disposal in some developing countries where the lack of existing waste disposal and incineration infrastructure means that kilns are the most economical option. Even where good waste disposal infrastructure exists, it may be useful to increase local capacity through use of cement kilns. The use of cement kilns for waste disposal may be less desirable than other approaches, such as recycling or reprocessing, but is a useful alternative to landfill or Kåre Helge Karstensen [email protected] Page 30 of 420 dumping. The industry should avoid disposing of wastes that could be more effectively handled by other means. There are many sources of waste materials and by-products that can be used as alternative fuels, raw materials, and cement constituents. Recycling wastes from one process as raw materials and fuels for another creates a web of relationships between industries that moves society closer to a zero-waste economy. Treatment of AFRs must meet strict environmental, health, and safety standards, and must not impair the quality of the final product. Figure 1 AFRs used in the cement industry (WBCSD, 2005). Kåre Helge Karstensen [email protected] Page 31 of 420 3.2 Replacement practise Local and national governments are recognizing that the cement industry can play an important role in efficient waste management. The substitution of fossil fuels and virgin raw materials with alternatives is a well-developed practice in a small number of countries. Some countries have been using it for almost 30 years, and some national governments actively promote this approach. Table 1 Use of alternative fuels (WBCSD, 2005) Country or region % Substitution Netherlands 83 Switzerland 47.8 Austria 46 Norway 35 France 34.1 Belgium 30 Germany 42 Sweden 29 Luxembourg 25 Czech Republic 24 EU (prior to expansion in 2004) 12 Japan 10 United States 8 Australia 6 United Kingdom 6 Denmark 4 Hungary 3 Finland 3 Italy 2.1 Spain 1.3 Poland 1 Ireland 0 Portugal 0 Greece <1% Kåre Helge Karstensen [email protected] Page 32 of 420 Table 2 Types of alternative fuels and raw materials (WBCSD, 2005) Kåre Helge Karstensen [email protected] Page 33 of 420 3.3 Ability to destroy hazardous chemicals - inherent features In the burning of cement clinker it is necessary to maintain material temperatures of up to 1450 °C in order to ensure the sintering reactions required. This is achieved by applying peak combustion temperatures of about 2000 °C with the main burner flame. The combustion gases from the main burner remain at a temperature above 1200 °C for several seconds. An excess of oxygen – typically 2-3 % – is also required in the combustion gases of the rotary kiln as the clinker needs to be burned under oxidising conditions. These conditions are essential for the formation of the clinker phases and the quality of the finished cement. The retention time of the kiln charge in the rotary kiln is 20-30 and up to 60 minutes depending on the length of the kiln. The figure below illustrates the temperature profiles for the combustion gases and the material for a preheater/precalciner rotary kiln system. While the temperature profiles may be different for the various kiln types, the peak gas and material temperatures described above have to be maintained in any case. The burning conditions in kilns with precalciner firing depend on the precalciner design. Gas temperatures from a precalciner burner are typically around 1100 °C, and the gas retention time in the precalciner is approximately 2-3 seconds. Under the conditions prevailing in a cement kiln – i.e. flame temperatures of up to 2000 °C, material temperatures of up to 1450 °C and gas retention times of up to 10 seconds at temperatures between 1200 and 2000 °C – all kinds of organic compounds fed to the main burner with the fuels are reliably destroyed. The combustion process in the main flame of the rotary kiln is therefore complete. No (hydrocarbon type) products of incomplete combustion can be identified in the combustion gases of the main burner at steady-state conditions. The cement manufacturing process is an industrial process where large material volumes are turned into commercial products, i.e. clinker and cement. Cement kilns operate continuously all through the year – 24 hours a day – with only minor interruptions for maintenance and repair. A smooth kiln operation is necessary in a cement plant in order to meet production targets and to meet the quality requirements of the products. Consequently, to achieve these goals, all relevant process parameters are permanently monitored and Kåre Helge Karstensen [email protected] Page 34 of 420 recorded including the analytical control of all raw materials, fuels, intermediate and finished products as well as environmental monitoring. With these prerequisites – i.e. large material flow, continuous operation and comprehensive process and product control, the cement manufacturing process seems to be well suited for co-processing by-products and residues from industrial sources, both as raw materials and fuels substitutes and as mineral additions. The selection of appropriate feed points is essential for environmentally sound co- processing of alternative materials, i.e.: • Raw materials: mineral waste free of organic compounds can be added to the raw meal or raw slurry preparation system. Mineral wastes containing significantly quantities of organic components are introduced via the solid fuels handling system, i.e. directly to the main burner, to the secondary firing or, rarely, to the calcining zone of a long wet kiln (“mid-kiln”). • Fuels: alternative fuels are fed to the main burner, to the secondary firing in the preheater/precalciner section, or to the mid-kiln zone of a long wet kiln. • Mineral additions: mineral additions such as granulated blast furnace slag, fly ash from thermal power plants or industrial gypsum are fed to the cement mill. In Europe, the type of mineral additions permitted is regulated by the cement standards. In addition to regulatory requirements, the cement producers have set up selflimitations such as • To prevent potential abuse of the cement kiln system in waste recovery operations • To assure the required product quality • To protect the manufacturing process from operational problems • To avoid negative impacts to the environment, and Kåre Helge Karstensen [email protected] Page 35 of 420 • To ensure workers’ health and safety. Figure 2 Gas and material profiles in cyclone preheater/precalciner system in compound operation (CEMBUREAU, 1999) The cement manufacturing process is a large materials throughput process with continuous operation and comprehensive operational control. Therefore, it has a large potential for co-processing a variety of materials from industrial sources. Wastes and hazardous wastes in the environment represent a challenge for many countries, but cement kiln co-processing can constitute a sound and affordable recovery option. Cement kilns can destroy organic hazardous wastes in a safe and sound manner when properly operated and will be mutually beneficial to both industry, which generates such wastes, and to the society who want to dispose properly of such wastes in a safe and environmentally acceptable manner. The added benefit of non renewable fossil energy conservation is important, since large quantities of valuable natural fuel can be saved in the manufacture of cement when such techniques are employed. Kåre Helge Karstensen [email protected] Page 36 of 420 Since the early 70s, and particularly since the mid 80s, alternative – i.e. non-fossil – raw materials and fuels derived mainly from industrial sources have been beneficially utilised in the cement industry for economic reasons. Since that time, it has been demonstrated both in daily operations and in numerous tests that the overall environmental performance of a cement plant is not impaired by this practice in an appropriately managed plant operation. Cement kilns make full use of both the calorific and the mineral content of alternative materials. Fossil fuels such as coal or crude oil are substituted by combustible materials which otherwise would often be landfilled or incinerated in specialised facilities. The mineral part of alternative fuels (ashes) as well as non-combustible industrial residues or by-products can substitute for part of the natural raw materials (limestone’s, clay, etc.). All components are effectively incorporated into the product, and – with few exceptions – no residues are left for disposal. The use of mineral additions from industrial sources substituting clinker saves both raw material resources and energy resources as the energy intensive clinker production can be reduced. With the substitution of fossil fuels by (renewable) alternative fuels, the overall output of thermal CO2 is reduced. A thermal substitution rate of 40% in a cement plant with an annual production of 1 million tons of clinker reduces the net CO2 generation by about 100,000 tons. Substitution of clinker by mineral additions may be more important as both thermal CO2 from fossil fuels and CO2 from the decarbonation of raw materials is reduced. Since only moderate investments are needed, cement plants can recover adequate wastes at lower costs than would be required for landfilling or treatment in specialised incinerators. In addition, public investment required for the installation of new specialised incinerators would also be reduced. Substitute materials derived from waste streams usually reduce the production cost in cement manufacturing, thus strengthening the position of the industry particularly with regard to imports from countries with less stringent environmental legislation. It will also facilitate the industry’s development of technologies to further clean up atmospheric emissions. Kåre Helge Karstensen [email protected] Page 37 of 420 In order to co-process organic hazardous wastes in cement kilns properly, it is important to know and control the parameters given in the table below. Table 3 Information needed for combustion of waste materials Critical waste incineration parameters Physical and chemical properties Ultimate analysis C, H, O, N, H2O, S and ash composition Metals Na, K, Cu, V, Ni, Fe, Pb, Hg, Tl etc. Halogens Chlorides, bromides, fluorides Heating value Joule or cal/gram Solids Size, form and quantity Liquids Viscosity, specific gravity and impurities Gases Density and impurities Organic portion Percentage Special characteristics Corrosiveness, reactivity, flammability Toxicity Carcinogenicity, aquatic toxicity, etc. 3.3.1 Types of hazardous waste used by the cement industry For the hazardous waste to serve as a suitable supplemental fuel, it must be combustible and have significant energy content. Although the recent regulations only require the hazardous waste fuel to have an energy content of 5,000 Btu per pound (U.S. EPA, 1991), typical hazardous waste fuel can have energy content greater than 10,000 Btu per pound (Peters et al., 1986). Since the primary function of the hazardous waste is to replace a portion of the conventional fuel, a cement production facility does not burn hazardous waste that is either corrosive, reactive, or toxic, unless it is also combustible with a significant energy content. Highly corrosive and reactive wastes are generally avoided, since they could damage either the cement kiln itself or the tanks, piping, and valves associated with the cement manufacturing process. Kåre Helge Karstensen [email protected] Page 38 of 420 Restrictions other than combustibility and energy content exist. For example, the chlorine content of a hazardous waste fuel is restricted. When chlorinated wastes, such as those containing carbon tetrachloride or trichlorobenzene, are burned in a cement kiln, hydrogen chloride (HCl) is typically generated. This acid gas reacts with potassium and sodium oxide in the kiln form alkali salts, which volatilize in the burning zone and condense in the cooler portions of the kiln. If large quantities of these salts are formed, due to high chlorine content in the waste, blockages can occur in the kiln system. These blockages upset the cement manufacturing process (Weitzman, 1983). For this reason, the chlorine content of the waste is strictly monitored by the cement production facility. Restrictions on the metal content of the hazardous waste also exist, even if the majority of the metals are incorporated into the process solids (i.e. clinker or CKD). Since the setting of the cement can be adversely affected when the concentrations of certain metals exceeds 0.1%, these metal concentrations in the hazardous waste fuel must be regulated (Kerton and Murray, 1983). This restriction alludes to a significant point. The cement produced by a company must meet strict performance standards set by the American Society for Testing and Materials (ASTM). Consequently, the cement industry does not burn any hazardous waste fuel that would compromise the quality of its cement and impair its ability to sell the cement it produces. In addition to the waste restrictions and requirements discussed above, the cement industry chooses not to burn polychlorinated biphenyl (PCB) waste (i.e. wastes containing greater than 50 ppm of PCBs). The major reason for this decision is the quality of the PCB wastes. PCB wastes are highly chlorinated and, as discussed above, these types of wastes are avoided. When all of the restrictions and requirements are considered, only a select stream of hazardous waste can be effectively utilized by the cement industry. Examples of hazardous waste burned by the cement industry are spent organic solvents that originate from the “paint and coatings, auto and truck assembly, solvent reclamation, ink and printing, cosmetics, toy, medical and electronic” industries (Engineering Digest, 1989). In general, only combustible waste with a energy, low chlorine, and low metal content are burned in a cement kiln. Kåre Helge Karstensen [email protected] Page 39 of 420 3.3.2 Fossil fuel versus hazardous waste fuel Although petroleum coke, oil, and natural gas are sometimes burned, the most common fuel used by the cement industry is coal (Weitzman, 1983). Similar to the raw materials and the hazardous waste fuel, coal can contain significant quantities of metals and halogens. Thus, coal may contain antimony, arsenic, barium beryllium, cadmium, chromium, lead, mercury, nickel, selenium, silver, thallium, vanadium zinc, bromine, chlorine, fluorine, and iodine. Average concentrations of these components are listed in Table 2. Ranges are presented when these data were available. The actual metal and halogen concentrations of a specific coal depend on the area in which it is mined. For comparative purposes, the metal and halogen concentrations in used oil are also presented in Table 2. The status of used oil (i.e. hazardous versus nonhazardous) depends on the constituents present (40 CFR 266.40). Although some metals such as zinc and lead might be higher in used oil, other metals such as thallium might be higher in coal. Although coal contains metals and halogens, the majority of coal, as is the case for the hazardous waste fuel, is organic (Kirk-Othmer Encyclopedia of Chemical Technology, 1979). The organic compounds on coal are generally aromatic. Consequently, when coal is burned, aromatic compounds, such as toluene and benzene, are emitted (Branscome et al. 1985). For the same reasons discussed previously with regard to the raw materials, the presence of metals, halogens, and organic compounds in the coal can complicate the interpretation of the emission testing conducted at a cement kiln burning hazardous waste. Kåre Helge Karstensen [email protected] Page 40 of 420 Table 4 Concentration (ppm) of metals and halogens in coal and used oil (Mantus (1992) Constituent Coal Used Oil Antimony 1.19a NDAb Arsenic 9-50 <0.01-100c Barium 24.5a 0-3,906c Berylluim 2.27a NDA Cadmium 0.1-10 4 Chromium 5-80 <5-50 Lead 11-270 10-21,700 Mercury 0.24a NDA Nickel 20-80 3-30 Metals Selenium a 3.56 NDA Silver 0.06a NDA Thallium 0.2-4 <0.02 Vanadium 30-50 NDA Zinc 16-220 240-3,000 Bromine 7-11 NDA Chlorine 100-2,800 100-2,200 Fluorine 50-370 NDA Iodine 0.8-11.2 NDA Halogens 3.4 Resource consumption in cement production Cement manufacturing is a “high volume process” and correspondingly requires large quantities of resources, i.e. raw materials, fossil fuels and electrical power. A “mediumsized” modern rotary kiln with a clinker production of 3000 tons per day or 1 million tons per Kåre Helge Karstensen [email protected] Page 41 of 420 year corresponds to a cement production of 1.23 million tons per year (based on average figures for the clinker content in cement in Europe). Conservation of natural resources can be achieved through increased substitution of natural raw materials and fossil fuels by industrial by-products and residues in the manufacturing process. Cement manufacturing is an energy intensive process. The specific thermal energy consumption of a cement kiln varies between 3000 and 7500 MJ per ton of clinker, depending on the basic process design of the plant. The dominant use of energy in cement manufacture is as fuel for the kiln. The main users of electricity are the mills (raw grinding, finish grinding, cement mills and coal mills) and the exhaust fans (kiln/raw mill and cement mill) which together account for more than 80% of electrical energy usage. On average, energy costs, in the form of fuel and electricity, represent 50% of the total production cost involved in producing a tonne of cement. Electrical energy represents approximately 20% of this overall energy requirement (IPPC, 2001). The theoretical energy use for the burning process (chemical reactions) is about 1700 to 1800 MJ/tonne clinker (IPPC, 2001). The actual fuel energy use for different kiln systems is in the following ranges (MJ/tonne clinker): • about 3000 for dry process, multi-stage cyclone preheater and precalciner kilns; • 3100-4200 for dry process rotary kilns equipped with cyclone preheaters; • 3300-4500 for semi-dry/semi-wet processes; • up to 5000 for dry process long kilns; • 5000-6000 for wet process long kilns; Kåre Helge Karstensen [email protected] Page 42 of 420 • 3100-4200 for vertical shaft kilns. The actual use of energy for the production of one ton of clinker is from 70 to 250 percent higher than the theoretical energy need. This clearly shows the potential for improvement of energy use through upgrades and process optimisation. The specific electrical energy consumption ranges typically between 90 and 130 kWh per ton of cement. A technique to reduce energy use and emissions from the cement industry, expressed per unit mass of cement product, is to reduce the clinker content of cement products. This can be done by adding fillers, for example sand, slag, limestone, fly-ash and pozzolana, in the grinding step. In Europe the average clinker content in cement is 80-85 %. Many manufacturers of cement are working on techniques to further lower the clinker content. One reported technique claims to exchange 50% of the clinker with maintained product quality/performance and without increased production cost. Cement standards define some types of cement with less than 20 % clinker, the balance being made of blast furnace slag (IPPC, 2001). Recycling of collected dust to the production processes lowers the total consumption of raw materials. This recycling may take place directly into the kiln or kiln feed (alkali metal content being the limiting factor) or by blending with finished cement products. The use of suitable wastes as raw materials can reduce the input of natural resources, but should always be done with satisfactory control on the substances introduced to the kiln process. Kiln systems with 5 cyclone preheater stages and precalciner are considered standard technology for ordinary new plants, such a configuration will use 2900-3200 MJ/tonne clinker (IPPC, 2001). To optimise the input of energy in other kiln systems it is a possibility to change the configuration of the kiln to a short dry process kiln with multi stage preheating and precalcination. This is usually not feasible unless done as part of a major upgrade with an increase in production. The application of the latest generation of clinker coolers and Kåre Helge Karstensen [email protected] Page 43 of 420 recovering waste heat as far as possible, utilising it for drying and preheating processes, are examples of methods which cut primary energy consumption. Electrical energy use can be minimised through the installation of power management systems and the utilisation of energy efficient equipment such as high-pressure grinding rolls for clinker comminution and variable speed drives for fans. Energy use will be increased by most type of end-of-pipe abatement. Some reduction techniques will also have a positive effect on energy use, for example process control optimisation. 3.5 Benefits of burning hazardous waste in cement kilns The benefit s of burning hazardous waste in a cement kilns include recovering the energy value of the hazardous waste, conserving nonrenewable fossil fuels, reducing manufacturing costs, and using an existing technology to incinerate large volumes of hazardous waste. 3.5.1 Recovery of energy value from hazardous waste A large quantity of hazardous waste generated in the U.S. has a significant energy content. This source of potential energy is one of the primary reasons for the cement industry’s interest in burning hazardous waste. Because of the waste in burned as a fuel in a manufacturing process and therefore, the energy value of the waste is recovered, this practice has been designated as “recycling” in the US (Mantus, 1992). This practice is consistent with the national waste management policy, whose primary goal is to reduce the quantity of waste that is generated. If waste is generated, then it should be recycled or reduced. The preferred management option for the nonrecyclable potion of the waste is treatment by either incineration or physical, chemical, or biological methods. If incineration is chosen as the treatment option, then a device such as a cement kiln that Kåre Helge Karstensen [email protected] Page 44 of 420 recovers the energy value is preferred. The least preferred waste management option is longterm storage (e.g. landfilling) (Mantus, 1992). This preference is supported by the Hazardous and Solid Waste Amendments to the Resource Conservation and Recovery Act (RCRA). These amendments required the U.S. EPA to develop restrictions on the types of wastes that should be landfilled (U.S. EPA, 1989a). As a result, the amount of hazardous waste that must be treated prior to landfilling has dramatically increased. 3.5.2 Conservation of nonrenewable fossil fuels One of the most significant advantages of using hazardous waste as a supplemental fuel in the cement industry is the conservation of nonrenewable fossil fuels, such as coal and oil. The amount of fossil fuel that could be saved by this practice is substantial. For example, if 25% of the energy used in the production of cement in the U.S. were replaced by hazardous waste, then 3.8 million tons of domestic coal or 14.4 million barrels of domestic crude oil could be saved each year (Mantus, 1992). This estimate of fossil fuel savings is conservative because the regulations that govern the burning of hazardous waste in cement kilns allow more than 25% of the conventional fuel to be replaced by hazardous waste (U.S. EPA, 1991). A practice that could save this quantity of nonrenewable resource deserves serious consideration. 3.5.3 Reduction in production costs The production of cement is an energy-intensive process. The portion of manufacturing costs attributed to fuel can range from 20% to 25% (Engineering Digest, 1989). Consequently, cement production costs are heavily driven by fuel prices. As a result, “most cement plants have made the capital investment necessary to achieve fuel flexibility and can select energy sources according to cost” (Engineering Digest, 1989). Since the hazardous waste fuel is substantially cheaper than any of the conventional fossil fuels, the industry has an incentive to use this potential source of energy. Kåre Helge Karstensen [email protected] The Page 45 of 420 replacement of even a fraction of the conventional fuel with hazardous waste fuel can significantly reduce manufacturing costs. 3.5.4 Use of existing technology to treat large volumes of hazardous waste The rate at which hazardous waste was produced far exceeded the capacity for treatment and disposal in a manner that prevents long-term exposure (U.S. Congress, 1989). Innovative ideas and new technologies to manage hazardous waste was needed. Unfortunately, the design and construction of new hazardous waste treatment and disposal facilities are extremely expensive processes. One of the advantages of using cement kilns is that the technology and the facilities are already in place. In addition, the use of a cement kiln, as opposed to the construction of a new facility, does not result in the creation of a new source of emissions. Therefore, cement kilns provide an attractive option for the incineration of large volumes of certain types hazardous waste. The cement kiln option for the disposal of large volumes of hazardous waste does not promote the generation of hazardous waste. Interest in the reduction of waste might be lost when the generator also owns the treatment facility or when treatment is more profitable than reduction or recycling. However, such is not the case for cement production facilities because they do not generate the hazardous waste fuel they burn. Since the generator still must pay for treatment or disposal of the waste, the incentive for reduction or recycling remains. Therefore, cement kilns do not provide an incentive to generate more hazardous waste, but a means of treating some types of hazardous waste that cannot be minimized or otherwise recycled. Kåre Helge Karstensen [email protected] Page 46 of 420 4. Environmental significance of cement production The main environmental impacts of the manufacture of cement in general are related to the following categories: • Dust from stack emissions and fugitive sources; • Gaseous atmospheric emissions of CO2, NOx, SO2, VOC and others; • Other emissions like noise and vibrations, odour, process water, production waste, etc. 4.1 Dust Historically, the emission of dust – particularly from kiln stacks – has been the main environmental concern in cement manufacture. “Point source” dust emissions originate mainly from the raw mills, the kiln system, the clinker cooler, and the cement mills. A general feature of these process steps is that hot exhaust gas or exhaust air is passing through pulverised material resulting in an intimately dispersed mixture of gas and particulates. Primary reduction measures are therefore hardly available. The nature of the particulates generated is linked to the source material itself, i.e. raw materials (partly calcined), clinker or cement. Dust emissions in the modern cement industry have been reduced considerably in the last 20 years, and state-of-the-art abatement techniques now available (electrostatic precipitators, bag filters) result in stack emissions which are insignificant in a modern and well managed cement plant. Dust from dispersed sources in the plant area (“fugitive dust”) may originate mainly from materials storage and handling, i.e. transport systems, stockpiles, crane driving, bagging, Kåre Helge Karstensen [email protected] Page 47 of 420 etc., and from traffic movement on unpaved roads. Techniques for control and containment of fugitive dust include dedusting of material transfer points, closed storage installations with proper ventilation, or vacuum cleaning equipment, etc. As the chemical and mineralogical composition of dust in a cement plant is similar to that of natural rocks, it is commonly considered as a “nuisance”. Reduction and control of dust emissions in a modern cement plant requires both investments and adequate management practices but is not a technical problem. Kiln dust collected from the gas cleaning devices is highly alkaline and may contain trace elements such as heavy metals corresponding to the contents in the source materials. Usually, kiln dust is completely returned to the process – either to the kiln system or to the cement mill. In rare cases, it is not possible to recycle kiln dust or bypass dust completely in the process. This residual dust is disposed of on site (or in controlled landfills) or is treated and sold to other industries, i.e. as binder for waste stabilisation or even as fertiliser. Heavy metals delivered by either conventional raw materials and fuels or by alternative raw materials and fuels from industrial sources will be mainly incorporated in clinker or – to a lesser extent – in kiln dust. Bypass dust extracted from the kiln system may be highly enriched in alkalis, sulphates and chlorides and – similarly to filter dust – in some cases cannot be completely recycled to the process. For both types of dust, conditioning and safe disposal avoiding contamination of groundwater or soil is a site-specific requirement. 4.2 Gaseous atmospheric emissions Gaseous emissions from the kiln system released to the atmosphere are the primary environmental concern in cement manufacture today. Major gaseous emissions are CO2, NOx and SO2. Other emissions of less significance are VOCs (volatile organic compounds), CO, ammonia, and heavy metals. CO2 as the main greenhouse gas is released in considerable quantities. Kåre Helge Karstensen [email protected] Page 48 of 420 Other gaseous emissions such as hydrochloric acid or hydrofluoric acid are nearly completely captured by the inherent and efficient alkaline scrubber effect of the preheater cement kiln system. Natural raw materials used for clinker production may contain volatile components in small quantities. These components will be volatilised and partly emitted under the conditions prevailing in the preheater section of a dry process cement kiln or in the drying/preheating zone of a VSK or before entering the burning zone of the long wet or long dry rotary kiln. 4.2.1 Carbon dioxide Carbon dioxide emissions arise from the calcination of the raw materials and from the combustion of fossil fuels. CO2 resulting from calcination can be influenced to a very limited extent only. Emissions of CO2 resulting from fuel combustion have generally been reduced due to the strong economic incentive for the cement industry to minimise fuel energy consumption. CO2 reduction of some 30% in the last 25 years – arising mainly from the adoption of more fuel efficient kiln processes – leaves little scope for further improvement. Potential is mainly left to the increased utilisation of renewable alternative fuels or other waste derived fuels and to the production of blended cements with mineral additions substituting clinker. 4.2.2 Nitrogen oxides NOx formation is an inevitable consequence of the high temperature combustion process, with a smaller contribution resulting from the chemical composition of the fuels and raw materials. Nitrogen oxides are formed by oxidation of molecular nitrogen in the combustion air (“thermal” NOx is the sum of nitrogen oxides; in cement kiln exhaust gases, NO and NO2 are dominant, > 90% NO, < 10% NO2). Thermal NOx formation is strongly Kåre Helge Karstensen [email protected] Page 49 of 420 dependent on the combustion temperature with a marked increase above 1400 °C. “Hard” burning required by certain raw mixes – i.e. at a higher temperature profile – increases NOx formation. While thermal NOx is the dominant contribution to total NOx generation, a smaller part may also result from nitrogen compounds contained in the fuels which are oxidised in the flame as well (“fuel NOx”). In the main burner flame, the contribution of fuel NOx is much lower than that of thermal NOx. In the secondary firing of a preheater/precalciner kiln with a flame temperature of not more than 1200 °C, the formation of thermal NOx is much lower compared to the main burner flame. Therefore, in precalciner kilns where up to 60% of the total fuel can be burnt in the calciner flame, fuel NOx may be a higher proportion of the reduced total NOx emissions. Natural raw materials such as clays or shale’s may also contain nitrogen compounds. Part of these compounds may be released and oxidised upon heating in the kiln system and may thus in certain cases considerably contribute to the total NOx emissions. NOx formation is reduced if fuel is burnt in a more “reducing” atmosphere with low oxygen content. Operation under reducing conditions is limited due to process requirements in order to maintain good clinker quality and undisturbed kiln operation. NOx emissions in cement kilns (expressed as NO2) typically vary between 300 and 2000 mg/m3. 4.2.3 Sulfur oxides Sulfur compounds enter the kiln system either with the fuels or with the raw materials. Sulfur compounds in raw materials are present mainly as sulphates (for example, calcium sulphate CaSO4) or as sulphides (i.e. pyrite or marcasite FeS2). Sulphates in the raw materials are thermally stable up to temperatures of 1200 °C, and will thus enter the sintering zone of the rotary kiln where they are decomposed to produce SO2. Part of the SO2 combines with alkalis and is incorporated into the clinker structure. The Kåre Helge Karstensen [email protected] Page 50 of 420 remaining part of SO2 is carried back to the cooler zones of the kiln system where it reacts either with calcined calcium oxide or with calcium carbonate thus being reintroduced to the sintering zone again (“chemical SO2 absorption”). Inorganic and organic sulfur compounds introduced with the fuels will be subject to the same internal cycle consisting of thermal decomposition, oxidation to SO2 and reaction with alkalis or with calcium oxide. With this closed internal cycle, all the sulfur which is introduced via fuels or via raw material sulphates will leave the kiln chemically incorporated in clinker, and will not give rise to gaseous SO2 emissions. Sulphides (and also organic sulfur compounds) in raw materials however, are decomposed and oxidised at moderate temperatures of 400 to 600 °C to produce SO2 when the raw materials are heated by the exhaust gases. At these temperatures, not enough calcium oxide is available to react with the SO2. Therefore, in a dry preheater kiln about 30% of the total sulphide input may leave the preheater section as gaseous SO2. During direct operation – i.e. with the raw mill off – most of it is emitted to the atmosphere. During compound operation – i.e. with the raw mill on-line – typically between 30 and 90% of that remaining SO2 is additionally adsorbed to the freshly ground raw meal particles in the raw mill (“physico-chemical absorption”). In grate preheater kilns SO2 absorption is also good because the gas is passing through the turbulent flow of material from grate to kiln and then passing at low velocities firstly through the bed of material which is partly calcined and then through the moist calcium carbonate in the drying chamber. In long dry and long wet kilns, the chemical absorption capacity for SO2 is generally less efficient due to the reduced contact between kiln exhaust gas and raw materials. In these kiln systems, all kinds of sulfur input may partially contribute to SO2 emissions, and the general emission level may be higher than in dry preheater kilns. Gaseous emissions such as SO2 or VOC are to a large extent determined by the chemical characteristics of the raw materials used, and not by the fuel composition. Emissions are lowest with raw materials low in volatile components. Kåre Helge Karstensen [email protected] Page 51 of 420 4.2.4 Organic compounds Natural raw materials such as limestone’s, marls and shale’s may also contain up to 0.8 % w/w of organic matter (“kerogene”) – depending on the geological conditions of the deposit. A large part of this organic matter may be volatilised in the kiln system even at moderate temperatures between 400 and 600 °C. Kiln tests with raw meals of different origin have demonstrated that approximately 85 to 95% of the organic matters in the raw materials are converted to CO2 in the presence of 3% excess oxygen in the kiln exhaust gas, and 5 to 15% are oxidised to CO. A small proportion – usually less than 1% – of the total organic carbon (“TOC”) content may be emitted as volatile organic compounds (“VOC”) such as hydrocarbons. The emission level of VOC in the stack gas of cement kilns is usually between 10 and 100 mg/Nm3, with a few excessive cases up to 500 mg/Nm3. The CO concentration in the clean gas can be as high as 1000 mg/Nm3, even exceeding 2000 mg/Nm3 in some cases. The carbon monoxide and hydrocarbon contents measured in the stack gas of cement kiln systems are essentially determined by the content of organic matter in the raw materials, and are therefore not an indicator of incomplete combustion of conventional or alternative fuels. Organic matter introduced to the main burner and to the secondary firing will be completely destroyed due to the high temperatures and the long retention time of the combustion gases. 4.3 PCDD/PCDF emissions The Stockholm Convention requires Parties to take measures to reduce or eliminate releases of persistent organic pollutants (POPs) from intentional production and use, from unintentional production and from stockpiles and wastes. Kåre Helge Karstensen [email protected] The chemicals intentionally Page 52 of 420 produced and currently assigned for elimination under the Stockholm Convention are the pesticides aldrin, chlordane, dieldrin, endrin, heptachlor, hexachlorobenzene (HCB), mirex and toxaphene, as well as the industrial chemical Polychlorinated Biphenyls (PCBs). The Convention also seeks the continuing minimisation and, where feasible, elimination of the releases of unintentionally produced POPs such as the by-products from wet chemical and thermal processes, polychlorinated dibenzo-p-dioxins/-furans (PCDD/Fs) as well as HCB and PCBs. Cement kilns co-processing hazardous waste are explicitly mentioned in the Stockholm Convention as an “industrial source having the potential for comparatively high formation and release of these chemicals to the environment”. Emission data from US cement kilns in the 1980s and first part of the 1990s indicated that cement kilns co-processing hazardous waste as a co-fuel had much higher PCDD/F emissions than kilns co-processing non-hazardous wastes or using conventional fuel only. In recent documents however, the US EPA has explained the most probable cause for these findings, namely that cement kilns burning hazardous waste were normally tested under “worst” scenario trial burn conditions, i.e. typically high waste feeding rates and high temperatures in the air pollution control device, conditions today known to stimulate PCDD/F formation. Cement kilns burning non-hazardous waste or conventional fossil fuel only were however tested under normal conditions, no “worst” scenario conditions, making a comparison between hazardous waste burning and non-hazardous waste burning kilns dubious. Reducing the temperature at the inlet of the air pollution control device is one factor which has shown to limit dioxin formation and emissions at all types of cement kilns, independent of waste feeding, as lower temperatures are believed to prevent the postcombustion catalytic formation of PCDD/Fs. The US EPA concluded in 1999 in the new Maximum Achievable Control Technology regulation that hazardous waste burning in cement kilns does not have an impact on PCDD/F formation because they are formed postcombustion, i.e. in the air pollution control device. The World Business Council for Sustainable Development initiated a study where the objective was to compile data on the status of POPs emissions from the cement industry, to share state of the art knowledge about PCDD/F formation mechanisms in cement production Kåre Helge Karstensen [email protected] Page 53 of 420 processes and to show how it’s possible to control and minimise PCDD/F emissions from cement kilns utilising integrated process optimisation, so called primary measures. This is the most comprehensive study available on POPs emission from the cement industry. (Karstensen, 2007). Around 2200 PCDD/F measurements, many PCB measurements and a few HCB measurements made from the 1970s until recently was. The data represents emission levels from large capacity processing technologies, including wet and dry process cement kilns, performed under normal and worst case operating conditions, with and without the coprocessing of a wide range of alternative fuel and raw materials and with wastes and hazardous wastes fed to the main burner, to the rotary kiln inlet and to the preheater/precalciner. Vertical shaft kilns was not dealt with due to lack of emission data. The PCDD/F data evaluated shows that: • Most modern cement kilns can today meet an emission level of 0.1 ng TEQ/Nm3; • Co-processing of alternative fuels and raw materials, fed to the main burner, kiln inlet or the precalciner does not seem to influence or change the emissions of POPs; • Data evaluated from dry preheater and precalciner cement kilns in developing countries show very low emission levels, much lower than 0.1 ng TEQ/Nm3. • The emissions from modern dry preheater/precalciner kilns seem generally to be slightly lower than emissions from wet kilns. The study also provides a large number of measurements of PCDD/F in products and residues from the cement industry. The levels are normally low and in the same magnitude as found in foods like fish, butter and breast milk as well as soil, sediments and sewage sludge. For new cement plants and major upgrades the best available techniques for the production of cement clinker is a dry process kiln with multi-stage preheating and precalcination. A smooth and stable kiln process, operating close to the process parameter set points is beneficial for all kiln emissions as well as for the energy use. Kåre Helge Karstensen [email protected] Page 54 of 420 The most important primary measures to achieve compliance with an emission level of 0.1 ng TEQ/Nm3 is quick cooling of the kiln exhaust gases to lower than 200oC in long wet and long dry kilns without preheating. Modern preheater and precalciner kilns have this feature already inherent in the process design. Feeding of alternative raw materials as part of raw-material-mix should be avoided if it includes organic material and no alternative fuels should be fed during start-up and shut down. Since PCDD/F is the only group of POPs commonly being regulated up to now, there are fewer measurements available for HCB and PCBs. However, the more than 50 PCB measurements referred to in this report show that all values are below 0.4 µg PCB TEQ/m3, many at a few nanogram level or below the detection limit. 10 HCB measurements show a concentration of a few nanograms per cubic meter or concentrations below the detection limit. 4.3.1 Trace elements During the clinker burning process, all mineral input delivered by the raw materials – be it natural or alternative raw materials sources – is converted into the clinker phases at the high temperatures prevailing in the sintering zone of the kiln. Combustion ashes from conventional and alternative fuels used in rotary kilns are also completely incorporated into the clinker minerals. Therefore cement kiln systems do not generate combustion ashes which require separate disposal. Consequently, the fuel ashes substitute for part of the (natural) raw materials input. In order to maintain a good clinker quality, the ash composition of the fuels has to be taken into account in the raw mix design. Trace elements such as heavy metals are naturally present in low concentrations in the raw materials and fuels used for the manufacture of cement clinker. The behaviour of these metals in the burning process depends largely on their volatility. • Non-volatile metals remain completely within the product and leave the kiln system fully incorporated in the mineral structure of the clinker – similarly to the main elements. Most of the common metals are non-volatile. Kåre Helge Karstensen [email protected] Page 55 of 420 • Semi-volatile elements such as cadmium or lead may in part be volatilised with the high temperature conditions in the sintering zone of the kiln system. They condense on the raw materials in cooler parts of the kiln system and are reintroduced to the hot zone again. A major part of cadmium and lead will be incorporated in clinker; the remaining part will precipitate with the kiln dust and will be collected in the filter systems. • Volatile metals such as mercury and thallium are more easily volatilised and condense on raw material particles at lower temperatures in the kiln system (thallium at approximately 300-350 °C, mercury at 120-150 °C). Whereas thallium is nearly completely precipitated onto the kiln dust particles, only part of the mercury will be collected within the filter system. Volatile metals are retained in the clinker minerals to a very small extent only. Being the only metal which can be emitted with the clean gas in gaseous form, the input of mercury with raw materials and fuels has to be carefully controlled. 4.4 Other emissions Heavy machinery and large fans used in the cement manufacture may give rise to emissions of noise and vibrations. Odour emissions are seldom a problem with a well operated plant, but may be mainly related to emissions from handling and storage of conventional or alternative fuels. In exceptional cases, nitrogen compounds in the raw materials may lead to ammonia emissions which – even at low concentrations – may give rise to odour. Process water in cement manufacturing will usually be completely evaporated or recycled in the process. Filtrate water from filter presses used in the semi-wet process is Kåre Helge Karstensen [email protected] Page 56 of 420 fairly alkaline and contains suspended solids requiring site-specific treatment and/or disposal options. Emergencies such as fire, explosions or spillage/leakage are extremely rare in the modern cement industry but minor explosions can be experienced in VSKs if the coal/coke in the black meal contains high concentrations of volatile matters. Potential consequences for the environment are minimised by adequate prevention and protection measures such as fire and explosion proof design of machinery and emergency response schemes. 4.5 Normal emission levels from rotary kilns Average emission data (long term average values) from European rotary cement kilns in operation are summarised in the table below. The figures given are representative of the ranges within which kilns normally operate. Due to the age and design of the plant, the nature of the raw materials, etc., individual kilns may operate outside these ranges. 4.6 Pollution reduction Major emissions from cement manufacturing plants traditionally are airborne pollutants and powered dust from the kiln and its emissions. Pollutants are mainly particulates from a number of solid processing and handling operations, CO2, SO2 and NO2. Relatively speaking, SO2 and NO2.emissions from cement industries are small, and they represent less than 2% of the total emitted of these compounds in USA and Europe. In recent years, as a result of advanced control technology and equipment design, such as electro static precipitator and bag filter facilities, significant progress has been reached in reducing air emissions from the cement industrial sector. For a new plant today, air pollution emissions are significantly lower than those from typical facilities built 30-40 years ago. Kåre Helge Karstensen [email protected] Page 57 of 420 Table 5 Long term average emission values from European cement kilns (CEMBUREAU, 1999) mg per standard cubic meter [mg/Nm3] Emission Dust 20 – 200 NOx 500 – 2000 SO2 10 – 2500 Total organic carbon (TOC) 10 – 100 CO 500 – 2000 Fluorides <5 Chlorides < 25 PCDD/F < 0.1 [ng/Nm3] Heavy metals: - class 1 (Hg, Cd, Tl) < 0.1 - class 2 (As, Co, Ni, Se, Te) < 0.1 - class 3 (Sb, Pb, Cr, Cu, Mn, V, Sn) incl. Zn < 0.3 World wide, the cement industry produces about 5 % of global manmade CO2 (Worrell et al, 2001). As the industry produces an equal weight of CO2 and clinker, any cost imposed on the reduction of CO2 emission to the atmosphere and any management plan can have a significant impact on the industry’s financial performance. At the present rate of many CO2 management expenses on the market - in the range of $ 10 to $ 25/ton and expected to rise as the public demand its treatment - many cement enterprises will not be able to foot the bill, unless their production capacities are increased and are big enough to bear the cost. Increasing the use of alternative fuels and raw materials can reduce the use of virgin materials including limestone and petroleum products, and can reduce CO2 emission and production costs. Alternative and substituted materials as fly ash from power plants, steel mill slugs, and pozzolanic substances can be used in cement to replace some of the limestone, and the quality of the product is not affected in applications. The following measures are recommended with regards to achieve emission reduction: Kåre Helge Karstensen [email protected] Page 58 of 420 1. A well defined emission inventory and reporting process with emission reduction cost estimates; 2. A program for effective communication with the local stakeholders including regulatory personnel; 3. A program to define the emission reduction targets and timetable; 4. In order to win confidence, the industry needs an effective way of monitoring and reporting emissions which can address the safety concerns of the public and product quality concerns of the users. 4.6.1 Water pollution and dust recovery Water pollution is not generally an important issue for cement production. On the other hand, close attention must be paid to deal the problems of solid waste, especially cement kiln dust, which needs to be recycled to the largest degree possible. By the implementation of cleaner production, the waste minimization/recycling/reuse process is not limited to powdered dust recovery generated by the cement sector. It also extends to wastes from other industries including steel mills, powdered coal dust from power plants, sulfate gypsum from chemical industries and coal residue from industrial boilers. 4.6.2 Health and safety The cement industry can reduce the number of injuries and fatalities; techniques for safety and health performance are well known and established: Kåre Helge Karstensen [email protected] Page 59 of 420 1. Incorporating safety into the working culture of the enterprise through continuous reinforcement and education about safe working practices and conditions; establishing safety awards; and awareness-raising of senior management; 2. A systematic program for tracking, reporting, and analyzing all safety related incidents, including those “near-miss” cases; 3. Communication and dissemination systems within enterprises or groups to expedite the distribution and sharing all safety-related information to avoid repeated instances; and 4. Ongoing analysis of incidents, responses, and progress to provide information on continuous improvement. 4.6.3 Impacts on land use Before building new plants, environmental and social impact assessments must be carried out, including the publication of quarry management plans, its influence on biodiversity protection, and the handling of plant and quarry closures in a responsible way, environmentally and socially. 1. Apply EIA (environmental impact assessment) and social impact assessment for all new cement projects; 2. In consultation with local communities, develop land use management plans for all such plants; 3. Share the quarry rehabilitation plans provided by the plants in writing with those communities. Update plans as needed to reflect the current technology and the changing community’s requirement; Kåre Helge Karstensen [email protected] Page 60 of 420 4. Develop the necessary advanced planning for plant closures. Dialogues with community leaders should be held at the regular intervals. 4.6.4 Communication The cement industry has had a history of limited engagement with stakeholders outside the area of that industry. Developed countries has encouraged cement plants to communicate to the public, and announced that this represents a key element for a “license to operate”. In fact, effective ways to communicate must be tailored to the particular audience at the local level. 1. Identify what needs to be communicated, the background extent of understanding, biases, and public opinion on these issues; 2. Identify and work together with the decision makers that affect the local facilities; 3. Understand the local circumstances, environment, and other critical issues; 4. Engagement with the community on a regular and on-going basis both from a business perspective and by personal contacts through interactions of individual employees. 4.7 Air pollution control in cement production Particulate matter, commonly called dust, is the primary emission in the manufacture of cement. For the control of dust the cement industry employs mechanical collectors, i.e. cyclone collectors and to a lesser degree small size gravity settling chambers, further fabric Kåre Helge Karstensen [email protected] Page 61 of 420 type dust collectors, gravel bed filters and finally electrostatic precipitators. To meet the emission standards, sometimes combinations of these collectors are employed, depending on the intensity and temperature of the effluents. In all modern kiln systems, the exhaust gases are finally passed through an air pollution control device for separation of the dust before being released to the atmosphere via stacks. Today, two types of dust separators are most commonly used in the modern cement industry, electrostatic precipitators and bag filters. Gravity settling chambers will always be of importance for pre-cleaning of high dust laden gases; they work on the principle of removing the dust by reducing the velocity of the gas or air stream. The gas is directed from the dust generating equipment into the large volume of settling chambers, where velocity drops low enough to let large dust particles drop out by gravity. Dust settling chambers are sometimes equipped with deflectors, to change the direction of gas flow and so to shorten the settling path of the particles, improving collection efficiency. Because of the simple construction, gravity settling chambers are the lowest in cost, but at the same time also the least effective dust collection devices. Only relatively coarse particles are removed. For removing of fine dust particles, e.g. in the range of 20 microns, large size gravity settling chambers would be required, with a length of about 35 m. Therefore settling chambers are used only to reduce the dust load ahead of more efficient dust collectors such as bag filters or electric precipitators. The efficiency of gravity settling chambers is in the range of 30-70% when handling typical dust of a cement plant. The gas velocity in the settling chambers should not exceed 0.5 m/sec (Duda, 1985). Cyclones as dust collection devices were in use long before their mode of operation was theoretically explained and calculable. A cyclone consists essentially of two sections; a cylindrical and a conical one. At the top of the cylindrical section the gas enters tangentially and spirals along the walls downward into the conical section (outside vortex); from here it starts to occupy the center space of the cyclone, and spirals upward (inside vortex) to the outlet thimble. Centrifugal forces push the dust particles toward the wall where they accumulate and descend down by gravity as well as under the influence of the outer vortex. Most of the particles fall down to the bottom into a hopper from where they are removed by rotary valves or screw conveyors. The ascending gas vortex represents the clean gas, but it always contains a certain amount of fine particulates. The inside vortex occupies only a small part of the cyclone’s cross-section, and along its axis there is the so-called neutral sector; if the size of this sector is taken away with the escaping gases. From this it results that the Kåre Helge Karstensen [email protected] Page 62 of 420 longer distance a dust particle has to cover for reaching the boundary gas layer, the less particles are separated in the cyclone; therefore it can be said that the efficiency of a cyclone diameters of 225, 400, 600 and 3150 mm, the corresponding efficiencies equal 96.7, 92.6, 88.2, and 57.5% (Duda, 1985). In the cement industry, cyclones are for application with rotary kilns, great clinker coolers, crushers, dryers, grinding mills, conveyors, etc. They are low cost dust collectors, without moving parts, and can be furnished with refractory linings for high temperatures up to 975°C. Cyclones can be designed for high pressure drop as well as for medium throughput, and high dust collection efficiency. Cyclones are built with diameters from 300 to 2300 mm in arrangements of one, two, four or six units combinations. The size of the particular cyclones depends (besides the required throughput and collection efficiency) also on the dust load, the particle size as well as on the properties of the dust. Units of cyclones may be installed in parallel for large gas volumes, and in series for higher efficiencies, or in combinations of series and parallel for high throughput and high efficiency. It was learn from practical experience that the diameters of cyclones with the best efficiency are in the range of 50 to 300 mm. However, the capacity of such cyclones is low and in the range of about 25 m3/min (Duda, 1985). Therefore for higher gas volumes a multitude of small diameter cyclones are combined into groups of cyclones, commonly called multicyclones. Multicyclones are enclosed units and arranged in banks of parallel flow with feed gas from a plenum chamber and with a common dust discharge hopper; multicyclones units can contain up to 400 individual cyclones. The efficiency of multicyclone dust collectors is in the range of 85-94%, collecting dust particles of 15 to 20 micron diameter an up, with a pressure drop of 130-180 mm of water column. A disadvantage of multicyclones is occasional plugging of the small tubes. In country with less stringent air pollution regulations, the multicyclone is in the cement industry a major component in collection of dust from kiln gases, grate clinker coolers, dryers, grinding mills, etc. However, in countries with stricter dust control regulations, the multicyclone serves mostly as a primary dust collector ahead of high efficiency dust collectors. Kåre Helge Karstensen [email protected] Page 63 of 420 Fabric filters used in the cement industry are generally of the bag type, e.g. tubes with 300 mm diameter or less, and up to 10 m high; they consist of woven or felted cloth, made from natural or synthetic fibers. Fabric filters can handle small particles in the submicron range at high efficiencies of 99.95%. Depending on the kind of fabric, these filters can be applied to gas temperatures up to 285°C. The dust laden gas flows through a porous medium – the filter fabric – and deposits particles in the voids. After filling the voids, a cake starts to build up on the fabric’s surface, which does most of the filtering. During the precoating period which lasts only moments, the efficiency may drop. When the dust layer on the fabric becomes too thick, an increase in pressure drop results; this requires cleaning of the fabric. Depending on the characteristic of the dust and the type of the fabric, there are generally four methods of filter cleaning in use: • Bag swinging; this is a method which imparts a gentle oscillating motion to the tops of the filter bags; this helps to dislodge the dust cake. • Reverse air; this method collapses the filter tube by differential air pressure, thus releasing the filter cake. • Pulse pressure; the plenum chamber of the isolated compartment is for about 300 milliseconds supplied with a burst of compressed air of about 7 kg/cm. This pulse of air expands rapidly and sets up a shock wave which flexes the fabric, thus dislodging the dust cake. For the pulse air a small separate compressor is required. • Sonic cleaning; this method employs sound generators which produce a low frequency sound (<200 Hz/sec., intensity 100-150 dB), causing the filter bags to vibrate. These vibrations combined with reversed air loosen dust particles from the surface of the fabric. Cleaning is accomplished periodically, mostly in response to a timer. Sometimes two different cleaning methods are applied to one filter for a better cleaning. During cleaning action there is no airflow through the filer bag in the normal direction; this requires that the period of cleaning, the particular dust collector compartment most be taken off-stream. Therefore for continuous automatic dust collection a fabric dust type collector must have one Kåre Helge Karstensen [email protected] Page 64 of 420 compartment in excess of the capacity required by the gas volume. Bag filter performance is not susceptible to process disturbances or “CO peaks”. Electrostatic precipitators use electrostatic forces to separate the dust from the exhaust gas. By means of discharge electrodes, the dust particles are negatively charged and can be separated on corresponding collecting electrodes. The particles are then discharged from the collecting electrodes to dust hoppers by electrode rapping. In contrast to bag filters, the design of electrostatic precipitators allows the separate collection of coarse and fine particles. ESP's are susceptible to process changes such as CO peaks. The dedusting efficiency can be increased by making use of more than one electric “field” operating in series. Dust collectors are evaluated by their efficiencies. The efficiencies of dust collection equipment are the ratio of the quantity of precipitated dust to the total quantity of dust introduced into the dust collection device, expressed in percent. Thus, if from an introduced dust quantity of 100 g, the dust collector retains 95 g, the efficiency of the dust collector is 95%. With a dedusting efficiency of up to 99.99% in modern control devices, it is possible to achieve a dust emission level from the stack below 20 mg per cubic meter of gas. In the dry process, the kiln exhaust gases have relatively high temperature and low humidity. Therefore, they can be utilised for drying of the raw materials in the raw mill during “compound operation”, i.e. when the raw mill is in operation. During “direct operation” (with the raw mill off), the hot exhaust gases have to be cooled down by means of water injection in a conditioning tower to a temperature suitable to the dust collector. With this procedure the gas volume is reduced, too, and the precipitation characteristics of the dust in the filter system are improved. The dust collected in the filter devices can be fed back to the process, either by reintroducing it to the raw materials preparation system (dry process), by insufflations into the sintering zone (wet kilns), or by feeding the dust to the cement mill (if allowed in the cement standards). Kåre Helge Karstensen [email protected] Page 65 of 420 In certain cases where the level of alkali elements is limited in cement clinker (“low alkali” clinker), not all the kiln dust can be returned to the system. Whereas an electrostatic precipitator allows the high alkali part of the dust to be separated and rejected, such a separation cannot be achieved with a bag filter and all the dust would have to be rejected. The other main sources of dust in the cement manufacturing process which require dedusting are the clinker cooler, the raw mill and the cement mills. Due to its low temperature, exhaust air from cement mills does not require cooling. Depending on the process stage where it is extracted, the chemical and mineralogical composition of the dust corresponds respectively to that of the raw meal, the clinker or the cement, or their intermediate products. 4.7.1 Inherent "scrubbing" of exit gases in preheater kiln In all kiln systems, the finely ground raw material moves in counter-current flow to the hot combustion gases. Thus, it acts perfectly as an integrated multi-stage exhaust gas cleaning system very similar to the operating principle of a circulating fluidised bed absorber or "dry scrubber". Components resulting from the combustion of the fuels or from the transformation of the raw materials remain in the exhaust gas only until they are absorbed by the fresh raw meal flowing in counter-current. The raw meal with its large specific surface and its high alkalinity provides an excellent medium to retain gas components within the kiln system. For instance, calcined or partly calcined raw meal with its high content of reactive calcium oxide has a high absorption capacity for acid gases such as sulfur dioxide and hydrochloric or hydrofluoric acid, but also for other pollutants such as heavy metals. Wet kilns and long dry kilns provide intimate contact between gas and solid particles mainly at the kiln inlet with its chain system for heat exchange. Semi-dry and semi- wet kilns provide this “scrubber effect” mainly in the grate preheater section of the kiln system, and also in heated crushers or dryers when these are used. Kåre Helge Karstensen [email protected] Page 66 of 420 Suspension preheater kilns with 4 to 6 cyclone stages are especially well suited to achieve a “multi-stage” scrubber effect especially when operating together with the raw mill (compound operation). At least 5 scrubber stages operate in series at different temperature levels between 100 and 800 °C consuming roughly 1 kg of absorbent (i.e. raw meal/hot meal) per Nm3 of exhaust gas. Kåre Helge Karstensen [email protected] Page 67 of 420 5. Regulation of co-processing in the cement industry The regulatory requirements for using cement kilns for hazardous waste co-processing are somewhat different in the EU and the US regulation. In the EU, cement kilns coprocessing hazardous wastes must comply with emission limit values for dusts, HCl, HF, NOx, SO2, 12 heavy metals, total organic carbon (TOC) and PCDD/F's laid down in the Council Directive 2000/76/EC on the Incineration of Waste (Council Directive, 2000). The Directive recognizes that co-processing in cement kilns is a viable solution for waste treatment, destruction and recovery of energy and raw materials. The emission limit values for dioxins and furans (PCDD/F’s) are more stringent in the EU regulation than in the US. However, no test burn is required to verify the performance in Europe. The combustion of hazardous waste in cement kilns has been regulated by the US Environmental Protection Agency (EPA) since 1991. In September 1999, under the Clean Air Act, EPA published new, more stringent regulations governing hazardous waste combustion. These rules, called Maximum Achievable Control Technology (MACT) standards, were developed over a 6-year period. They contain technology-based limits on emissions of hazardous air pollutants (PCDD/F's, total chlorine, 6 heavy metals, dust and hydrocarbons) and no other form of combustion is regulated more stringently in the US than the use of hazardous waste as fuel in cement kilns (Federal Register, 1999; CKRC, 2003; Balbo et al., 1998). The US TSCA PCB incineration criteria require a temperature of 1,200oC and 2 seconds retention time at 3% oxygen; the EU Directive 2000/76/EU require a temperature of 850oC for at least 2 seconds for the incineration of non-chlorinated hazardous waste and 1,100oC and 2 seconds retention time for organic substances containing more than 1% halogen at 2% oxygen. These regulations seek to assure environmental quality and control mechanisms that allow cement kiln co-processing to be a viable, fully qualified method for the treatment of and recovery from hazardous wastes. Kåre Helge Karstensen [email protected] Page 68 of 420 5.1 Waste definition Hazardous wastes are often defined differently from country to country and also by various international organisations. The reason for this is that the hazardous property can be based on different parameters and properties, like the origin of the waste, the chemical composition, the physical form as well as biological, chemical and physical properties. The Basel Convention for example, mention 45 categories of wastes that are presumed to be hazardous, but hese categories of waste need to exhibit one or more hazardous characteristics: flammable, oxidising, poisonous, infectious, corrosive or ecotoxic. UNEP says the following: “Wastes other than radioactive wastes which, by reason of their chemical activity or toxic, explosive, corrosive or other characteristics cause danger or are likely to cause danger to health or the environment”. The US EPA lists three categories: 1) The waste that is listed in EPA regulations; 2) The waste is tested and meets one of the four characteristics established by EPA, ignitable, corrosive, reactive and toxic; 3) The waste is declared hazardous by the generator. The European waste Catalogue have a core list of 850 types of waste, of these, around 420 are classified as hazardous wastes, and these are divided into 19 main categories. Cement kilns have utilised various hazardous wastes for energy replacement since the early 1970s. However, such practice imposes strict permit requirements. In Europe, cement kilns utilising hazardous wastes as co fuel must comply with the emission limit values laid down in the Council Directive 2000/76/EC on the Incineration of Waste. Industrial facilities and cement kilns in the US combusting hazardous wastes must comply with emission limit values laid down in the National Emission Standards for Hazardous Air Pollutants (Federal Register, 1999). In addition, they have to perform a Test Burn to demonstrate the incinerator performance on selected Principal Organic Hazardous Constituents (POHC). An introduction to regulatory issues of burning hazardous wastes in cement kilns in the US is given in the next sub-chapter. Two relevant EU-directives are provided in the Annex. Kåre Helge Karstensen [email protected] Page 69 of 420 5.2 Introduction to co-processing of hazardous waste in the US Typically, a cement kiln is fired with coal, petroleum coke, oil, or natural gas. However, cement kiln operators in the US began recovering energy from organic waste materials as early as 1974 (Mantus, 1992). That practice became commonplace by 1987 and since 1991 US cement kilns have used roughly 1,000,000 tons per year of hazardous waste as fuel. Some of the US kilns are permitted to replace up to 100 % of their conventional fuels with waste-derived fuels (CKRC, 2002). Trial burns have consistently shown that destruction and removal efficiencies of 99.99 to 99.9999 % can be achieved for very stable organic wastes, including chlorinated compounds, using cement kilns (Greer et al, 1992). Other types of supplemental fuel commonly used include natural gas, fuel oil, automobile tires, used motor oil, sawdust, and scrap wood chips. 5.2.1 Hazardous waste in the US A hazardous waste is a material that no longer has commercial value and requires disposal, and that either specifically listed by the U.S. EPA or meets one of the four characteristics defined by the U.S. EPA. The characteristics (ignitability, corrosivity, reactivity, and toxicity) are defined by an extensive list of criteria (Title 40 of the U.S. Code of Federal Regulations, Part 261 (40 CFR 261)). Typically, if a waste meets one of these criteria, it is labeled as a hazardous waste. The criteria for each of the four characteristics are outlined below. An ignitable waste is defined as one of the following (40 CFR 261.21): - a liquid with a flash point of less than 140ºF excluding an aqueous alcohol solution with less than 24% by volume of alcohol (Celsius and Fahrenheit temperatures can be interconverted as follows: C = (F - 32) × 100/180; F = (C × 180/100) + 32. Celsius and Kelvin can be interconverted as follows: C = (K - 273.15); K = (C + 273.15). Kåre Helge Karstensen [email protected] Page 70 of 420 - a substance that ignites “through friction, absorption of moisture or spontaneous chemical changes and burn so vigorously and persistently that it creates a hazard” (40CFR 261.21). - an ignitable compressed gas specifically listed by the U.S. EPA. - an oxidizer specifically listed by the U.S. EPA. Volumes of Hazardous Waste Burned for Energy Recovery in U.S. Cement Kilns Tons (in thousands) 1200 1000 800 600 400 200 19 89 19 90 19 91 19 92 19 93 19 94 19 95 19 96 19 97 19 98 19 99 20 00 0 Figure 3 Volumes of hazardous waste used in US cement kilns 1989-2000 Examples of substances that could be classified as ignitable waste are acetone and methanol. A corrosive waste is defined as one of the following (40 CFR 261.22): - an aqueous acid (pH less than or equal to 2); Kåre Helge Karstensen [email protected] Page 71 of 420 - an aqueous base (pH greater than equal to 12.5); - a liquid that corrodes steel at a rate greater than 0.250 inches per year at a temperature of 130ºF. Examples of substances that could be classified as corrosive waste are acetic acid and ammonia. A reactive waste is defined as one of the following (40CFR 261.23): - an unstable substance that undergoes violent change without exploding; - a substance that react violently with water; - a substance that combines with water to create an explosive mixture; - a substance that produces a significant quantity of toxic fumes when mixed with water; - a cyanide or sulfide containing substance that releases a significant quantity of toxic fumes on exposure to an environmental with a pH range of 2 to 12.5; - an explosive substance that is either capable of detonation or specifically by the U.S. EPA as an explosive. Examples of substances that could be classified as reactive wastes are trinitrotoluene (TNT) and nitroglycerine. The designation of a waste as toxic as somewhat more obscure than the designations discussed above. Officially, the U.S. EPA defines a toxic waste that contains components that have demonstrated mutagenicity, carcinogenicity, or teratogenicity (40 CFR 261.11). Benzene is an example of a compound that could be classified as a toxic waste. The generic toxic label also includes two U.S. EPS classifications: a “toxicity characteristic” waste and an “acute hazardous” waste. These classifications are defined in the following way. If an extract of a representative sample of a waste contains concentrations of components listed by the U.S. EPA that equal or exceed the limits set by the U.S. EPA, then Kåre Helge Karstensen [email protected] Page 72 of 420 the waste is designated as a “toxicity characteristic” waste (40 CFR 261.24). The individual limits set by the U.S. EPA for the listed components represent the concentrations above which the listed components exhibit the characteristic of toxicity. An example of a component that has been listed by the U.S. EPA is lead. An “acute hazardous” waste is one of that contains components that are either fatal or believed to be fatal to humans in small quantities (40 CFR 261.11). Potassium cyanide is an example of a compound that could be classified as an “acute hazardous” waste. With lists of the hazardous waste criteria, the process of classifying a waste would appear to be straightforward. If a waste meets one of the hazardous waste characteristics or is specifically listed by the U. S. EPA, then it should be classified as hazardous. Because of the large number of exemptions, the hazardous waste classification system is not as simple as it appears. For example, household waste is specifically exempt, although some household waste such as turpentine, oven cleaner, and many automotive fluids would meet at least one of the criteria discussed above. However, because of its exemption status, this waste is not evaluated. As a result, many types of waste that are in principle hazardous do not have the official U.S. EPA hazardous waste label. 5.3 Hazardous waste incineration in the EU The Directive 2000/76/EC on the incineration of waste defines an ‘incineration plant’ to mean any stationary or mobile technical unit and equipment dedicated to the thermal treatment of wastes with or without recovery of the combustion heat generated. This includes the incineration by oxidation of waste as well as other thermal treatment processes such as pyrolysis, gasification or plasma processes in so far as the substances resulting from the treatment are subsequently incinerated. This definition covers the site and the entire incineration plant including all incineration lines, waste reception, storage, on site pretreatment facilities, waste-fuel and airsupply systems, boiler, facilities for the treatment of exhaust gases, on-site facilities for treatment or storage of residues and waste water, stack, devices and systems for controlling incineration operations, recording and monitoring incineration conditions; Kåre Helge Karstensen [email protected] Page 73 of 420 A ‘co-incineration plant’ means any stationary or mobile plant whose main purpose is the generation of energy or production of material products and which uses wastes as a regular or additional fuel; or in which waste is thermally treated for the purpose of disposal. If coincineration takes place in such a way that the main purpose of the plant is not the generation of energy or production of material products but rather the thermal treatment of waste, the plant shall be regarded as an incineration plant. This definition covers the site and the entire plant including all co-incineration lines, waste reception, storage, on site pretreatment facilities, waste-, fuel and air-supply systems, boiler, facilities for the treatment of exhaust gases, on-site facilities for treatment or storage of residues and waste water, stack devices and systems for controlling incineration operations, recording and monitoring incineration conditions; The Directive 2000/76/EC on the incineration of waste specifies the following operating requirements: 1. Incineration plants shall be operated in order to achieve a level of incineration such that the slag and bottom ashes Total Organic Carbon (TOC) content is less than 3% or their loss on ignition is less than 5% of the dry weight of the material. If necessary appropriate techniques of waste pretreatment shall be used. Incineration plants shall be designed, equipped, built and operated in such a way that the gas resulting from the process is raised, after the last injection of combustion air, in a controlled and homogeneous fashion and even under the most unfavorable conditions, to a temperature of 850 °C, as measured near the inner wall or at another representative point of the combustion chamber as authorized by the competent authority, for two seconds. If hazardous wastes with a content of more than 1% of halogenated organic substances, expressed as chlorine, are incinerated, the temperature has to be raised to 1 100 °C for at least two seconds. Each line of the incineration plant shall be equipped with at least one auxiliary burner. This burner must be switched on automatically when the temperature of the combustion gases after the last injection of combustion air falls below 850 °C or 1 100 °C as the case may be. It shall also be used during plant start-up and shut-down operations in order to ensure that the temperature of 850 °C or 1 100 °C as the case Kåre Helge Karstensen [email protected] Page 74 of 420 may be is maintained at all times during these operations and as long as unburned waste is in the combustion chamber. During start-up and shut-down or when the temperature of the combustion gas falls below 850 °C or 1 100 °C as the case may be, the auxiliary burner shall not be fed with fuels which can cause higher emissions than those resulting from the burning of gasoil as defined in Article 1(1) of Council Directive 75/716/EEC, liquefied gas or natural gas. 2. Co-incineration plants shall be designed, equipped, built and operated in such a way that the gas resulting from the co-incineration of waste is raised in a controlled and homogeneous fashion and even under the most unfavorable conditions, to a temperature of 850 °C for two seconds. If hazardous wastes with a content of more than 1% of halogenated organic substances, expressed as chlorine, are co-incinerated, the temperature has to be raised to 1 100 °C. 5.3.1 Hazardous waste definition The Hazardous Waste Directive (1991) is one of the oldest EU legislative acts on waste. Its provisions are indispensable for safeguarding a high level of environmental protection; and the differentiation it introduces between hazardous and non hazardous waste is along with the differentiation between recovery and disposal laid down in the Waste Framework Directive a key element of waste management policy. Categories or generic types of hazardous waste are listed according to their nature or the activity which generated them. Waste may be liquid, sludge or solid in form. Properties of wastes which render them hazardous are given in the Annex III of the Hazardous Waste Directive (1991). H1 ‘Explosive’: substances and preparations which may explode under the effect of flame or which are more sensitive to shocks or friction than dinitrobenzene. Kåre Helge Karstensen [email protected] Page 75 of 420 H2 ‘Oxidizing’: substances and preparations which exhibit highly exothermic reactions when in contact with other substances, particularly flammable substances. H3-A ‘Highly flammable’: liquid substances and preparations having a flash point below 21 ºC (including extremely flammable liquids), or substances and preparations which may become hot and finally catch fire in contact with air at ambient temperature without any application of energy, or solid substances and preparations which may readily catch fire after brief contact a source of ignition and which continue to burn or to be consumed after removal of the source of ignition, or gaseous substances and preparations which are flammable in air at normal pressure, or substances and preparations which, in contact with water or damp air, evolve highly flammable gases in dangerous quantities. H3-B ‘Flammable’: liquid substances and preparations having a flash point equal to or greater than 21 ºC and less than or equal to 55 ºC. H4 ‘Irritant’: non-corrosive substances and preparations which, through immediate, prolonged or repeated contact with the skin or mucous membrane, can cause inflammation. H5 ‘harmful’: substances and preparations which, if they are inhaled or ingested or if they penetrate the skin, may involve limited health risks. Kåre Helge Karstensen [email protected] Page 76 of 420 H6 ‘Toxic’: substances and preparations (including very toxic substances and preparations) which, if they are inhaled or ingested or if they penetrate the skin, may involve serious, acute or chronic health risks and even death. H7 ‘Carcinogenic’: substances and preparations which, if they are inhaled or ingested or if they penetrate the skin, may induce cancer or increase its incidence. H8 ‘Corrosive’: substances and preparations which may destroy living tissue on contacts. H9 ‘Infectious’: substances containing viable micro-organisms or their toxins which are known or reliably believed to cause disease in man or other living organisms. H10 ‘Teratogenic’: substances and preparations which, if they are inhaled or ingested or if the penetrate the skin, may induce non-hereditary congenital malformations or increase their incidence. H11 ‘Mutagenic’: substances and preparations which, if they are inhaled or ingested or if they penetrate the skin, may induce hereditary genetic defects or increase their incidence. H12 Substances and preparations which release toxic or very toxic gases in contact with water, air or an acid. H13 Substances and preparations capable by any means, after disposal, of yielding another substance, e.g. a leachate, which possesses any of the characteristics listed above. H14 ‘Ecotoxic’: substances and preparations which present or may present immediate or delayed risks for one or more sectors of the environment. 5.3.2 Hazardous constitutents Kåre Helge Karstensen [email protected] Page 77 of 420 Wastes having the constituents given below which render them hazardous or the properties described in the previous chapter are regarded to be hazardous (Annex II): C1 beryllium; beryllium compounds; C2 vanadium compounds; C3 chromium (VI) compounds; C4 cobalt compounds; C5 nickel compounds; C6 copper compounds; C7 zinc compounds; C8 arsenic; arsenic compounds; C9 selenium; selenium compounds; C10 silver compounds; C11 cadmium; cadmium compounds; C12 tin compounds; C13 antimony; antimony compounds; C14 tellurium; tellurium compounds; C15 barium compounds; excluding barium sulfate; C16 mercury; mercury compounds; Kåre Helge Karstensen [email protected] Page 78 of 420 C17 thallium; thallium compounds; C18 lead; lead compounds; C19 inorganic sulphides; C20 inorganic fluorine compounds, excluding calcium fluoride; C21 inorganic cyanides; C22 the following alkaline or alkaline earth metals: lithium, sodium, potassium, calcium, magnesium in uncombined form; C23 acidic solutions or acids in solid form; C24 basic solutions or bases in solid form; C25 asbestos (dust and fibres); C26 phosphorus: phosphorus compounds, excluding mineral phosphates; C27 metal carbonyls; C28 peroxides; C29 chlorates; C30 perchlorates; C31 azides; C32 PCBs and/or PCTs; Kåre Helge Karstensen [email protected] Page 79 of 420 C33 pharmaceutical or veterinary compounds; C34 biocides and phyto-pharmaceutical substances (e.g. pesticides, etc.); C35 infectious substances; C36 creosotes; C37 isocyanates; thiocyanates; C38 organic cyanides (e.g. nitriles, etc.); C39 phenols; phenol compounds; C40 halogenated solvents; C41 organic solvents, excluding halogenated solvents; C42 organohalogen compounds, excluding inert polymerized materials and other substances referred to in this Annex; C43 aromatic compounds; polycyclic and heterocyclic organic compounds; C44 aliphatic amines; C45 aromatic amines C46 ethers; C47 substances of an explosive character, excluding those listed elsewhere in this Annex; C48 sulphur organic compounds; C49 any congener of polychlorinated dibenzo-furan; C50 any congener of polychlorinated dibenzo-p-dioxin; Kåre Helge Karstensen [email protected] Page 80 of 420 C51 hydrocarbons and their oxygen; nitrogen and/or sulphur compounds not otherwise taken into account in this Annex. 5.4 Emissions of dioxins - regulatory framework in the European Union Regulation of POPs emissions from cement kilns has mainly been confined to PCDD/F emissions and developed first of all in countries like the European Union (EU) and the United States of America (US). In many developing countries regulation and adequate legislation is not yet in place, were it is enforcement is weak or lacking. The availability of PCDD/F data from developing countries is still rare. In the early nineties the European Commission (EC) drafted the Directive 94/67/EC on the Incineration of Hazardous Waste (Bollmacher, 2001). The EC requested the European Committee for Standardization (CEN) to prepare well-validated and harmonized European Standard (EN 1948) to monitor several pollutants; special attention was paid to PCDD/Fs. The directive entered into force in December 1994 and all member states of the European Union (EU) had to bring into force their laws, regulations and administrative provisions necessary to comply with this directive before the end of 1996. In the directive a PCDD/F limit value of 0.1 ng TEQ/m³ was set as an average value measured over the sample period of a minimum of six hours and a maximum of eight hours. Apart from the emission limit value of 0.1 ng TEQ/m3, the following restrictions were also valid: • Even under the most unfavourable conditions a temperature of > 850 °C has to be maintained for at least two seconds to destroy PCDD/Fs and to avoid precursors. If more than 1 % of halogenated organic substances, expressed as chlorine, are incinerated, the temperature has to be raised to at least 1100 °C. • Sampling and analysis of PCDD/Fs shall be carried out as specified in EN 1948. • At least two measurements per year shall be carried out (one measurement every two months for the first twelve months of plant operation). All measurements shall meet the emission limit values. Kåre Helge Karstensen [email protected] Page 81 of 420 • The measurement results are based on standard conditions (273 K, 101.3 kPa, dry gas, 10 % O2, or 3 % O2 in case of waste oil). • The determination of the emission limit values for co-incineration of hazardous waste must be calculated according to equation: where V is the exhaust gas volume resulting from the incineration of hazardous waste or from the plant process, C is the total emission limit value, Cwaste is emission limit value for plants to incinerate hazardous waste only (0.1 ng TEQ/m³), Cprocess is the emission limit value of the normal process laid down in the permit; in the absence of this data the mass concentrations are used. • The emission limit value shall not apply to existing incineration plants before 31 December 2006. • Any member state of the EU is allowed to maintain or introduce more stringent measures for the protection of the environment. The Directive 2000/76/EC on the incineration of waste entered into force in December 2000. This directive includes the incineration of waste and hazardous waste as well as coincineration of hazardous waste in cement kilns; the existing two Directives on waste and waste incineration shall be repealed from December 2005. With respect to the PCDD/Fs the new Directive 2000/76/EC specifies the same requirements as those stated in Directive 94/67/EG as well as the following important amendments: • If in a co-incineration plant more than 40 % of the resulting heat release come from hazardous waste, the complete emission limit value is 0,1 ng TEQ/m3. • At least two PCDD/F measurements per year shall be carried out (one measurement at least every three months for the first twelve months of plant operation). Kåre Helge Karstensen [email protected] Page 82 of 420 • EC shall decide, as soon as appropriate measurement techniques are available, the date from which continuous measurements shall be carried out for PCDD/F monitoring. • At least one PCDD/F measurement every six months (one at least every three months for the first twelve months of plant operation) shall be carried out for water discharges from the cleaning of exhaust gases at the point of the waste water discharge. The limit value is 0.3 ng TEQ/l. The measurements shall not exceed the limit value. • The directive shall apply to existing plants as from December 2005. In all EU Directives the principles of integrated pollution prevention and control (IPPC), specifically laid down in Directive 96/61/EC, covering all aspects of environmental performance in an integrated manner, shall be taken into account. Also Best Available Technique Reference Documents (BREFs) established by the European IPPC Bureau have to be taken into account by the authorities for issuing permits. Also the Protocol on persistent organic pollutants signed by the EU within the framework of the United Nations Economic Commission for Europe (UN-ECE) Convention on long-range transboundary air pollutions sets a legally binding PCDD/F emission limit value of 0.1 ng TEQ/m3 for incinerating more than 3 tonnes per hour of municipal solid waste and 0.5 ng TEQ/m3 for installations burning more than 1 ton per hour of medical waste, and 0.2 ng TEQ/m3 for installations incinerating more than 1 ton per hour of hazardous waste. 5.4.1 PCDD/F emission limit values for cement kilns Gaseous emissions from cement kiln using conventional fuels are regulated within the EU under the so-called Air Framework Directive 84/360/EEC (Eduljee, 1998). A technical note defining Best Available Techniques (BAT) for the manufacture of cement was published in 2000 (IPPC) and includes the emission levels achievable when using conventional fuels within the kiln, but does not identify BAT achievable emission levels using secondary or Kåre Helge Karstensen [email protected] Page 83 of 420 substitute fuels. The European cement industry has argued that prescriptive regulations designed to ensure combustion in dedicated waste incinerators are inappropriate for the regulation of fuel substitution in industrial furnaces such as cement kilns. The nature of the thermal processes governing cement manufacture is such that emissions arising from the combustion of the alternative fuel should be treated separately to emissions arising from the raw materials feeding the kiln. This principle has been accepted by the EU and applied in Directive 2000/76/EC on the incineration of waste, regulating the use of hazardous waste as a alternative fuel in cement kilns, by recognising and providing for the practice of ”co-incineration”. Individual Member States have also accepted the need to take account of emissions from raw materials in setting emission controls on exhaust gases from cement kilns. For example, in France emission limits for sulfur dioxide are set according to the sulfur content in the raw materials. In Germany the national waste incineration regulation 17.BimSchV makes specific provision for the exemption of carbon monoxide and total organic carbon emissions from cement plants burning waste supplementary fuels on the grounds that the emission of these substances is not a function of the fuel used or the amount of waste burnt, and is also not a relevant parameter for ensuring the safe combustion of secondary fuels in such plants. In general, the European cement industry has argued that regulatory decisions concerning the use of secondary fuels in cement plants are best taken at national level, thereby allowing regulators to take into account specific local conditions in writing permits. This position has been endorsed by the EU in Directive 96/61/EC on IPPC, in which national regulatory authorities are requested to base operating permits on BAT, while taking into account the technical characteristics of processes, their geographic location and local environmental conditions. As a safeguard, permits must not allow any EU environmental quality standards to be breached. Notwithstanding the derogations on emissions of substances such as sulfur dioxide and carbon monoxide, the cement industry has accepted the emission standard for dioxins of 0.1 ng TEQ/m3 generally applied throughout EU to regulate dioxin emissions from municipal and hazardous waste incineration. Emission levels shall be corrected to 273 K, 101.3 kPa, 10 % O2 and dry gas. Kåre Helge Karstensen [email protected] Page 84 of 420 The EU procedures for calculation of air emission limit values when co-incineration of waste in industrial facilities and the subsequent total emission limit values for cement kilns co-incinerating waste are given in figure 7 and 8 respectively. 5.4.2 Sampling and analysis Today sampling of PCDD/Fs in exit gas are in most cases undertaken by using one of two methods based on (or following that of) the US EPA Method 23 or the EN 1948. The EN 1948 offers three possible sampling principles: the filter/condenser, the dilution and the cooled probe method. In the US EPA Method 23, stack gases are sampled iso-kinetically through a sharpedged nozzle, heated glass probe and particulates collected on a filter. From the filter, gases pass through a condenser and XAD-2 resin trap, then through two impingers connected in series. Sampling is usually conducted over a period of 4 to 6 hours in order to extract a volume of duct gas sufficient for reliable determination of all PCDD/F congeners. The EN 1948 also requires the gas to be sampled iso-kinetically in the duct. The PCDD/Fs both adsorbed on particles and in the gas phase, is collected in the sampling train. The collecting parts can be a filter, a condensate flask and a solid or liquid adsorbent appropriate to the sampling system chosen. The German VDI Dilution Method 3499, an option in EN 1948, a known volume of flue gas is extracted iso-kinetically from the duct via a heated glass sampling probe. The sample is mixed in a glass chamber with a known volume of dried and filtered dilution air, lowering the temperature of the gas to below 50 oC. The particulate fraction and condensates of the gas are collected on a glass fibre filter, with the vapour phase fraction passing through a pre-conditioned polyurethane foam filter. In practice, iso-kinetic flue gas sampling conditions are not always achieved. This is primarily due to limitations imposed by the flue gas duct design and position of the sampling Kåre Helge Karstensen [email protected] Page 85 of 420 points, particularly in older installations. Uncertainties associated with the sampling and analytical procedures involved in sampling trace species such as PCDD/Fs have been estimated to have a 95 % confidence limit of 65 % to 200 %, depending on duct gas concentrations (Alcock et al, 1999). Since no reference materials are available for PCDD/Fs in exhaust gases, the accuracy of the sampling method it not possible to determine (EN 1948, 1996). 5.4.3 Development and validation of the EN-1948 At the end of the 1980s about 17 different sampling methods and a multitude of variants for clean-up and analysis existed in Europe (Bollmacher, 2001). Low and high resolution mass spectrometers (MS) were employed. Most of the measurement methods were not, or not well, validated. Only a few of them, e.g. the German VDI Dilution Method 3499, were partly validated for monitoring limit values of 0.1 ng TEQ/m3. CEN started therefore to develop a European Standard with reliable performance characteristics. Three different sampling methods out of the 17 existing ones were chosen and tested in a comparative field test at a municipal waste incinerator. The analytical part was fixed and carried out by two laboratories. Due to the fact that there is no reference flue gas material the "true" PCDD/F emission concentration could only be checked by comparing the different measurement systems. The repeatability and reproducibility were determined by having three sampling teams, each of which representing one of the three sampling methods, perform duplicate measurements. The measurements were carried out at the same time with a sampling duration of eight hours. All tests were performed within one week. The results of the field test showed that all three sampling methods (filter/condenser method, dilution method and cooled probe method) gave equivalent results. The sampling systems are as follows: • The filter/condenser method: The filter is placed downstream of the nozzle (in the stack) or after the probe (out of the stack). The filter has to be kept below 125 °C, but above the flue gas dew point. Downstream, a filter (particle diameter of 0.3 µm) is attached. The sample gas is cooled below 20 °C and the condensate is collected in a Kåre Helge Karstensen [email protected] Page 86 of 420 flask. The gaseous and aerosol parts of the PCDD/Fs are captured by impingers and/or solid adsorbents. In a variant, a system with division of flow can be used. • The dilution method: The sample gas is collected via a heated probe. The waste gas is cooled very rapidly to temperatures below 40 °C in a mixing channel using dried, filtered ambient air. After dilution a filter is used to collect the particulate PCDD/Fs contained in the waste gas stream. For the separation of the gaseous PCDD/Fs a solid adsorbent is linked downstream. The dilution avoids the temperature of the sampling gas falling below the flue gas dew point. • The cooled probe method: The sample gas passes the nozzle and a water-cooled probe. The sample gas is cooled below 20 °C. The condensate is caught in a flask. Downstream, impingers and/or solid adsorbers are linked to collect the gaseous PCDD/Fs. Before the last impinger or adsorbent, there is a filter to separate particles and to break aerosols. After showing the equivalency of the sampling methods two validation field tests were performed at municipal waste incinerators to determine the performance characteristics. Three sampling teams, representing one of the sampling systems each, carried out the validation test at each of the incinerators. The samples were distributed to six analytical laboratories and to a seventh which performed cross checks for quality assurance. Due to discrepancies a third field test at a municipal waste incinerator followed and 19 laboratories in 11 European countries were involved. One of the challenges was to find an incineration plants with PCDD/F emissions as near 0.1 ng TEQ/m³ as possible. If the concentrations were above 0.1 ng TEQ/m³, EC would not accept them because they were out of the monitoring concentration range. Also, the PCDD/F concentration in the cross section of the duct had to be identical; otherwise the six sampling trains (two duplicate measurements by each of the three sampling teams) would collect different PCDD/F concentrations. Certified 13 C12- labelled standards had to be organized and checked for their applicability as sampling, extraction and syringe standards; it had to be tested and defined which of these standards was to be taken for the calculation of results. Iso-kinetic sampling had to be applied and minimum resolution of the MS had to be fixed. And last but not least, at that time, some laboratories were not well trained for this concentration range. Kåre Helge Karstensen [email protected] Page 87 of 420 The EN 1948 was finalized in time before mid-1996. It is subdivided in three parts. Part 1 describes sampling, Part 2 extraction and clean-up, and Part 3 identification and quantification. For each of the three steps, very stringent requirements are specified and illustrated by examples. EN 1948 has been accepted by all EU and EFTA states. 5.4.4 Analysis and recovery PCDD/F analysis is usually carried out using high resolution mass spectrometry (GCMS). Quality control procedures are required in each stage of the analysis and recovery spike concentrations associated with both sampling and extraction. The US EPA Method 23 specifies that all recoveries should be between 70 % and 130 %. Spike recoveries of 13 C12 congeners (added before the sample is collected to monitor the collection efficiency during sampling) ranged from 30 to 110 % in the UK emission inventory done in 1995-1997 (Alcock et al, 1999). The inventory collected 75 samples from different source categories and the analytical blanks for the analysis using Method 23 ranged from less than 0.005 ng to 0.1 ng TEQ. 5.4.5 Detection/quantification limits and interferences The Lower Detection Limit (LOD) measured during the validation test of EN 1948 at a municipal solid waste incinerator varied between 0.0001 - 0.0088 ng/m3 for the 17 individual PCDD/F toxic congeners (EN 1948 -3, 1996). In the new draft of EN 1948-3 of February 2004, Annex B, the uncertainty for the complete procedure is given to be 30-35 % and the external variability is estimated to be ± 0.05 ng I-TEQ/m3 at a mean concentration 0.035 ng I-TEQ/m3. Taking into account the toxic equivalence factors for the individual congeners the resulting over all detection limits varies between 0.001 and 0.004 ng I-TEQ/m3. It’s reasonable to assume that concentrations lower than 0.001 ng I-TEQ/m3 should be considered as being below the detection limit. Kåre Helge Karstensen [email protected] Page 88 of 420 In a Canadian study performed in 1999 the variability of sampling and analysis of 53 sets of PCDD/F emission data from 36 combustion facilities was investigated. The Limit of Quantification (LOQ) for PCDD/F was estimated to be 0.032 ng TEQ/m3 (Environment Canada, 1999). Interferences should be expected to occur from compounds that have similar chemical and physical properties to PCDD/Fs (EN 1948 -3, 1996). 5.4.6 HCB and PCBs Hexachlorobenzene and PCBs are for the time being not required to be monitored on a routine basis in cement plant emissions in the EU or the US. 5.5 Dioxin emission standards in the US Under the authority of the Clean Air Act, EPA promulgated national emission standards for new and existing cement kilns burning non-hazardous waste in May 1999 (Federal Register, 1999a; 2004). The regulations are specific to the I-TEQ concentration in the combustion gases leaving the stack. Existing and new cement kilns either combusting or not combusting hazardous waste as auxiliary fuel cannot emit more than 0.2 ng I-TEQ/m3 (corrected to 25 0C, 7 % O2 and dry gas). In addition, the temperature of the combustion gases measured at the inlet to the air pollution control device cannot exceed 232 °C. The rule requires owners or operators of facilities to test for PCDD/Fs every 2½ years and the Office of Air Quality Planning and Standards (OAQPS) expects this rule to reduce I-TEQ PCDD/Fs emissions from existing and new facilities by 36 % over the next few years (Federal Register, 1999a and 2004). Most air pollution control devices (APCDs) used at cement kilns in the US between 1987 and 1995 were considered to be hot-sided control devices. A hot-sided control device is one that operates at kiln exhaust gas temperatures above 232 °C (some EPA rules use different definitions for hot-sided control devices for different industries). Most APCDs Kåre Helge Karstensen [email protected] Page 89 of 420 currently used at cement kilns are cold-sided devices (i.e., they operate at kiln exhaust gas temperatures below 232 °C. The US regulation also require operators of US cement kilns that use hazardous waste as fuel to periodically demonstrate that the kilns achieve a minimum DRE of 99.99 %. Based on the above criteria, the most common POHCs selected for these DRE tests are tetrachloroethylene, trichlorobenzene, 1,2-dichlorobenzene, and trichloroethylene. These chlorinated organic compounds are extremely thermally stable. POHCs selected for DRE testing should possess the following characteristics: 1. The POHC should be representative of the hazardous waste feed composition. 2. The POHC should be easily distinguished from other organics that may be emitted from the stack. 3. The POHC should function within all operating, testing, and analytical limitations. 4. The POHC must demonstrate the unit’s ability to destroy compounds that are difficult to destroy, including demonstration of both thermal and oxidation failure modes. EPA is currently developing CKD storage and disposal requirements. In 1999, a proposed rule for the standards for the management of CKD was developed by EPA (Federal Register, 1999b). Under the rule, CKD would remain a non-hazardous waste, provided that proposed management standards are met, which would protect groundwater and control releases of fugitive dust. Additionally, the rule proposes concentration limits on various pollutants in CKD used for agricultural purposes (Federal Register, 1999c). 5.6 The main emission regulation in the US Kåre Helge Karstensen [email protected] Page 90 of 420 The regulatory situation in the US for hazardous waste combustors, including cement kilns, is quite complex at this time due to several legal issues that have affected the status of the principal regulation governing hazardous waste combustion: the Hazardous Waste Combustor (HWC) NESHAP (National Emission Standards for Hazardous Air Pollutants). EPA first promulgated the HWC NESHAP, also call HWC MACT (Maximum Achievable Control Technology) in 1999. Those standards were vacated (i.e., rendered fatally flawed and therefore inapplicable) by a reviewing court in 2000. As a consequence, in 2001, EPA and the industry negotiated Interim Standards (EPA, 2002a) that are the standards we have complied with since 2004 (new regulations have a 3-year compliance schedule). In 2005, EPA published HWC MACT Replacement Standards (Federal Register, 2005). Those, too, have been subject of legal challenges and many parts of these most recent regulations will have to be redone by EPA. The "main regulation" in the US with respect to the cement kiln standards, very little has really changed between the Interim Standards that currently apply and the Replacement Standards, which are applicable in October 2008. Kåre Helge Karstensen [email protected] Page 91 of 420 Figure 4 Summary of emission limit values for existing sources (Federal Register, 2005) Kåre Helge Karstensen [email protected] Page 92 of 420 Figure 5 Summary of emission limit values for new or reconstructed (Federal Register, 2005) Kåre Helge Karstensen [email protected] sources Page 93 of 420 5.7 The main emission regulation in the EU The main emission regulation in the EU is given in the EU Directive 2000/76/EC on the incineration of waste. The EU procedures for calculation of air emission limit values when co-incineration of waste in industrial facilities and the subsequent total emission limit values for cement kilns co-incinerating waste are given in figure below.. Figure 6 Procedure given in the EU Directive 2000/76/EC on the incineration of waste for calculation of air emission limit values when co-incineration of waste in industrial facilities. Kåre Helge Karstensen [email protected] Page 94 of 420 Figure 7 Special provisions for cement kilns co-incinerating waste given in the EU Directive 2000/76/EC. Kåre Helge Karstensen [email protected] Page 95 of 420 5.8 Waste input control There are two regulatory approaches to control input of certain waste categories or specific pollutants in wastes; to apply a negative list of waste categories, i.e. to specify explicitly certain waste categories which are not allowed or not accepted, or to apply a positive list of wastes with concentration limits of specific contaminants. Two examples would be the GTZ-Holcim (2006) requirement and the Swiss Agency for the Environment, Forests and Landscape (1998) respectively. The EU Directive 2000/76/EC 11 provides explicitly in Art. 4, paragraph 4 that "the permit granted by the competent authority for an incineration or co-incineration plant shall ... list explicitly the categories of waste which may be treated." They have choosen to leave this descision to the various countries/regulators. But the EU directive 2000/76/EC limits the total heat input from hazardous waste to 40% of the total heat generated and requires that the local permit shall list the categories of waste which may be treated. Norway has implemented the EU regulation (Council Directive, 2000) and developed local permit conditions, which allow one of the cement plants to feed maximum 50 kg PCB's per hour, and maximum 110 kg halogens to the main burner and 35 kg halogens to the kiln inlet and the precalciner per hour (SFT, 1997). 5.8.1 GTZ-Holcim Guidelines The GTZ-Holcim Guidelines on Co-Processing Waste Materials in Cement Production mention that enforceable standards are needed on emission control and on the selection of wastes but that the regulatory framework must provide rules that are easy to enforce. National emissions standards must be applied by the concerned authorities and implemented by permits in each case. Within the given standards, the technical specifications for co-processing and the waste to be used may vary from country to country or even from one cement plant to another. Kåre Helge Karstensen [email protected] Page 96 of 420 Special attention must be given to reliable emissions control and monitoring, as this is one of the most sensitive areas of the co-processing activity. In many countries, industrial emissions standards already exist but do not cover emissions from cement factories using AFR. The GTZ-Holcim Guidelines has derived from the EU waste catalogue, a list of wastes suitable for co-processing has been prepared (GTZ-Holcim, 2006). This list indicates that coprocessing is applicable for a wide range of waste and not limited to a certain type of waste. However, the decision on what type of waste can be finally used in a certain plant cannot be answered uniformly; it must be based on the clinker production process, the raw material and fuel compositions, the feeding points, the gas-cleaning process, the current existing local regulations, if any, and the given waste management problems. The GTZ-Holcim Guidelines states that wastes accepted as AFR must give an addedvalue for the cement kiln, i.e. a calorific value from the organic part and/or a material value from the mineral part. The GTZ-Holcim Guidelines statets also that kilns sometimes can be used for the safe disposal of special wastes such as obsolete pesticides, PCBs, or out-dated pharmaceutical products. However, for this type of treatment, regulatory authorities and cement plant operators must come to individual agreements and standards on a case-by-case basis. Such disposal activity should be done as a joint effort between the public and the private sector. The GTZ-Holcim Guidelines mention a wide range of waste materials may be used as AFR. The most common ones are mixed dirty paper, cartons, plastics, textiles, packaging material, tires, wood, and sorted wastes from households, commerce, or production and service industries. There are liquid waste products such as used oil, solvents or coal slurries as end-of-line products from the transport sector or derivates from industrial activities. Some waste materials can be delivered as single batches directly to the cement plant while others must be pre-processed to meet the required conditions. In some cases (e.g. municipal garbage, hospital waste), co-processing can only be applied after pre-processing phases such as segregation, sorting, making inert, neutralization, or thermal treatment. Regular quality control of the collected and delivered waste will help to ensure a smooth use of the AFR in the kiln. Kåre Helge Karstensen [email protected] Page 97 of 420 The GTZ-Holcim Guidelines states that the quality of what goes in determines the quality of what comes out. Therefore attention must be paid to the selection of raw materials and fuels, whether they come from primary or secondary sources. All natural resources used in cement production (raw material and fuels) contain pollutants such as heavy metals; so a pre-AFR baseline emissions study is recommended. Data from this study helps operators to understand the pollution content of traditional inputs and to demonstrate later whether the use of AFR offers environmental improvements. Process requirements, product quality targets, and emissions regulations all have a bearing on the choice of the chemical and physical parameters of the potential waste material considered for use. In selecting and using AFR, the aims are to fulfill any legal requirements about pollution, health, safety, and technical standards to assure that the waste used as AFR undergoes its most favorable treatment compared to possible other technologies to exclude damaging effects to the product or the production process to minimize the net financial and economic costs of waste management. The GTZ-Holcim Guidelines mention that many countries regulators have produced lists of maximum pollutant values allowed for selected waste to be transferred into AFR and for the pre-processed AFR itself. No agreed threshold limit values exist, as different criteria are applied, depending on the local situation. Such criteria include: national environmental policies; significance of the impact of the cement industry in the context of regional industrial development; efforts to harmonize supra regional environmental laws and standards; pollutants in traditional raw materials; treatment alternatives for the available waste; fixed minimum calorific value; toxicity level of pollutants in waste; requirements for cement quality. Kåre Helge Karstensen [email protected] Page 98 of 420 The GTZ-Holcim Guidelines states that all countries where co-processing will be used, such lists should be prepared and regularly reviewed by national or local authorities in cooperation with the cement associations. The aim is to define standard values appropriate for the local circumstances and requirements (on a country-wide basis or on a plant-by-plant approach). This sensitive task should be given special attention during any capacity development activity. According to the GTZ-Holcim Guidelines, the main objective of the permission and controlling process is to assure that only suitable wastes will be used and the AFR operations run properly. Regulators and kiln operators should be able to track the progress of the waste through the waste treatment path, either directly from a waste generator or through collecting/pre-treatment companies. The quality of the material designated for co-processing is crucial. Quality data and emissions monitoring data form the basis for scientific discussions with external stakeholders. They are also helpful tools for reducing local concern and the notion that cement plants are misused as trash bins for uncontrolled disposal of wastes. To avoid an overload of case-by-case decisions, permitting should be done for types of wastes; though there are exceptions to this (GTZ-Holcim, 2006). According to the GTZ-Holcim Guidelines, co-processing should only be applied if not just one but all tangible pre-conditions and requirements of environmental, health and safety, socio-economic and operational criteria are fulfilled. As a consequence, not all waste materials are suitable for co-processing. The GTZ-Holcim Guidelines, gives an overview for the justification of waste not being recommended for co-processing in cement plants. The GTZ-Holcim Guidelines recommends that cement plant operators must know the quantity and characteristics of the available wastes before applying for a permit for coprocessing. However, an open communication channel and regular consultations between the public and the private sector will help to reduce possible friction and misunderstandings and to develop a permit process most suitable for all involved. Kåre Helge Karstensen [email protected] Page 99 of 420 Table 6 List of waste material not suited for co-processing and the main reasons for the exclusion from co-processing (GTZ-Holcim, 2006) Enrichment Emission of values OH & S Potential pollutants in Landfilling Negative for as better impact recycling option the clinker kiln operation Electronic waste X X X Entire Batteries X X X X Infectious & biol. active medical X waste Mineral acids and X corrosives Explosives X Asbestos X X X X Radioactive waste Unsorted municipal waste 5.8.2 X X X X X X X X The Swiss Agency for the Environment, Forests and Landscape (1998) The Swiss Agency for the Environment, Forests and Landscape issued in 1998 “Guidelines for disposal of wastes in cement kilns”. The Guidelines acknowledge that both the raw materials and the fossil fuels (mainly hard coal and heavy oil) may be substituted in part by waste of suitable composition and that this is desirable in terms of conservation of resources. The Guidelines states “It must, however, be guaranteed that waste is valorised or disposed of in cement plants in an ecologically sound way. The quality of the clinker and Kåre Helge Karstensen [email protected] on Page 100 of 420 cement products must be maintained both in terms of material composition and in their use as building materials, and they must not be misused as a sink for heavy metals. The heavy metals should be concentrated and recycled as far as possible by suitable technical means. The use of waste in cement plants must also not lead to significantly higher emission of pollutants in the flue gases. It is therefore necessary to specify quality requirements for the waste employed, and in certain cases, to restrict the use of waste”. The Guidelines refer to technical and scientific principles, ecological objectives and specific proposals for the requirements for disposal of waste in cement plants. The criteria selected are based on the concept of least total impact on the ecosystem combined with optimum deployment of resources reconciling the demands of holistic environmental protection, waste and resource policy, waste economy and the CO2 problem. The positive list (list of permitted waste), is tailored to the waste situation in Switzerland with its 28 municipal waste and 5 special waste incineration plants, and also contains exceptions for specific categories of waste. The resulting requirements are intended to be simple and easy to use, to optimize the disposal of waste in cement plants in the overall interest of ecology (as far as we understand it today). The basic principles and requirements are the following: Waste may be disposed of in cement plants provided this: is ecologically more advantageous that any other form of disposal and is in accord with the waste planning of the Confederation and the cantons and is not in competition with more ecological deployment of resources The requirements are: Disposal in cement plants must fulfill the re-use objective, i.e. substitution of the required fuels and materials (basic materials, grinding additives and process materials). Unavoidable dilution of extraneous substances to the cement production process must be minimized. Kåre Helge Karstensen [email protected] Page 101 of 420 The process must provide an overall solution for the relevant waste, i.e. no subsequent disposal problem should arise for the community as a whole. 5.8.3 The Stockholm Convention The Stockholm Convention expert group on BAT/BEP - Cement Kilns firing Hazardous Waste, submitted February 2006 to the Stockholm Secretariat and recommended the following on input control: • Consistent long-term supply of alternative fuels (supplies of a month or more) is required to maintain stable conditions during operation; • Careful selection and control of substances (sulphur, nitrogen, chlorine, metals and volatile organic compounds); entering the kiln • Continuous supply of fossil fuel and alternative fuel with specification of heavy metals, chlorine (limitation, product/process dependent), sulphur; • Feeding of waste through the main burner or the secondary burner in precalciner/preheater kilns (ensure temperature > 900o C); • No waste feed as part of raw mix, if it includes organics; • No waste feed during start-up and shutdown. 5.9 Test burn Kåre Helge Karstensen [email protected] Page 102 of 420 In the United States cement kilns co-processing hazardous wastes must also perform a test burn to demonstrate the combustion performance on selected hazardous wastes to demonstrate the DRE for POHCs in the waste stream (Federal Register, 1999). POHCs are hazardous organic substances in the waste feed that are representative of those constituents most difficult to burn and most abundant in the waste (Taylor et al., 1990). A destruction and removal efficiency of 100% will never be possible to establish or demonstrate due to limitations in the analytical instruments. A test burn is usually designed to determine how effectively a kiln is able to operate under specifiable ”worst cases” and constitutes the foundation in the decision making process (Burton, 1989; Gorman et al., 1986; Newman, 1994). The test burn must fulfil three major requirements regarding combustion performance, whereas the DRE is the most important: POHCs must be destroyed and/or removed to efficiency (DRE) of 99.99% or better; PCDD/F’s and PCB’s wastes must achieve a DRE of 99.9999%. The remaining two requirements are dealing with emissions of particulates (approximately 70 mg/m3) and gaseous hydrogen chloride (approximately 90 mg/m3), which in most cases are easily achievable for most kilns (Federal Register, 1999). The operating conditions selected for the test burn should represent the worst case conditions under which the kiln may expect to operate. These conditions establish the outer limits on where the kiln should be permitted to operate. The conditions selected typically include the following: • Waste containing hardest-to-burn POHC; • Highest concentrations of all POHCs selected; • Maximum combustion airflow rate (minimum residence time); • Maximum carbon monoxide (CO) level in by-pass stack gas, main stack is not regulated (Lee et al., 2000). • Minimum combustion temperature; • Minimum O2 level in stack gas; • Maximum Cl content of waste feed; Kåre Helge Karstensen [email protected] Page 103 of 420 • Maximum ash content of waste feed; • Minimums or maximums on other relevant operating conditions. It is usually recommended to carry out three replicate runs on any set of operating conditions and waste feed characteristics. However, it may be acceptable to make these runs with each done at different conditions. The regulatory agency must approve the test burn plan, which in turn must state the number of runs under different conditions, the times required, the amount of waste feed needed, etc. Since each of these runs may require 8 hours to complete, adequate quantities of feed material for repeated tests must be available. Test burns have failed to demonstrate a satisfactory DRE due to low concentration of hazardous components in the waste feeds or not enough waste (Burton, 1989). The US permitting of hazardous waste combustion facilities has historically been a very complicated and timeconsuming, it could take years to obtain a permit (Lee et al., 2000). Kåre Helge Karstensen [email protected] Page 104 of 420 6. Co-processing of hazardous wastes – fate of contaminants Cement kilns have utilised hazardous wastes for energy replacement since the early 1970s. However, such practice imposes strict permit requirements. In Europe, cement kilns utilising hazardous wastes as co fuel must comply with the emission limit values laid down in the Council Directive 2000/76/EC on the Incineration of Waste. Industrial facilities and cement kilns in the US combusting hazardous wastes must comply with emission limit values laid down in the National Emission Standards for Hazardous Air Pollutants (Federal Register, 1999). In addition, they have to perform a Test Burn to demonstrate the incinerator performance on selected Principal Organic Hazardous Constituents (POHC). The rule requires that new and existing facilities demonstrate 99.99 % Destruction and Removal Efficiency (DRE) for POHC in the waste stream. Achieving this level of DRE "will ensure that constituents in the waste are not emitted at levels that could pose significant risk". On the other hand, a destruction and removal efficiency of 100 % will never be possible to establish or demonstrate due to detection limits in the analytical instruments. This means that a demonstrated DRE of 99.99 % can be higher in reality. The principal organic hazardous constituents should be representative of the compounds in the waste stream that are the most abundant and the most difficult to destroy. Accordingly, chlorinated and aromatic compounds are often chosen because they are difficult compounds to destroy. 6.1.1 Fate of the constituents in the hazardous waste fuel The hazardous waste used as a fuel by the cement industry consists mainly of organic material, but may also contain trace amounts of metal components. To determine whether or not a cement kiln can burn hazardous waste fuel effectively, the fate of the organic constituents has to be determined. In other words, what happens to the components in the combustion process? Kåre Helge Karstensen [email protected] Page 105 of 420 6.1.2 Organic constituents Complete combustion of an organic compound composed only of carbon and hydrogen produces carbon dioxide and water. If the organic compound contains chlorine, then hydrogen chloride or chlorine gas is also produced, depending on the combustion conditions. In addition, if organic compound contains nitrogen or sulfur, then oxides of these elements (e.g. NOx or SOx) are produced. An organic compound is considered to be destroyed if the products mentioned above are the only ones formed. If combustion conditions are not conductive to the complete destruction of the organic compounds, Products of Incomplete Combustion (PICs) can be emitted from the combustion device. One of the steps in determining whether a cement kiln can burn hazardous waste effectively is the demonstration of the destruction of the organic components. It should however be emphasised that waste should not be fed under kiln stops and start up or shut down. Testing of cement kiln emissions for the presence of organic chemicals during the burning of hazardous materials has been undertaken since the 1970s, when the practice of combusting wastes in cement kilns was first considered. Lauber (1987), Ahling (1979) and Benestad (1989) describe some of these early tests on US, Swedish and Norwegian kilns, which confirmed the ability of cement kilns to destroy the organic component of a waste feed. For example, the DRE for chemicals such as methylene chloride, carbon tetrachloride, trichlorobenzene, trichloroethane and PCBs has typically been measured at 99.995 % and better. Comprehensive emission studies have been performed when a conventional fuel such as coal was burned, and when hazardous waste was introduced, and these have generally concluded that no significant differences could be measured between usages of the two fuels. For example, Branscome et al. (1985) observed that ”no statistically significant increase in emission rates were observed when the waste fuel (as opposed to coal) was burned”. Early Kåre Helge Karstensen [email protected] Page 106 of 420 studies on dioxin emissions have also come to this conclusion (Branscome et al., 1985; Lauber, 1987; Garg, 1990). 6.2 Metals Although a metal compound is changed in the combustion process, a metal, like any element, is not destroyed in a combustion device. Accordingly, metals will be present in either the emissions, the CKD, or the clinker. The US BIF rule places limits on the concentration of 10 metals that can be emitted from the stack. In addition, the concentrations of 12 metals in the CKD are indirectly regulated by the BIF rule. The facility must prove that the concentrations of these metals in the CKD do not significantly change when burning hazardous waste or show that the concentrations of these metals that leach from the dust do not exceed the health-based limits set by the U.S. EPA. The BIF rule does not regulate the composition of the clinker produced from a cement production facility burning hazardous waste. However, the concentrations of metals in the clinker are limited because the quality of the cement cannot be adversely affected if the cement is to meet ASTM standards. Regardless of these regulations and requirements, determining the fate of the metal constituents is important. 6.2.1 General behavior of metals in the cement kiln Since lead was considered to be the major metal component in waste fuel that was also associated with adverse health effects, the earliest investigations focused on the fate of this metal. Branscome and Mournighan (1987) have reviewed the results of the early tests. The results from the St. Lawrence cement company in Canada represent the general trend. When waste oil containing a high concentration of lead, but a low halogen content, was burned in their dry process cement kiln, no increase in lead emissions was observed. The majority of the lead was retained in the clinker. However, when chlorinated wastes with a low lead content were burned in their wet process cement kiln, lead emissions increased. In this case the majority of the lead was retained in the CKD. Similar results from one dry process and Kåre Helge Karstensen [email protected] Page 107 of 420 two wet process cement kilns also reviewed by Branscome and Mournighan (1987) support this observation. These results indicate that lead emissions can increase when burning chlorinated solvents. In addition, the distribution of the lead shifts from the clinker to the CKD because of the formation of the more volatile lead chloride. The most significant observation, however, is that the majority of the lead is retained in the process solids (i.e. clinker or CKD). Branscome and Mournighan (1987) conclude that the cement kiln can retain at least 99% of the lead in the process solids, whereas a boiler burning waste oil will retain only 40 to 50% of the lead from the waste oil in the ash. The other 50 to 60% of the lead is emitted from the stack as opposed to the 1% emitted from a cement kiln stack. Other studies have focused on the metals that might be present in the raw materials or fuel involved in the cement production process. Sprung (1985) investigated the behavior of arsenic, cadmium, chromium, lead, nickel, thallium, and zinc. The majority of these metals fed into the kiln were retained in the process solids. Sprung’s (1985) investigation indicated that the distribution of a metal between the clinker and the CKD can depend on the quantity of the metal fed into the kiln, the chloride content, or the manufacturing process. For example, the distribution of zinc was relatively insensitive to both the production process and the chloride content, and was largely bound in the clinker. However, the distribution of lead in the process solids depended on both the manufacturing process and the chloride content. Arsenic, chromium, and nickel behaved like zinc; cadmium behaved like lead. Thallium was the most volatile of the metals investigated. Less than 5% of the thallium intake was bonded in the clinker. Because of the high volatility of this metal, Sprung (1985) recommended that its intake be strictly monitored. The most extensive study investigating the fate of metals in the cement kiln system was carried out by von Seebach and Tompkins (1991). Three dry process cement kilns equipped with precalciners, two dry process cement kilns equipped with preheaters, and one wet process cement kiln were used in the investigation. Hazardous waste was burned in two of the kiln systems. The metals investigated were antimony, arsenic, barium, beryllium cadmium, chromium, lead nickel, selenium, silver, vanadium, and zinc. The concentration of metals fed into the kiln systems was varied by least 1 order of magnitude. The total input and output of the metals were analyzed to estimate the retention in the process solids versus the Kåre Helge Karstensen [email protected] Page 108 of 420 concentrations in the emissions. In all but one case, greater than 99% of the metals were retained in the process solids. Selenium was the exception. Its retention rate was greater than 95%. No difference in the emissions of these metals was noted when a portion of the coal was replaced by hazardous waste fuel. Although the emission of the metals was generally less than 1% of the metals fed into the kiln, the authors suggest that the input of antimony, cadmium, lead, selenium, silver, and zinc be carefully monitored regardless of the fuel being burned. The fate of the more volatile metals (e.g. mercury and thallium) were examined by von Seebach and Tompkins (1991) under the test conditions described above. Variability between the kiln systems made the test results difficult to interpret. Regardless of this problem, the retention of thallium averaged 90% and the retention of mercury averaged 61%. Because of the lower retention of these metals within the process solids, the authors noted that the input of these metals into the kiln should be carefully monitored and recommended further investigation of the behavior of these metals. The studies discussed above focused on the fate of the metals fed into the cement kiln. The results indicate that the majority of the metals entering in with either the raw feed or fuel are retained in the process solids and that the emissions are not significantly different when a portion of the conventional fuel is replaced by hazardous waste. 6.2.2 Emissions Although the results of the studies discussed above indicate that metal emissions do not significantly change when burning hazardous waste fuel, metal emissions continue to be a major issue. Kåre Helge Karstensen [email protected] Page 109 of 420 Table 7 Comparison of metal emission (mg/sec) from cement kilns (Mantus, 1992) CKs burning conventional fuel Metal Antimony Arsenic Barium Avg. 0.685 0.991 10.7 Beryllium Std. Dev Min CKs burning hazardous waste fuel Max. Avg. 1.58 <0.0100 5.76 0.808 1.65 <0.0073 5.70 0.592 Std. Dev. 1.78 Min. Max. <0.0100 0.890 <0.00723 6 37.7 0.0354 5.08 2.80 166 19.9 47.3 .00218 144.7 6 0.108 0.0438 <0.0005 <0.369 00 0.110 <0.00049 0.0452 9 <0.32 6 Cadmium 0.344 0.376 <0.0220 1.29 0.309 0.317 <0.0218 1.34 Chromiu 20.6 58.5 <0.0100 264 12.5 52.4 <0.0100 299.1 1.95 2.37 0.527 12.0 5.83 10.4 0.0210 50.8 0.984 2.39 0.537 10.7 2.14 2.96 0.132 m Lead Mercury 9.84 Nickel 17.3 40.1 Selenium <0.0663 138 11.0 <0.0073 0.0719 0.0678 6 34.5 0.0696 171.4 0.00029 <0.19 0.0648 0.260 0.0455 5 Silver 0.555 1.04 <0.0220 3.96 0.886 2.26 <0.0217 7.94 Thallium 1.40 1.95 <0.0073 5.77 0.806 1.78 <0.00723 6 Vanadium 0.338 0.221 <0.0886 5.08 <0.620 0.359 0.245 <0.0868 0.62 Zinc 2.97 2.51 0.334 7.80 Kåre Helge Karstensen [email protected] 1.53 1.58 0.147 6.48 Page 110 of 420 The raw data used to compile the summary table were evaluated to determine statistically significant differences in the metal emissions (Springborn, 1991). The statistical model attempted to minimize the variation between kilns due to differences in engineering or testing methods. As a result, the model identified those differences in metal emissions due only to replacement of conventional fuel with hazardous waste fuel. One final note on the evaluation of these data concerns values reported at less than the detection limit. When a facility indicated that the result was less than the detection limit, the detection limit was used in the generation of the summary table and in the evaluation of the data for statistical significance. This method ensured that the most environmentally conservative result was achieved. The results of the statistical analysis indicate that for the majority of metals no statistically significant differences exist in the emissions from cement kilns burning hazardous waste as opposed to those burning only conventional fuel. The two exceptions are lead and mercury, which appear to exhibit statistically significant higher emissions from cement kilns using hazardous waste fuel. Although statistically significant differences in the lead and mercury emissions were noted, the average emissions for these two metals indicate that the differences are less than an order of magnitude. These differences are not substantial in terms of potential for adverse health effects. The statistical analysis also suggested that selenium emissions from cement kilns burning hazardous waste fuel are significantly lower than those from kilns burning only conventional fuel. The lack of a significant difference for a majority of the metal emissions might be surprising in light of the results of a trial burn conducted in 1983 at a wet process cement kiln, in which emissions of cadmium, copper, lead, mercury and selenium were significantly higher when hazardous waste fuel (Bolstad et al., 1985). Although these emissions increased, the nickel emissions were found to significantly decrease when hazardous waste fuel was burned. These differences could be due to the quality of the hazardous waste burned in the early 1980s. In her review of results from trial burns conducted in Norway in 1983 and 1987 with a dry process cement kiln, Benestad (1989) noted that the concentrations of lead and cadmium decreased significantly in the typical waste fuel between 1983 and 1987. As a result of this decrease, significant differences in lead and cadmium emissions in the 1987 Norwegian tests Kåre Helge Karstensen [email protected] Page 111 of 420 were not observed when hazardous waste was burned. These results suggest that the hazardous waste fuel in the U.S. may have experienced the same trend. As more data are collected and compiled in the CRI database (Mantus, 1992), the results presented above could change. This assumption is supported by the fact that a preliminary statistical analysis of data initially compiled in the CRI database indicated that no significant differences existed in any metal emissions (Kelly and Pascoe, 1991). As more data are collected and compiled from compliance burns, which present the worst-case scenarios with the highest metal inputs, additional significant differences in the emissions might be indicated. Table 8 Metal emissions comparisons a (Mantus, 1992) Metal CK/HWF b vs. CK/CF c Antimony No significant difference Arsenic No significant difference Barium No significant difference Beryllium No significant difference Cadmium No significant difference Chromium No significant difference Lead CK/HWF > CK/CF d Mercury CK/HWF > CK/CF d Nickel No significant difference Selenium No significant difference e Silver No significant difference Thallium No significant difference Vanadium No significant difference Zinc No significant difference a Conclusions based on a 95% confidence level (i.e., 95% confidence that the results were not obtained by random change). b CK/HWF = cement kiln burning hazardous waste fuel. c CK/CF = cement kiln burning only conventional fuel (e.g., coal) Kåre Helge Karstensen [email protected] Page 112 of 420 d CK/HWF > CK/CF = emissions from cement kiln burning hazardous waste greater than emissions from cement kiln burning only conventional fuel. e Statistical trends suggest CK/HWF > CK/CF. 6.3 Results from trial burns In the mid-1970s, a series of tests were conducted at the St. Lawrence cement plant in Canada to measure the destruction of various chlorinated waste streams being fed into their wet process cement kiln. The overall DRE established for the chlorinated compounds was greater than 99.986 %. This value was considered to be artificially low because the water used to slurry the raw feed was contaminated with low molecular weight chlorinated compounds (Mantus, 1992). In 1978, a series of tests was conducted at the Stora Vika Cement Plant in Sweden to evaluate the efficiency of their wet process cement kiln in destroying various chlorinated waste streams. Although chloroform was found in the stack gas, the majority of the chlorinated compounds were not detected. A DRE greater than 99.995 % was determined for methylene chloride and a DRE greater than 99.9998 % was demonstrated for trichloroethylene (Mantus, 1992). 6.3.1 Results from trial burns conducted in the 1980s Trial burns conducted in the 1980s continued to demonstrate that high DREs could be obtained for the organic constituents in the hazardous waste fuel burned in cement kilns. The results of trial burns of one wet and one dry process cement kiln illustrate the typical values obtained for DREs. The principle organic hazardous constituents selected for the trial burns were methylene chloride, 1,1,2-trichloro-1,2,2-trifluoroethane (Freon 113), methyl ethyl ketone, 1,1,1-trichloroethane and toluene. As summarized in the table below, the majority of the DREs were greater than 99.99 %. DREs less than 99.99 % resulted from either laboratory contamination problems or improper selection of the POHCs (Mantus, 1992). Kåre Helge Karstensen [email protected] Page 113 of 420 Table 9 Average DREs for a wet and a dry process cement kiln (Mantus, 1992) _________________________________________________________________ Selected POHCs Wet process kiln Methylene chloride Dry process kiln 99.983 % 99.96 % >99.999 % 99.999 % Methyl ethyl ketone 99.988 % 99.998 % 1,1,1-Trichloroethane 99.995 % >99.999 % Toluene 99.961 % 99.995 % Freon 113 6.3.2 Results from trial burns conducted in the 1990s Trial burns conducted in the 1990s have focused on the selection of compounds as POHCs that would not typically be present as contaminants or generated as PICs from the combustion of conventional fuel. Use of this criterion has resulted in more accurate DREs being obtained. In a DRE testing of a dry process cement kiln equipped with a preheater, carbon tetrachloride and trichlorobenzene were chosen as the POHCs. When fed to the burning zone of the kiln, DREs obtained were greater than 99.999 % for carbon tetrachloride and greater than 99.995 % for trichlorobenzene. To determine the limits of the system, DREs were also determined when these POHCs were fed to the kiln inlet (i.e. cool end) of the kiln along with tyres. DREs obtained were greater than 99.999 % for carbon tetrachloride and greater than 99.996 % for trichlorobenzene. DRE testing conducted at a cement kiln owned by United Cement supports the foregoing results. Sulfur hexafluoride was chosen as the POHC because of its thermal stability and ease of measurement in the stack gases. In addition, "contamination" problems and PIC interferences are unlikely with the use of this compound. DREs greater than 99.9998 % were obtained in every case. Kåre Helge Karstensen [email protected] Page 114 of 420 6.3.3 Results from newer trial burns In 1999 a test burn with pesticide contaminated soil fed into the kiln inlet was performed in a dry process kiln in Colombia. The test burn result showed a DRE of >99.9999 % for all the introduced pesticides. A test burn with two expired chlorinated insecticide compounds introduced at a rate of 2 tons per hour through the main burner was carried out in Vietnam in 2003. The DRE for the introduced insecticides was >99.99999 %. 6.3.4 Results from trial burns that focused on PCBs The results of trial burns involving PCBs provide additional support for the ability of a cement kiln to destroy the organic constituents in the hazardous waste fuel. Because of their useful characteristics, such as thermal stability, exceptional dielectric properties, and nonflammability, PCBs were once widely used but were banned by the U.S. Congress in 1976. At the same time, the TSCA, which regulated the disposal of PCBs, was passed. Incineration was recognized as the only acceptable method for the disposal of significant concentrations (i.e., greater than 500 ppm) of PCBs. A DRE of 99.9999 % is required by TSCA for the incineration of these compounds. The potential for using cement kilns to incinerate PCBs has been investigated in several countries. Since PCBs are such thermally stable compounds, the ability of a cement kiln to destroy these compounds indicates the overall ability to destroy organic constituents in hazardous wastes. The DREs determined from several trial burns conducted in many countries indicate that cement kilns are effective at destroying PCBs. However, the majority of cement kilns burning hazardous waste as fuel have chosen not to burn PCB wastes for the reasons of perception and possible bad publicity. Kåre Helge Karstensen [email protected] Page 115 of 420 6.3.5 Trial burns – a summary Earlier data which indicated cement kiln DRE results below 99.99 % are most probably either from outdated sources or improperly designed tests, or both. In the early years of development of this concept and the sampling and analytical techniques to evaluate its environmental performance, there were several instances where POHCs were selected that did not meet the necessary criteria. For example, a major problem with many early tests was that the POHCs selected for DRE evaluation were organic species that are typically found at trace levels in the stack emissions from cement kilns that burn solely fossil fuel. While these PICs were emitted at very low levels, they nonetheless greatly interfered with the measurement of POHC destruction. Practitioners quickly learned that DRE could not be properly measured if POHCs used in testing were chemically the same or closely related to the type of PICs routinely emitted from raw materials. For that reason, early DRE test results (i.e., before 1990) should always be treated with caution. In some cases however, operational factors during the testing or sampling and analytical techniques contributed to the low DRE results. These typically were problems that occurred only in the earliest tests conducted during the developmental stages of this technology and should be possible to avoid today. Trial burn is a good way of demonstrating a kilns performance and ability to destroy wastes in an irreversible and sound way, but the design and the conditions of the trial is very crucial. Kåre Helge Karstensen [email protected] Page 116 of 420 7. Formation, relase and control of PCDD/PCDFs The Stockholm Convention on Persistent Organic Pollutants (POPs) entered into force on 17 May 2004 and aims among others to prevent and minimise as much as possible formation and releases of unintentional POPs such as polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB). Four main source categories are listed in the Annex of the Stockholm Convention as “having the potential for comparatively high formation and release of these chemicals to the environment” (UNEP 2001). Cement kilns co-processing hazardous waste is one of these. 7.1 Formation of PCDD/PCDFs in thermal processes Most of the research done on PCDD/PCDF formation mechanisms in thermal processes is from municipal solid waste (MSW) incinerators. From these we know that PCDD/PCDFs can result from a combination of formation mechanisms, depending on kiln and process configuration, process and combustion conditions, feed characteristics, and type and operation of the APCD. Lustenhouwer et al. (1980) advanced three theories to explain the presence of PCDD/PCDFs. The theories may now be described as: 1. If there are PCDD/PCDFs in the fuel, waste or raw materials, trace amounts can survive and be emitted; 2. PCDD/PCDFs can be formed from gas-phase precursors which are chemically similar to PCDD/PCDFs, such as chloroaromatics, via: a. Homogeneous gas-gas phase reactions, or; b. Heterogeneous gas-solid phase condensation reactions between gas-phase precursors and a catalytic particle surface. Kåre Helge Karstensen [email protected] Page 117 of 420 3. De novo synthesis of PCDD/PCDFs from carbon sources that is chemically quite different from the PCDD/PCDF ring structures. De novo synthesis involves heterogeneous, surface-catalyzed reactions between carbonaceous particulate and an organic or inorganic chlorine donor. It is now generally accepted that Theory (1) cannot explain the levels of PCDD/PCDFs emissions which have been measured from MSW combustors. Most combustors units do not burn PCDD/PCDF contaminated wastes, and Schaub and Tsang (1983) noted that the gas-phase thermal destruction efficiency for PCDD/PCDFs is high at the flame temperatures typically achieved in normal combustion units. PCDD/PCDFs decompose rapidly at temperatures above 900 °C. Theory (2a) is also believed to play a relatively minor role in the PCDD/PCDF emissions from MSW combustion facilities. Kinetic models have suggested that the homogeneous gas-phase rate of formation could not account for observed yields of PCDD/PCDFs. At the high temperatures in a combustion zone, the multi-step process necessary for PCDD/PCDF formation cannot compete with destruction. Although Sidhu et al. (1994) and others have subsequently demonstrated pure gas-phase formation of PCDD/PCDF, the minor role of homogenous gas-phase formation is evidenced by numerous field measurements which show higher PCDD/PCDFs downstream of the combustion chamber than in the flue gases immediately exiting the combustion chamber (Gullett and Lemieux, 1994). PCDD/PCDF emissions from MSW combustion devices are now believed to result primarily from heterogeneous, surface-catalyzed reactions in the post-furnace cooler regions of the unit (Theories 2b and 3). Experimental evidence suggests that these reactions occur within a temperature range of approximately 200 °C to 450 °C or wider, with maximum formation occurring near 350 °C (Kilgroe et al., 1990). Theories (2b) and (3) are both characterized by heterogeneous, surface-catalyzed reactions. Theory (2b) can be distinguished from (3) by reactions involving gas-phase chloroaromatic precursors which might already be present in the fuel or feed, or which could be formed as products of incomplete combustion (Dickson and Karasek, 1987; Karasek and Dickson, 1987; Dickson et al., 1992). Theory (3) does not require that chloroaromatic precursors are present on fly ash Kåre Helge Karstensen [email protected] Page 118 of 420 or dust particles or in the gas stream. Instead, both the chloroaromatic precursors and the PCDD/PCDFs may be synthesized de novo from gas-solid and solid-solid reactions between carbon particulates, products of incomplete combustion (PICs) or organics volatilised from the raw material, with the presence of a catalyst, air, moisture and (inorganic) chlorides (Stieglitz et al., 1989a and 1989b). Studies performed to quantitatively determine the relative predominance of the two heterogeneous formation pathways have shown that yields of PCDDs from the precursor compound pentachlorophenol were 72-99,000 times greater than yields formed from reactions of activated charcoal, air, inorganic chloride and divalent copper catalyst under identical reaction conditions (Altwicker et al., 1994; Gullett and Lemieux, 1994). Dickson et al. (1992) postulated that “fast reactions involving chloro-aromatic precursors may be expected to predominate in the post-combustion and heat exchanger sections of a MSW combustor, where the temperatures range from 600 °C to 250 °C and the residence time of the gas stream and entrained particulates is on the order if 1 second”, and “slower processes such as de novo synthesis may influence PCDD/PCDF emissions in dry pollution control equipment, where particulate residence times vary from 1 to about 1000 seconds.” From the previous it can be deducted that the possibilities for formation of PCDD/PCDF in cement kilns will be restricted to the “cooler” cyclone preheater zone and the post-preheater zone, comprising the cooler, mill dryer and APCD (figure 4) (Karstensen, 2007). 7.2 Factors influencing formation of PCDD/PCDFs in cement production For the convenience of discussion, it's practical to divide a preheater kiln process in three thermal zones; the high temperature rotary kiln zone, the cyclone preheater zone and the post-preheater zone. The high temperature rotary kiln zone includes the burning or sintering zone were the combustion gases from the main burner remain at a temperature above 1200 °C for 5-10 seconds, with peak gas phase temperatures up to 2000 oC. In the cyclone preheater zone, at Kåre Helge Karstensen [email protected] Page 119 of 420 the upper end of the kiln where the raw meal is added, the gas temperatures typically range from approximately 850 °C to 250 oC and can have a retention time up to 25 seconds. In this area, moisture is evaporated and the raw material is partly calcined. In modern kilns, a second precalciner burner is installed between the kiln and the preheater. The post-preheater zone constitutes the cooler, the mill dryer and the air pollution control device, with gas temperatures typically in the range from approximately 250 oC to 90 °C from the top of the preheater to the exit stack outlet. The retention time of the kiln material charge in the rotary kiln is 20-30 and up to 60 minutes depending on the length of the kiln. While the temperature profiles may be different for the various kiln types, the peak gas and material temperatures are valid for any case. Figure 8 Rotary kiln with cyclone preheater and gas dust collection. The frames define three distinct thermal zones (Karstensen, 2007). 7.3 Products of incomplete combustion - from the fuel Kåre Helge Karstensen [email protected] Page 120 of 420 Organic emissions from cement kilns can have three potential sources: they can be related to the fuels, including wastes, the raw material or they can be formed as new compounds via reactions in the preheater, i.e. they are products of incomplete combustion (PICs). Fuels are fed finely milled to burners and exposed to the gas phase temperatures up to 2000 °C and 850-1200 °C in the primary and the precalciner burner respectively. Combustion theory suggests that cement kilns provide sufficient reaction time, oxygen concentration, and high temperatures to destroy all the organic present in the fuel and waste fuel feed and efficient burnout of the organic components should therefore result in limited carryover of PICs to the cyclone preheater zone and the post-preheater zone, potential precursors to PCDD/PCDF (Eduljee and Cains, 1996; Eduljee, 1998). This was to some extent confirmed by Waltisberg (2001) who measured volatile organic carbons (VOC) and benzene at the kiln inlet in a preheater kiln to investigate if organic materials from the fossil fuel could survive the main flame temperature; all the measurements were however below the detection limit. Suderman and Nisbet (1992) investigated emissions with and without fuel substitution and concluded that there is "no significant difference in stack emissions when 20-40% of the conventional fuel is replaced by liquid wastes", implying complete destruction of the fuels. An improper mixing of fuel and oxygen can potentially result in poor combustion and thus leads to emissions, especially from the precalciner were the residence time and temperature is less than in the main burner. 7.3.1 Products of incomplete combustion - DRE of hazardous wastes Many studies have been measuring the DREs of hazardous wastes fed together with normal fuels. Already in 1975 Mac Donald et al. (1977) carried out test burns with hazardous chlorinated hydrocarbons containing up to 46% chlorine in a wet cement kiln in Canada and concluded that "all starting materials, including 50% PCBs, were completely destroyed to at least 99.98 percent efficiency in all cases" and emissions of high molecular weight chlorinated hydrocarbons were not detected. Similar tests with chlorinated and fluorinated hydrocarbons conducted in a wet kiln in Sweden showed that the destruction and removal efficiency of PCBs was better than 99.99998% and that there were no change in product quality or any influence on process conditions with a chlorine input up to 0.7% of the clinker production (Ahling, 1979). Also, "no TEQ PCDD/PCDF or furans could be detected". Kåre Helge Karstensen [email protected] Page 121 of 420 Viken and Waage (1980) carried out test burns in a wet kiln in Norway feeding 50 kg PCBs per hour, showing a DRE better than 99.9999% and no traces of PCB in clinker or dusts could be detected. Benestad (1989) carried out two studies in a dry preheater cement kiln in Norway and concluded that the "type of hazardous waste used as a co-fuel" does not influence the emissions and that the destruction of PCBs was better than 99.9999%. 3 "0.2 ng 3 PCDD/PCDFs N-TEQ/m and 0.1 ng PCDD/PCDFs N-TEQ/m were measured when feeding hydrocarbon waste (fatty acid esters, solvents and paint residues) and PCB-waste respectively". Thermal stable and refractory materials, such as carbon tetrachloride, perchloroethylene, chlorobenzenes, and sulphur hexafluoride have been used to demonstrate that cement kilns can achieve the best DREs when fed at the hot end of cement kilns and earlier data which indicated cement kiln DRE results below 99.99% for hazardous wastes are believed to be due to either outdated sources or improperly designed tests, or both (Chadbourne, 1997). 7.3.2 Products of incomplete combustion - formation in the preheater Measurements of organic emissions from a cement kiln burning hazardous waste have indicated that PICs may be formed in the preheater. Trenholm and Hlustick (1990) carried out detailed identification of organic emissions from a preheater/precalciner kiln with a bypass when feeding liquid wastes to the main burner and solid wastes spiked with monochloro-benzene (MCB) to the kiln inlet. Organic concentration in the by-pass, which is a duct at the kiln inlet, was generally much lower than in the main stack, reflecting the high temperature conditions and destruction ability in the kiln. Organic emissions in the main stack were believed to be related to organic material in the raw meal (raw material mix) and/or the coal combustion in the precalciner forming PICs. And they found a strong correlation between MCB and the chlorine concentration; the MCB concentration increased with increasing input of chlorine when benzene was present. That MCB can be formed in the preheater was confirmed in another study, where tests on the preheater stack measured a greater quantity of MCB coming out than introduced into the preheater (Lamb et al., 1994). Also, a strong correlation between the emissions of MCB Kåre Helge Karstensen [email protected] Page 122 of 420 and the input chlorine was observed experimentally, concluding that MCB was formed in the preheater as a result of surface catalysed chlorination of organic compounds. Eduljee (1998) postulated that both chlorobenzenes and chlorophenols can be formed as PICs within the preheater, but as cement kilns tend to operate at lower oxygen concentrations compared to MSW incinerators, chlorobenzenes may be formed in preference to chlorophenols. The difference in PCDD profiles between cement kiln emissions and MSW incinerator emissions suggests that different reaction pathways are dominant in the two types of plant, perhaps as a result of different types or differences in the relative quantities of precursors formed. A reaction pathway dominated by chlorobenzenes would tend to favour the higher chlorinated congeners of PCDDs at the expense of the lower chlorinated congeners, and hence lower the I-TEQ value of the emission sample relative to a reaction in which chlorophenols dominated (Eduljee, 1998). Abad et al. (2004) found however that the major contribution to total TEQ came from the lower chlorinated congeners of PCDFs, especially 2,3,7,8-tetrachlorodibenzofuran and 2,3,4,7,8-pentachlorodi-benzofuran. Altwicker et al. (1994) studied the effect of dichloro- and tetrachlorobenzene (TCB) on de novo reactions on fly-ash surfaces at a temperature of 300 oC and found that high levels of dichlorobenzene (DCB) inhibited the formation of PCDD: an overall 22% reduction of yield for PCDDs and 53% reduction for PCDFs was evident when 1,2-DCB was passed over fly-ash at concentrations of 10-100 mg/m3, while for 1,4-DCB the percentage reductions were over 80% compared to the yield from the de novo reaction, i.e. when DCB was not present. However, when 1,2,4,5-TCB was present in the reaction, the yield of hexa, hepta and octachloro-CDDs increased dramatically by over 100%, while reductions in yields were still evident for the remaining PCDDs and all the PCDFs relative to the de novo yields. The increase in yield for the higher chlorinated PCDDs was due to the conversion of 1,2,4,5-TCB within the reaction to a tetrachlorophenol, a more potent precursor for the higher PCDDs than the chlorobenzenes. 7.4 Feeding of hazardous wastes Kåre Helge Karstensen [email protected] Page 123 of 420 Krogbeumker (1994) compared the emissions with the burning of coal only and the use of substitute fuels like tyres, refuse derived fuel and solvents with varying amounts of chlorine. The tests resulted in an increase in PCDD/PCDF emissions, from a low base of 0.002-0.006 ng TEQ/m3 to 0.05 ng I-TEQ/m3 for solvents, and to 0.08 ng I-TEQ/m3 in the case of used tyres. PCDD/PCDF emissions data are available for most hazardous waste burning cement kilns in the US. The US EPA has during the last 25 years published extensive sets of data from testing of cement kilns; approximately 750 measurements can be found in various databases (Federal Register, 1999, 2000, 2002a and 2002b). The results range from 0.004 to approximately 50 ng TEQ/m3 and are highly variable among different kilns and in some multiple tests on a single kiln; the US EPA states that the confidence to many of the results is low (Chadbourne, 1997; EPA, 2000; HWC MACT Data Base NODA Documents, 2002). Emissions testing of US cement kilns in the 1980s and 1990s often showed that cement kilns co-processing hazardous waste as a co-fuel had much higher PCDD/PCDF emissions than kilns co-processing non-hazardous wastes or using fossil fuel only. One reason for this difference can be attributed to the fact that cement kilns burning hazardous waste were normally tested under “worst” scenario test burn conditions to identify the outer control limits, while cement kilns burning non-hazardous waste or fossil fuel only were tested under normal operating conditions, no “worst” scenario conditions, making a comparison difficult. Worst case conditions often implied testing with high temperature in the APCD, conditions known today to increase the risk for higher emissions of PCDD/PCDF. Another reason is that the dominating technology at that time was long wet and long dry kilns, often without exit gas coolers. The Thai Pollution Control Department and UNEP carried out a joint emission inventory of Thai industry and among the facilities selected for sampling was a dry process cement plant with two kilns, with and without co-processing of liquid hazardous waste and/or tyres (UNEP/IOMC, 2001). PCDD/PCDF measurements were performed at both kilns under normal operation at full load when fuelled with a blend of lignite and petroleum coke as primary and secondary fuel, and with waste tyres or liquid hazardous waste (waste oils and contaminated solvents) to replace a certain percentage of the secondary fuel at the precalciner. The concentrations measured were all below 0.02 ng I-TEQ/m3 and as low as 0.0001 ng IKåre Helge Karstensen [email protected] Page 124 of 420 TEQ/m3; the means were 0.0105 ng I-TEQ/m3 and 0.0008 ng I-TEQ/m3 for the normal operation conditions and 0.003 ng I-TEQ/m3 and 0.0002 ng I-TEQ/m3 for the test performed with substitute fuels. The report concluded that “2,3,7,8-Cl4DD was not detected in any of the samples and results clearly revealed that the addition of tyres and/or liquid hazardous waste had no effect on the emission results". A Heidelberg Cement kiln in the South of Norway (3500 ton clinker/day) has been fired with a mix of coal, liquid and solid hazardous wastes, refuses derived fuel, petcoke and used oil, accounting for approximately 40% of the heat input, for the last 15 years (Haegermann, 2004). Annual PCDD/PCDF measurements have been performed since 1992 and the concentration has varied between 0.025 and 0.13 ng N-TEQ/m3 at 11% O2. Studies have not been able to establish any influences on the PCDD/PCDF emissions. The difference between the Nordic Toxicity Equivalency Factor N-TEF and the International I-TEF is negligible as the two schemes differ only in a single congener; the N-TEF scheme gives 1,2,3,7,8-Cl5DF a TEF of 0.01 whereas the I-TEF a value of 0.05. Holcim Colombia (Herrera, 2003) carried out a test burn with 900 tons of POPs contaminated soil (DDT, aldrin, dieldrin and pentachlorbenzene) fed to the kiln inlet of a 58 meter long five stage preheater kiln with a clinker production capacity of 3350 ton per day (fired with bituminous coal). The three PCDD/PCDF measurements performed during the test burn, including one blank measurement under normal operation ranged between 0.00023 0.0031 ng I-TEQ/Nm3 at 11% O2 and showed no influence of the POPs feeding. A test burn with used industrial solvents was carried out in Egypt (Farag, 2003). A baseline test was carried out before and after the test burn and all three results showed a PCDD/PCDF concentration less than 0.001 ng TEQ/m3. A test burn with and without a mix of two expired toxic chlorinated and fluorinated insecticide compounds (Fenobucarb and Fipronil) introduced at a rate of 2 tons per hour through the main burner was carried out in a preheater/precalciner cement kiln in Vietnam (Karstensen et al., 2006). The test burn showed destruction efficiency better than 99.999997% and 99.999985% for Fenobucarb and Fipronil respectively and the PCDD/PCDF results for both days were below the detection limit for all the 17 TEQ congeners. HCB was measured to be below the detection limit, <31 ng/m3 and <35 ng/m3 for the baseline and the Kåre Helge Karstensen [email protected] Page 125 of 420 test burn respectively. All the non-ortho and mono-ortho PCB congeners were also below the detection limit for the two day test. 7.5 Feeding of non-hazardous wastes Kuhlmann et al. (1996) carried out approximately 160 emission measurements at German cement kilns in the period 1989–1996 and covered 16 different dry preheater kilns, i.e. suspension preheater kilns and Lepol kilns, all equipped with electrostatic precipitators. Gas temperatures in the ESP typically ranged from 95 oC to 205 oC (suspension preheater kiln) and 120 oC to 150 oC (Lepol kilns). Secondary fuels such as used oil, bleaching earth, used car tyres or waste-derived fuels were used in some kilns and secondary raw material substitutes like e.g. fly ash, or contaminated sand were used as corrective ingredients in some kilns. The average concentration was about 0.02 ng I-TEQ/m3 at 11% O2. No significant difference in emissions from the type of fuel being used or any temperature correlation with the PCDD/PCDF concentration in stack could be established. Examinations also showed that the oxygen content as well as the dust concentration in stack did not correlate with the reported emission concentrations. The general level of substitution of fossil fuel and raw materials with AFR increased in German cement kilns from 23% in 1999 to nearly 35% in 2002 but no effects have been observed on the PCDD/PCDF emissions. In another study, 106 PCDD/PCDF measurements of 37 kilns showed that all values were below 0.065 ng ITEQ/m3 (11% O2), and in seven cases no PCDD/PCDF was detected (VDZ, 2002). Environment Australia (2002) have measured a range of Australian cement plants representing different operating and process conditions, different fuel sources and different raw materials. Both wet and dry process kilns have been investigated, as plants using gas and coal as primary fuels sources as well as plants using waste-derived fuels. No significant difference in PCDD/PCDF emissions due to use of waste derived fuels have been observed within plants. Results of repeated measurements over a decade showed that levels of PCDD/PCDF emissions from Australian cement manufacturing have consistently been below 0.1 ng I-TEQ/m3. 55 measurements showed the range 0.001-0.07 ng I-TEQ/m3, with subsequent emissions factors covering the range 0.0032-0.216 μg I-TEQ/t cement. Kåre Helge Karstensen [email protected] Page 126 of 420 The Japanese cement industry utilise a broad range of alternative fuels and raw materials (AFR) in their cement production and approximately 78 million tons of clinker was produced in 62 dry suspension preheater kilns in Japan in 2003. 54 measurements performed in 2000 showed that all kilns were below 0.0941 ng TEQ/m3; 53 measurements performed in 2001 showed that all kilns were below 0.126 ng TEQ/m3 and 57 measurements performed in 2002 showed that all kilns were below 0.096 ng I-TEQ/m3; all measurements corrected to 11% O2 (Japan Ministry of Environment, 2003). In the first phase of the Spanish PCDD/PCDF inventory 20 cement kilns (18 dry and 2 wet processes) were measured for PCDD/PCDF emissions under normal operating conditions (Fabrellas et al., 2002). The mean emission value was 0.00695 ng I-TEQ/m3 and the mean emission factor 0.014464 µg I-TEQ/ton cement. In the period 2000-2003 samples from 41 kilns were collected, representing 69.5% of the industry and 40.2 million ton cement. 58 samples were taken when using conventional fuels and 31 when alternative fuels were used. No evidence of higher PCDD/PCDF emissions when using alternative fuels could be found (Fabrellas et al., 2004). Heidelberg Cement (Haegermann, 2004) made a comparison between kilns using a high substitution rate of alternative fuels and kilns using fossil fuel only. Nine plants with a substitution rate of minimum 40% showed an average value of 0.007 ng TEQ/m³ (minimum 0.001 TEQ/m³, maximum 0.016 ng TEQ/m³) while the average of eight kilns using fossil fuel only was 0.016 ng TEQ/m³ (minimum 0.002 TEQ/m³, maximum 0.031 ng TEQ/m³). Five measurements from two German preheater kilns feeding a mix of coal and plastics to the main burner and tyres to the kiln inlet showed concentrations from <0.0021 ng TEQ/m3 up to 0.0057 TEQ/m³ (Haegermann, 2004). Measurements from 5 European dry kilns using waste fuel (3 t/h) and/or tyres (1.7-3 t/h) done in 2003 varied between 0.001-0.062, with an average of 0.011 ng I-TEQ/m3 at 10% O2. The subsequent emission factors varied between 0.0020.025 μg TEQ/t clinker (Haegermann, 2004). The effect of increasing the total thermal substitution rates with different alternative fuel and raw materials on the emissions of PCDD/PCDF, PCB and HCB was investigated in one suspension preheater/precalciner kiln by Holcim (Lang, 2004). The total thermal substitution rate increased from 23% in 1997 up to 60% in 2003 and covered solvents, animal meal, bleaching earth, rubber, waste oil, paper and film plastics, fly ash and waste wood; the Kåre Helge Karstensen [email protected] Page 127 of 420 thermal substitution rate to the precalciner increased in the same period from approximately 14% up to near 50% and the thermal substitution rate to the main burner remained more or less stable around 10%. All measurements (N=8) were unaffected by the increased substitution and showed that all PCDD/PCDF measurements were <0.004 ng I-TEQ/m3, PCB <4 µg/m3 and HCB <4 ng/m3. Holcim Chile (Jensen, 2004) reported two measurements of a kiln fed with 25% Petcoke and 75% coal showing a concentration of 0.0059 and 0.0194 ng I-TEQ/m3; one measurement was done with coal only, showing 0.0100 ng I-TEQ/m3 at, and two measurements done when introducing liquid alternative fuel: one with 20% liquid alternative fuel, 6% tyres, 18.5% petcoke and 55.5% coal showed a PCDD/PCDF concentration of 0.0036 ng I-TEQ/m3; another test with 12% liquid alternative fuel and 88% coal showed a PCDD/PCDF concentration of 0.0030 ng I-TEQ/m3; all corrected to 10% O2. Five dry preheater cement kilns were measured for PCDD/PCDF in the Philippines showing a concentration of 0.0073, 0.0093, 0.0059, 0.013 and 0.011 ng I-TEQ/m3 at 11% O2 (Lang, 2004). A test burn with 1200 tons out-of-spec dog food containing 1.28% of chlorine was carried out in a 5500 ton clinker/day preheater/precalciner kiln (80 m long and 5 m diameter) in the Philippines in 2004. Three test runs were performed with sampling of PCDD/PCDFs; one with coal only, one with 1750 kg/h and one with 3500 kg/h dog food fed to the precalciner. All runs were performed in compound mode and showed a concentration of 0.00038, 0.0012 and 0.0013 ng I-TEQ/m3 at 10% O2 respectively (Schimpf, 2005). Abad et al. (2004) investigated the influence of feeding waste materials to three Spanish dry preheater/precalciner kilns. The alternative fuels were fed to the preheater/precalciner at a rate of 4.8-14% of the heat input and consisted of meat meal and used tyres. The emission of PCDD/PCDFs ranged from 0.001 to 0.042 ng I-TEQ/m3 and the authors concluded that the levels were similar to those emitted during the use of conventional fuel. Capmas (2003) did 40 PCDD/PCDF measurements from cement plants using meat meal as a secondary fuel in France and compared with measurements from 22 plants using fossil fuel only; no differences could be established. Conesa et al. (2006) investigated the emissions of acids, gases, heavy metals, PCDD/PCDF, PAHs and VOCs when feeding Kåre Helge Karstensen [email protected] Page 128 of 420 various amounts of sewage sludge and tyres. The authors could not identify any influence of any of the emissions, which were all in compliance with European and Spanish regulation. Lafarge investigated the effect on PCDD/PCDF emissions of feeding different alternative fuels to the kiln inlet/precalciner (table 1); feeding rates were not available (Reiterer, 2004). Table 10 Feeding of alternative fuels to the kiln inlet/precalciner in Lafarge kilns and influence on PCDD/PCDF emissions (single or mean value) (Karstensen, 2007). Type of alternative fuel ng I-TEQ/m3 N Animal meal, plastics and textile 0.0025 4 Animal meal and impregnated saw dust 0.0033 4 Coal, plastic and tyres 0.0021 & 0.0041 2 Tyres 0.002 & 0.006 2 Petcoke, plastic and waste oil 0.001 1 Petcoke, sunflower shells and waste oil 0.012 1 Tyre chips 0.004 & 0.021 2 Solvents 0.07 1 Impregnated saw dust and solvents 0.00003 & 0.00145 2 Solvents 0.00029 & 0.00057 2 Sludge’s <0.011 1 Car waste 0.0036 & 0.07 & 0.0032 3 The European Cement Association reported 230 PCDD/PCDF measurements from 110 cement kilns and 11 countries in 2003 (van Loo, 2004). The countries covered by the survey were Belgium, Czech Republic, Denmark, France, Germany, Hungary, Italy, Norway, Spain, the Netherlands and United Kingdom; most countries practise co-processing of wastes. The measurements showed that the average concentration was 0.017 ng I-TEQ/m3 for all measurements. The lowest and highest concentration measured was <0.001 and 0.163 ng ITEQ/m3 respectively. The concentration distribution show that 98% of the 230 kilns have an Kåre Helge Karstensen [email protected] Page 129 of 420 exit gas concentration below 0.1 ng TEQ/m3 and that the majority of the kilns emit concentrations lower than 0.01 ng TEQ/m3. 0,18 ng TEQ/Nm3, 10%O2 0,16 0,14 0,12 0,1 0,08 0,06 0,04 0,02 0 0 Figure 9 15 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 Measurements 230 measurements in 110 kilns and 11 European countries (Karstensen, 2007). 160 140 142 # < detection limit 120 100 # measurements within the range 80 60 40 23 20 17 11 6 8 6 3 0 2 5 0 0,000,01 0,010,02 0,020,03 0,030,04 0,040,05 0,050,06 0,060,07 0,070,08 0,080,09 0,09- > 0,10 0,10 ng TEQ/Nm3 at 10% O2 Figure 10 Concentration distributions of 230 measurements (Karstensen, 2007). Eight international cement companies reported more than 500 recent PCDD/PCDF measurements representing a large number of countries, a production of more than 300 million tons of clinker, most production technologies and the use of wide variety of AFR. Kåre Helge Karstensen [email protected] Page 130 of 420 The concentration distribution showed that approximately 98% of the measurements are below 0.1 ng TEQ/m3. Table 11 Cement company emission measurements of PCDD/PCDF ng I-TEQ/m3 (Karstensen, 2007) Cement company N Concentration range Reference (average) Cemex 1999-2003 16 0.00049–0.024 Heidelberg 2001- >170 0.0003–0.44 2004 Quiroga, 2004. Haegermann, 2004. (0.020) Holcim 2001 71 0.0001–0.2395 Lang, 2004. (0.041) Holcim 2002 82 0.0001–0.292 Lang, 2004. (0.030) Holcim 2003 91 0.0003–0.169 Lang, 2004. (0.025) Lafarge 1996-2003 64 0.003–0.231 Reiterer, 2004. (0.0207) RMC 2000-2004 13 0.0014–0.0688 Evans, 2004. Siam 2003 4 0.0006–0.022 Siam Cement, 2004. Taiheiyo 67 0.011 Uniland 2 0.002–0.006 Taiheiyo, 2003. Latorre, 2004. Cimpor reported 14 PCDD/PCDF measurements done in Portugal, Spain and South Africa in the period from 1997–2003 (Leitao, 2004). Kåre Helge Karstensen [email protected] Page 131 of 420 Table 12 PCDD/PCDF measurements in Cimpor kilns (Karstensen, 2007). Country Plant Kiln ng I-TEQ/m3 Production process / 10 % O 2 type of kiln Date 0,0008 Dry kiln; cyclone preheater Electr. precip. / bag filter 117 3 13.12.1997 0,0009 Dry kiln; separated SLC-D precalcinator Electr. precip. / bag filter 106 6 08.12.1997 0,0009 Dry kiln; cyclone preheater Electr. precip. / bag filter 122 0,0006 Dry kiln; separated RSP precalcinator Bag filter 110 Alhandra 7 South Africa 7.6 T (ºC) 16.07.2001 Portugal Spain Gas 2 Souselas Oural Air pollution control system 2 06.12.1997 31.05.2000 0,02 03.12.2002 0,0009 13.02.2003 0,00039 11.06.2003 0,039 26.11.2003 0,02 Toral de los Vados 5 07.03.2002 0,00078 Cordoba 1 06.06.2001 0,0243 Niebla 1 2001 0,006 Simuma 1 11.07.2002 0,00053 0,001 Dry kiln; in line precalcinator Electrostatic precipitator - Dry kiln; in line ILC-E precalcinator Dry kiln; cyclone preheater Semi-dry; Lepol preheater Dry kiln; cyclone preheater Electrostatic precipitator - Bag filter 90 Bag filter 117 Electrostatic precipitator 113 114 PCDD/PCDFs in solid materials One cement kiln study in the US concluded that ”naturally occurring PCDD/PCDF found in the raw materials constitute a majority of all the PCDD/PCDF emitted from the system” (Schreiber et al., 1995). Liske et al. (1996) confirmed the identification of PCDD/PCDFs in the raw material feed. Solid materials used and produced in the cement industry were also analysed for PCDD/PCDFs in this study. The main purpose was to confirm the possibility of having naturally occurring PCDD/PCDFs in the raw meal feed, but also to look into the general concentration levels of release through products and dusts. Dusts are as much as possible Kåre Helge Karstensen [email protected] Page 132 of 420 reintroduced back to the process, often together with the raw material feed, and can potentially represent a source of PCDD/PCDFs. The following varieties of dust are generated in the operation of a cement plant (Duda, 1985): 1. Raw material dust, i.e. dust from limestone, marl, clay, iron ore, slag, etc. 2. Raw mix dust 3. Coal dust 4. Exit dust from raw material dryers 5. Exit dust from kilns (cement kiln dust) 6. Clinker dust 7. Raw gypsum dust 8. Cement dust By-products such as slag, ashes or liquid residues from exit gas cleaning are not produced in cement production. With the exception of the cement kiln dust (CKD), the kinds of dust enumerated above, show the same chemical composition as the original material. The kiln exit dust represents a mixture of cement raw mix and clinker; the chemical composition of the exit dust is among other factors also influenced by the size of the particles carried away by the kiln gases. The exit dust shows a considerable concentration of alkalies volatilized in the burning zone and subsequently condensed on the kiln dust particles. If coal is used as fuel, then part of the coal ash is carried away by the kiln exit gases. About 60-65% of the coal ash is adsorbed by the clinker, whereas 35-40% of the ash appears in the exit gas. Different kiln types produce different particle size fractions; in modern suspension preheater kilns up to 95% of the dust produced will be less than 10 micron while the particle fraction between 10100 microns will be dominating in wet and long dry kilns. Dyke et al. (1997) estimated that approximately 30 kg of CKD are produced per ton of clinker in long kilns; but this will vary depending on plant specific factors. Since CKDs are valuable "cement" materials, are they recycled and reintroduced into the process to the highest degree possible. However, sometimes CKDs must be removed from the process due to high content of sodium and potassium (Riney and Yonley, 1994). A range of concentrations of PCDD/PCDFs has previously been reported in CKD; 0.001-30 ng TEQ/kg (Dyke et al., 1997) Kåre Helge Karstensen [email protected] Page 133 of 420 for UK kilns and 1-40 ng TEQ/kg for German kilns (UNEP, 2003). US EPA characterized a wide range of cement kiln dusts in a Report to Congress (CKD, 1995). The average TEQ concentration in the CKD from kilns burning hazardous waste was 35 ng I-TEQ/kg; these results were influenced by a high concentration in one sample (UNEP, 2005). For kilns that did not burn hazardous waste, the average concentration in the CKD was 0.03 ng I-TEQ/kg. 64 percent of the CKD was recycled directly back into the kiln or raw feed system in the US. US EPA could not find organics, volatile and semi-volatile compounds in the CKD and PCDD/PCDF could not be detected in any clinker samples (CKD, 1995). This was however not the case in this study - PCDD/PCDFs could be detected in all solid sample categories analysed. The kiln feed samples comprised raw meal, pellets and slurry; alternative raw materials comprised sand, chalk and different ashes. Samples of CKD, clinker and cement were also analysed, with CKD not surprisingly having the highest concentrations. Table 13 PCDD/PCDF in solid materials from the cement industry (Karstensen, 2007) Sample type N Average Highest Samples below concentration concentration detection limit ng I-TEQ/kg ng I-TEQ/kg Kiln raw material feed 11 1.4 7.1 1 Alternative 10 0.99 3.3 1 CKD 90 6.7 96 5 Clinker 57 1.24 13 7 Cement 49 0.91 6.9 7 raw material 7.7 Organics in the raw material (raw meal) Field studies conducted at full-scale kilns have shown that total organics/hydrocarbon emissions are not very sensitive to the changes in combustion conditions (Trenholm et al., 1990; Dellinger et al., 1993). It has also been shown that organics present in the raw Kåre Helge Karstensen [email protected] Page 134 of 420 materials (e.g., clay, shale, gypsum, etc.) are the major sources of organic emissions from cement kilns. These hydrocarbons are volatilized from the raw materials prior to entering the high temperature regions of the kiln (Dellinger et al., 1993; Schreiber and Strubberg, 1994). The chlorination of these organics is a potential source of PCDD/PCDF precursors, such as MCB. Bench-scale, as well as full-scale tests by the industry has confirmed that organics from raw materials play a significant role in governing the production of PCDD/PCDFs (Sidhu and Dellinger, 1997). Although the operating conditions necessary for achieving high total organics emissions may vary by facility, maximum volatile organic carbon levels are likely to be achieved by some combination of high production rate, high gas temperatures at the raw material feed end of the kiln, and low oxygen at the raw material feed end of the kiln. Dellinger et al. (1993) observed an inverse relationship between total hydrocarbons and stack oxygen concentrations and Schreiber and Strubberg (1994) observed that raw-material-generated hydrocarbons decrease as kiln oxygen increases. However, raw material characteristics, i.e. the organic content are largely dictated by quarry location and are not easily controlled. Heating of eight raw meal samples from different process points (before and after each cyclone, bag house, grinding mill, and silo) under inert helium atmosphere showed that most of the organics were desorbed between temperatures of 250-500 °C (Sidhu and Dellinger, 1995; Sidhu et al., 2001). To speciate these desorbed organics, cement kiln raw meal samples were desorbed under cement kiln preheater zone conditions (4% O2, temperature range of 30500°C) showing that cement kiln raw meal contains a wide range organics including benzene, toluene, naphthalene, alkanes, C14-C18 carboxylic acids, phthalates and their derivatives and natural products like cholesterol (Saiz-Jimenez, 1994; Schulten, 1995; Sidhu and Dellinger, 1995; Sidhu et al., 2001). Alcock et al. (1999) showed that TEQ concentrations in stack emissions of a cement kiln collected within a few hours of each other on the same day could, in some cases, be very different. For example, the first sample collected measured 4.2 ng and the second, collected 5 hours later, 0.05 ng I-TEQ/m3. During the time period stack gas was sampled the plant was running normally and spike recoveries of both samples were within the normal range. One possible explanation of this variability in emissions would be unevenly distribution of raw material organics. Kåre Helge Karstensen [email protected] Page 135 of 420 7.8 Chlorine The input of chlorine in cement production needs to be monitored and controlled carefully to be able to comply with standard product quality criteria and to avoid process related problems. The availability of chlorine doesn't seem to be a limiting factor, i.e. there will be enough chlorine in the raw materials or in the fossil fuels to form PCDD/PCDFs under unfavourable conditions (Bragg et al., 1991). Molecular chlorine (Cl2) plays a role in PCDD/PCDF formation by chlorinating aromatic precursors through substitution reactions. Chlorination of phenol has shown to be three orders of magnitude greater with Cl2 than with HCl (Gullett et al., 1990). Although HCl does not directly participate in precursor chlorination to a significant degree, it can produce molecular chlorine via the Deacon reaction (Griffin, 1986). The Deacon reaction depends on the presence of a catalyst, eventually elevated temperatures to overcome kinetic limitations which would otherwise limit the production of Cl2 from HCl. However, the catalyst also serves another important function - once the aromatic rings have been chlorinated, the metal catalyst supports condensation reactions to form the PCDD/PCDF dual ring structure (Bruce et al., 1991). Formation of the dual ring structure (biaryl synthesis) can be enhanced up to three orders of magnitude in the presence of metal catalysts, such as divalent copper (Gullett et al., 1992). Based upon testing with nine different metals and oxidation states, divalent copper appears to demonstrate the strongest catalytic activity (Stieglitz et al., 1989a). Radical Cl also appears to play a role in PCDD/PCDF formation and persists to temperatures where hydrocarbon chlorination occurs (Gullett et al., 2000a). It has been believed that the highly alkaline environment in cement kilns scavenges available chlorine, making it unavailable for chlorination of organic material (Eduljee, 1998). Data presented by Lanier from testing conducted at a full-scale facility showed 97% acid gas capture by the alkali material, and no effect on PCDD/PCDF emissions due to variations in chlorine feed rate (Lanier et al., 1996). Equilibrium calculations show on the other side that chlorine capture is not effective at high temperatures and that HCl is converted to Cl2, suggesting that even a highly basic chemical species such as calcium hydroxide would not Kåre Helge Karstensen [email protected] Page 136 of 420 always be expected to effectively control chlorinated hydrocarbon formation (including PCDD/PCDFs) at temperatures above 200 oC (Dellinger et al., 1993). Lamb et al. (1994) confirmed the availability of chlorine and that this led to increased production of MCB in the lower part of the preheater. Any chlorine in the fuel enters the preheater zone as HCl and Cl2, eventually organic chlorides (Sidhu et al., 2001). The HCl to Cl2 ratio seems to be important, as Cl2 is a much superior chlorinating agent than HCl. Chlorine may also be initially present in the raw meal or may be captured from the gas-phase by alkali reactions of the raw meal (Sidhu et al., 2001). Chlorine can therefore be present in the preheater zone as organic chlorides, HCl, Cl2, alkali and alkaline earth chlorides, and transition metal chlorides and the chlorination of hydrocarbons can be catalysed by the alkali metal oxides and hydroxides present in the feed material at the temperatures normally found in preheaters (Eduljee, 1998). Consequently, higher temperatures and oxygen concentration downward the preheater will increase conversion rate of HCl to Cl2 by pushing the Deacon reaction towards molecular chlorine, and hence potentially the yield of PICs such as MCB (Dellinger et al., 1993). 7.9 Catalysts Gullett, Toutati and Lee (2000) showed that industrial boiler tube deposits became a sink and source for PCDD/PCDF reactants (copper and chlorine) and PCDD/PCDFs, resulting in continued formation and emissions long after waste cofiring had ceased in the boiler. Grandesso et al. (2006) confirmed that fly ash acts as an oxidation catalyst as well as a carbon and chlorine source, e.g. metal chlorides or chloride complexes. The role of deposits in PCDD/PCDF formation makes emissions dependent on current as well as previous firing conditions and may provide a partial explanation of the high PCDD/PCDF yields in MSW incinerators during shut-down and start-up operation when high soot levels are likely. Deposits in the cooler zones of cement production has not been investigated up to date but spiking wastes with copper was not observed to affect PCDD/PCDF emission rates during full-scale testing of a US cement kiln (Lanier et al., 1996). Dudzinska et al. (1998) carried out a test in a Polish cement kiln feeding 10% inorganic (containing 0.08% copper) and 10% Kåre Helge Karstensen [email protected] Page 137 of 420 organic hazardous waste without copper. The authors claim that Polish cement plants are mostly using coal with high sulphur content and that this may have disturbed the formation of PCDD/PCDF. The kiln was operated at 6% oxygen and the PCDD/PCDF emissions were 0.0515 ng I-TEQ/Nm3 with coal only, and 0.0819 and 0.0698 ng I-TEQ/Nm3 when feeding inorganic and organic waste respectively. 7.10 Particulates Schreiber et al. (1995) conducted a test with activated carbon injection between the kiln inlet and the electro static precipitator inlet on a cement kiln burning coal, liquid waste fuel and solid waste fuel. A reduction in PCDD/PCDF levels was anticipated, but the result gave a 100-fold increase in the PCDD/PCDF level in the CKD, from 0.5 to 34 ng/kg, and no improvement in stack emissions (0.32 ng/m3) and the authors concluded that ”addition of activated carbon as a control technology in cement kilns does not reduce PCDD/PCDF emissions”. This test actually added to the particulate loading of the ESP, which also was operated at a temperature of 270 o C, and thereby increasing the available surface area for heterogeneous surface-catalyzed reactions, as shown by the increase of PCDD/PCDFs in the CKD and actually confirms the theories regarding PCDD/PCDF formation. For a cement kiln to effectively utilize carbon injection, the carbon injection system must be installed after the APCD, along with a second APCD to collect the carbon (Eduljee, 1998). It has been suggested that capture and removal of particulate matter would result in a corresponding reduction in PCDD/PCDF emissions (Eduljee, 1998). A number of studies have however shown that the correlation between PCDD/PCDF emissions and particulate emissions is not necessarily observed in full-scale plant under all operating conditions, owing to the conflicting influence of a number of operating variables (Eduljee and Cains, 1996). When operating temperatures are reduced, the PCDD/PCDF present in the gas stream will adsorb onto the surface of particulate matter and a combination of reduced temperature and improved particulate abatement may result in lower PCDD/PCDF emissions. The data to support this contention on cement kilns has yet to be systematically collected, but it is Kåre Helge Karstensen [email protected] Page 138 of 420 instructive that within the EPA study (1994), the kilns operating with fabric filters show both lower particulate emissions and lower PCDD/PCDF emissions than the kiln operating with ESP’s (Eduljee, 1998). Whether this result is due to the lower operating temperature of the fabric filter relative to an ESP (therefore minimising PCDD/PCDF formation within the pollution control device) or due to increased adsorption onto and removal of particulate matter within a fabric filter operating at a lower temperature than an ESP has not been elucidated (Eduljee, 1998). 7.11 Temperature and operating conditions The operating envelope of cement kilns is dictated largely by standard specifications for their final product and these conditions are conducive to efficient organic destruction, which makes parameters related to the temperature of the burning zone generally less relevant for cement kilns than for incinerators. Although some cement kilns operate at elevated carbon monoxide levels, these levels are not necessarily indicative of poor combustion. The calcination process releases large quantities of carbon dioxide, which can subsequently decompose into carbon monoxide at the extremely high temperatures in the kiln. In addition, carbon monoxide may be formed at the kiln gas exit end where total hydrocarbons are volatilized from the raw materials and are partially oxidized. A study examining the influence of kiln design and operating conditions during the combustion of hazardous waste was undertaken by US EPA (1994). Data from 23 separate kilns (predominantly wet kilns with ESP pollution abatement equipment, comprising 86 data points) was analysed for correlations against various emissions and operational parameters. No correlation could be established between PCDD/PCDF emissions and the stack concentration of HCl, total hydrocarbons, oxygen or particulates for the same type of electro static precipitator. One positive correlation identified both in US and German studies (Kuhlmann et al., 1996) was that between PCDD/PCDF concentration and ESP/stack temperature, at high temperatures. This was confirmed by Schreiber (1993) which tested a cement kiln with the ESP temperature between 255 oC and 400 oC; the PCDD/PCDF emissions were highest at 400 oC, and decreased 50-fold at 255 oC. Harris et al. (1994) and Lanier et al. (1996) demonstrated that PCDD/PCDF emissions from cement kilns increase Kåre Helge Karstensen [email protected] Page 139 of 420 exponentially with increases in inlet temperatures to the air pollution control device APCD within the PCDD/PCDF formation window (250 to 450 oC). The US EPA suggested that PCDD/PCDFs from cement kilns could be controlled through a combination of low temperatures in the APCD, low carbon monoxide and elevated oxygen. Attempts by cement manufacturers to achieve the 0.20 ng TEQ/m3 limit proposed in 1996 clearly demonstrated that carbon monoxide and oxygen levels are relatively unimportant and that reduced APCD temperature gave mixed results (Chadbourne, 1997). Four of 33 cement kilns that burned hazardous waste had the ability to meet the originally proposed 0.12 ng TEQ/m3 limit. All of these facilities operated with an APCD temperature near 300 oC. In contrast, a kiln in Nebraska was operated with a 120 oC APCD temperature but did not meet the limit. Another plant in Michigan produced low PCDD/PCDFs while operating at nearly 250 oC with carbon monoxide averaging over 1500 ppm. But reducing the temperature and the carbon monoxide to 110 ppm increased the PCDD/PCDFs. A plant in Missouri, operated at 310 oC with 4.4 percent oxygen, reported two values well below 0.12 ng TEQ/m3. However, a third value under the same operating conditions was over ten times higher than the first two tests. Another plant in Missouri, with a 330 oC APCD temperature but oxygen above 10 percent and carbon monoxide near 100 ppm, produced an average of 50 ng TEQ/m3 (Chadbourne, 1997). A number of wet kilns have added flue gas quenching to reduce inlet APCD temperature, and these additions have reduced the US PCDD/PCDF emissions (EPA, 2000). Even if this suggests that maximum inlet temperature to the APCD system is a key control parameter related to PCDD/PCDF emissions from wet cement kilns, low temperatures do not necessarily guarantee low results, some kilns with relatively high temperatures have low PCDD/PCDF results. This indicates that other parameters are important in combination with the temperature and Chadbourne (1997) postulated that the formation of PCDD/PCDFs is proportional to precursor and/or organics concentration and time but exponential with respect to the temperature. 7.12 Inhibitors Kåre Helge Karstensen [email protected] Page 140 of 420 Sulphur has been shown to decrease PCDD/PCDF emissions and will be present in cement production in both the coal and in the raw material. Substantially lower PCDD/PCDF emissions are normally observed from coal-fired power plants than from municipal waste combustors, even though coal-fired utilities operate under conditions that should generally be conductive to PCDD/PCDF formation. The sulphur/chlorine ratio of the fuel may explain the difference. The typical S/Cl ratio in a municipal waste combustor is about 0.2, which is approximately an order of magnitude lower than that found in coal combustion (Raghunathan and Gullett, 1997). Significant PCDD/PCDF reduction has been demonstrated at S/Cl ratios as low as 0.64 in a natural-gas-fired furnace, as low as 0.8 in a coal-fired furnace (expressed as uncorrected furnace concentrations of parts per million SO2/HCl). Additional work has shown that PCDD/PCDF formation is substantially inhibited when the S/Cl ratio is greater than about 1:1 (Gullett and Raghunathan, 1997). Researchers have concluded that sulphur may interfere with PCDD/PCDF formation by SO2 depletion of Cl2, and eventually by SO2 poisoning of copper catalysts to prevent biaryl synthesis (Griffin 1986; Gullett et al., 1992; Raghunathan and Gullett 1996). It is also possible that poisoning of the copper catalyst may interfere with the Deacon reaction. Gullett, Dunn and Raghunathan (2000) showed that wall deposits in MSW incinerator act as sources and receptors of PCDD/PCDF precursors, reactants, and/or catalysts. They also proposed that an effect of higher sulphur dioxide concentration from cofiring coal in MSWI is to displace the sulphate/chloride equilibrium in the deposits, thereby decreasing chlorine contact with active sites and/or reducing catalytic activity through formation of metal sulphates rather than metal chlorides. Since the alkali raw materials may provide some control of acid gases, the S/Cl molar ratio in the stack may be more relevant than the ratio in the feed. Other potential PCDD/PCDF inhibitors, such as calcium, are already being present in the raw materials. Schreiber et al. (1995) intentionally added sulphur to a cement kiln to achieve PCDD/PCDF control and reductions were documented when the stack concentrations of SO2 increased from less than 20 ppm to above 300 ppm. Schreiber (1995) also documented PCDD/PCDF emissions reductions when Na2CO3 was injected at the fuel feed end to react with chlorine in the system. Kåre Helge Karstensen [email protected] Page 141 of 420 7.13 Factors influencing formation of PCDD/PCDFs in cement production a summary The very low emissions of PCDD/PCDFs from cement kilns, regardless of the type of fuel used can generally be attributed to the high temperatures and long residence times within the kiln. We have seen evidence, especially from data of newer origin, that fuels and wastes fed through the burners are properly destroyed, also hazardous wastes. Even if we cannot entirely exclude the possibility of having PICs and precursors formed from these two sources, they will normally be of minor importance compared to organics in the raw material. Raw material organics, seemingly to consist of mainly aromatic compounds, will be volatilised in the preheater and partially oxidized and/or pyrolyzed and made available in the gas stream. There seems to be enough chlorine, in different species and from various sources, which through the temperature gradient in the preheater and the post-preheater region will be available for surface catalyzed reactions on particulate surfaces. Additional chlorine feed, for example through waste feeding, does not seem to be of major importance. There are studies showing that monochlorobenzenes are formed in the preheater, probably by the chlorination of raw material organics, which again can form potent precursors like chlorophenols and/or PCDD/PCDFs directly. The preheater region of a cement kiln is unique, with a temperature gradient ranging from approximately 250 oC to 850 °C, with high gas volumes and a gas retention time up to 25 sec, and abundance of particle surfaces makes it ideal for heterogeneous surface-catalyzed reactions and de novo synthesis (if the post-preheater region is included). The lower parts of the preheater may even constitute a possible place for having homogeneous pure gas-phase formation of precursors and PCDD/PCDFs. We know for the time being nothing about the possible role of wall deposits or soot, but from other studies (Gullett et al., 2000b; Grandesso et al., 2006) it can be assumed to play a role also in cement kiln APCDs. Modern preheater/precalciner kilns seems to emit slightly less PCDD/PCDF than wetprocess cement kilns. This may be attributed to two main differences between the two: the inherent lower temperature of the APCD zone in modern dry kilns and the absence of an inline raw-mill-dryer in wet kilns. The dominating operational mode, representing the normal Kåre Helge Karstensen [email protected] Page 142 of 420 low emissions from modern preheater kilns, is to duct the hot exit gas from the kiln and the preheater through the raw-mill-dryer for heating the raw materials, before it enters the APCD and the stack (called compound mode). This mode of operation both reduces the exit gas temperature and seems to absorb PCDD/PCDF. When the raw mill dryer is shut off parts of the time (direct mode), the exit gas is cooled with water, as in wet kilns. The absorption seems however to be less effective in such a mode of operation, resulting in increased emissions (authors experience). Such mode of operation resemble wet kilns equipped with coolers and may, at least partly, explain the seemingly higher emissions from wet kilns; absorption on particles in the raw mill dryer is more effective than in water coolers. In early days when wet kilns ducted the exit gas directly from the kiln to the APCD without cooling, the temperature would be in the range of 200 to 400 0C in the APCD, making it an ideal place for de novo synthesis. Evidence from the US has shown that naturally occurring PCDD/PCDFs in the raw materials can be emitted from the system, probably through volatilisation. This study have identified and quantified two sources of input materials containing PCDD/PCDFs; raw material kiln feed and CKD. Raw material kiln feed may potentially contain two sources of PCDD/PCDFs, naturally PCDD/PCDFs and adsorbed PCDD/PCDFs from the raw-mill (when CKD are reintroduced back to the process together with the raw meal). It is therefore plausible that there is a region within the preheater and the raw mill dryer where the PCDD/PCDFs, from any origin, are circulating between gaseous and particle adsorbed phases; once they are adsorbed onto particles in the cooler parts, the material flow is moving downwards to higher temperatures, where they again will be volatilised and reintroduced to the hot exit gas from the kiln. A circulation of PCDD/PCDFs may interact with, and may even be controlled by the known circulation of alkali chlorides and sulphates in the upper parts of the kiln zone and in lower parts of the preheater. Such circulation may exhibit an inhibition effect due to equilibrium reactions between chlorine and sulphur; sulphur is present in both coal and raw material and the alkali materials are in abundance. We know from other studies that sulphur and the presence of alkaline materials has been shown to decrease PCDD/PCDF emissions (Schreiber et al., 1995), and a reverse correlation between the concentration of SO2 and the concentration of PCDD/PCDF in the flue gas may be expected. Kåre Helge Karstensen [email protected] Page 143 of 420 The net formation and release of PCDD/PCDFs in cement production may therefore be due to a complex combination of simultaneous formation and decomposition reactions (Karstensen, 2007): • destruction of PCDD/PCDFs in the kiln region; • formation of PICs and chlorinated organics in the preheater, basically from raw material organics; • gas-phase formation reactions between precursors in the lower part of the preheater can form PCDD/PCDFs directly; • heterogeneous surface-catalyzed formation of precursors and PCDD/PCDFs in the preheater; • an adsorption-desorption circulation process of naturally and adsorbed PCDD/ PCDFs in the preheater and the raw mill dryer; • interaction with equilibrium reactions and circulation of chlorine, sulphur and alkali materials in the upper parts of the kiln zone and lower parts of the preheater may lead to inhibition; • de novo synthesis and formation of PCDD/PCDFs in the APCD and the post preheater zone. The detailed understanding how PCDD/PCDFs are formed in cement production is not yet complete, but it seems that a combination of heterogeneous surface catalysed reactions and de novo synthesis in the preheater and the post-preheater zones are the most important. A comprehensive mass balance study would be needed to reveal this hypothesis. 7.14 Controlling emissions of PCDD/PCDFs Kåre Helge Karstensen [email protected] Page 144 of 420 Dioxin formation and subsequent emission requires the simultaneous presence of the following factors of influence: 9 Particulate surfaces, i.e. sites which can catalyse the formation; 9 Hydrocarbons and chloride(s); 9 Appropriate temperature window between 200 °C and 450 °C, with a maximum at around 350 °C; 9 Appropriate residence time, probably more than 2 seconds. The options for controlling PCDD/F emissions from cement kilns broadly fall into two categories: (1) controlling quality of the feed material; (2) controlling post-kiln operating conditions in wet kilns. The cement production process has an impact on the energy use and the emissions to air. For new plants and major upgrades the best available techniques (BAT) for the production of cement clinker is a dry process kiln with multi-stage preheating and precalcination. The following general primary measures (integrated process optimisation) seem to be sufficient to comply with an emission level of 0.1 ng PCDD/F I-TEQ/Nm3: A smooth and stable kiln process, operating close to the process parameter set points, is beneficial for all kiln emissions as well as for the energy use. This can be obtained by applying: Process control optimisation, including computer-based automatic control systems; The use of modern fuel feed systems. Kåre Helge Karstensen [email protected] Page 145 of 420 Minimising fuel energy use by means of: Preheating and precalcination to the extent possible, considering the existing kiln system configuration. Careful selection and control of substances entering the kiln can reduce emissions and when practicable, homogenous raw materials and fuels with low contents of sulfur, nitrogen, chlorine, metals and volatile organic compounds should be selected. Expert judgement by the European IPPC Bureau has played a key role in identification of Best Environmental Practice (BEP) and BAT for the cement industry (IPPC, 2001). In the Best Available Technique Reference (BREF) document, techniques and possible emission levels associated with the use of BAT are presented that are considered to be appropriate to the sector as a whole. Where emission levels “associated with best available techniques” are presented, this is to be understood as meaning that those levels represent the environmental performance that could be anticipated as a result of the application, in this sector, of the techniques described, bearing in mind the balance of costs and advantages inherent within the definition of BAT. However, they are not emission limit values and should not be understood as such. In some cases it may be technically possible to achieve better emission levels but due to the costs involved or cross media considerations, they are not considered to be appropriate as BAT for the sector as a whole. The concept of “levels associated with BAT” is to be distinguished from the term “achievable level”. Where a level is described as “achievable” using a particular technique or combination of techniques, this should be understood to mean that the level may be expected to be achieved over a substantial period of time in a well maintained and operated installation or process using those techniques. Kåre Helge Karstensen [email protected] Page 146 of 420 Actual cost of applying a technique will depend strongly on the specific situation regarding, for example, taxes, fees, and the technical characteristics of the installation concerned. It is not possible to evaluate such site-specific factors fully. It is intended that the general BAT could be used to judge the current performance of an existing installation or to judge a proposal for a new installation and thereby assist in the determination of appropriate “BAT-based” conditions for that installation. It is foreseen that new installations could be designed to perform at or even better than the general “BAT” levels. It is also considered that many existing installations could reasonably be expected, over time, to move towards the general “BAT” levels or do better. While the BAT and BEP levels do not set legally binding standards, they are meant to give information for the guidance of industry, States and the public on achievable emission levels when using specified techniques. The following primary measures are considered to be most critical in avoiding the formation and emission of PCDD/F from cement kilns: 9 Quick cooling of kiln exhaust gases to lower than 200 oC in long wet and long dry kilns without preheating. In modern preheater and precalciner kilns this feature is already inherent. 9 Limit or avoid alternative raw material feed as part of raw-material-mix if it includes organic materials. 9 No alternative fuel feed during start-up and shut down. 9 Monitoring and stabilisation of critical process parameters, i.e. homogenous raw mix and fuel feed, regular dosage and excess oxygen. For new cement kilns and major upgrades the BAT for the production of cement clinker is dry process kiln with multi-stage preheating and precalcination. A smooth and stable kiln process, operating close to the process parameter set points is beneficial for all kiln emissions as well as the energy use (UNEP, 2007). PCDD/PCDF control in cement production becomes a simultaneous effort to reduce the precursor/organic concentrations, Kåre Helge Karstensen [email protected] Page 147 of 420 preferably by finding a combination of optimum production rate and optimum gas temperatures and oxygen level at the raw material feed end of the kiln, and the reducing the APCD temperature. Feeding of alternative raw materials as part of raw-material-mix should be avoided if it includes elevated concentrations of organics and no alternative fuels should be fed during start-up and shut down. The most important measure to avoid PCDD/PCDF formation in wet kilns seems to be quick cooling of the kiln exhaust gases to lower than 200 o C. Modern preheater and precalciner kilns have this feature already inherent in the process design and have APCD temperatures less than 150 oC. Operating practices such as minimising the build-up particulate matter on surfaces can assist in maintaining low PCDD/PCDF emissions. 7.15 UNEP Standardized Toolkit default emission factors for cement production The Stockholm Convention Article 5, Annex C, Part II, is explicitly mentioning “Cement kilns firing hazardous waste” as a potential source of PCDD/F emissions to air and release in residues (cement kiln dust). The UNEP Standardized Toolkit has proposed four classes of default emission factors for cement production, differentiating between type of kiln and ESP temperature and refers to the US EPA statement in 1999 “that hazardous waste burning does not have an impact on PCDD/F formation, PCDD/F is formed post combustion” (Federal Register, 1999). The Toolkit states that the more detailed investigations of the US EPA study has suggested that provided combustion is good, the main controlling factor is the temperature of the dust collection device in the gas cleaning system, and says further “the plants equipped with low temperature electrostatic precipitators appear to have well controlled emissions with or without waste fuels”. Further “It is thought that the raw materials themselves can have a considerable influence on the emissions and the presence of high levels of organic matter in the raw materials has been associated with elevated emissions of PCDD/F. It should be noted that Kåre Helge Karstensen [email protected] Page 148 of 420 the higher emissions measured in the USA were from wet kilns whereas the lower emissions from European cement kilns were obtained from plants using the dry process.” Further: “The low results found in most of the modern European plants have been confirmed by the recent PCDD/F sampling and analysis program in Thailand (UNEP, 2001), where the results demonstrated that the addition of tyre and/or liquid hazardous waste had no effect on the emissions results”. Table 14 UNEP default emission factors for cement production (UNEP, 2005) Classification Emission factors - µg TEQ/t of cement Air Water Land Product Residue 1. Shaft kilns 5.0 ND ND ND ND 2. Wet kilns with ESP temperature >300 oC 5.0 ND ND ND NA 3. Rotary kilns with ESP temperature 0.6 ND NA ND NA 0.05 ND NA ND NA o 200-300 C 4. Wet kilns with ESP temperature <200 oC Dry kilns preheater/precalciner, T<200 oC The Toolkit states that the concentration of PCDD/F in the flue gases seems to be influenced by the temperature of the ESP. Low temperature (<200 oC) seems to indicate that typical concentrations will be under 0.1 ng TEQ/m3, temperatures over 300 oC increase the likelihood of finding higher emissions, typical concentrations would be 0.3 ng TEQ/m3 and above. In some cases much higher emissions may be found and these seem to be linked to high dust collector temperatures, high levels of organic matter in the raw materials and may be linked to use of certain wastes under inappropriate conditions. Kåre Helge Karstensen [email protected] Page 149 of 420 An emission factor of 5 µg TEQ/t of cement is applied to vertical shaft kilns and wet kilns with dust collectors over 300 oC. In some Asian countries, vertical shaft kilns (VSK) are used to produce clinker. These plants are relatively small with a daily capacity from 50 t/d up to around 300 t/d. However, no measurements of PCDD /F concentrations can be found in the literature. Thus for the purpose of this Toolkit and to make a first release estimate, the same emission factor as developed for old wet kilns (Class 2) will be applied to these plants. An emission factor of 0.6 µg TEQ/t is applied to wet kilns where the dust collector is between 200 oC and 300 oC. An emission factor of 0.05 µg TEQ/t is applied to all dry kilns and wet kilns where dust collector temperatures are held below 200 oC. The Toolkit also says that cement kilns, where materials have unusually high concentrations of organic matter and dust collector temperatures are high, should be noted for further consideration. Further, the Toolkit recommends that the use of wastes should be recorded noting the wastes used, the means used to introduce them to the kiln and any operational control (e.g. prevention of feeding during combustion upsets, etc.). The Toolkit states that releases of PCDD/F to water is not expected and that the releases in the cement product are expected to be small since the product has been exposed to very high temperatures. The Toolkit states the following with regards to potential releases to land and through residues (UNEP, 2005): "It should be mentioned that the dusts collected in air pollution control systems, typically electrostatic precipitators (ESP) or cyclones, mainly consist of raw materials fed into the kiln (at the end of the secondary burner). The remainder of the dust consists of emissions from the kiln that has passed the hot zone. Typically, the dusts from the ESPs/cyclones or bagfilters are re-introduced into the kiln. Therefore, the default Table 41 does not contain any emission factors for residues. In cases, where solid residues from flue gas cleaning equipment are not recycled into the kiln, an initial estimate of release of PCDD/PCDF in CKD would be based on the assumption that approximately 30 kg of CKD Kåre Helge Karstensen [email protected] Page 150 of 420 per ton of clinker (0.03 % of clinker production) is generated. This value is based on a report that gave 0.4 million tons CKD from 13.5 million tons of clinker/cement production (Dyke et al. 1997). Concentrations of PCDD/PCDF in the CKD are expected to vary and a range of concentrations from 0.001 to 30 ng TEQ/kg has been reported for UK kilns (Dyke et al. 1997), 1-40 ng TEQ/kg were summarized for German tests (SCEP 1994). 7.16 Dioxin emission inventories and release contribution of the cement industry Emission inventories and release contribution estimates for the cement industry are usually based on two types of information, earlier literature data or real measurements, providing considerably different results. Early inventories usually assigned high emission factors based on literature data, especially to hazardous waste burning kilns. Brzuzy and Hites (1996) estimated the total global annual emission of PCDD/PCDF to air to be 3000 ± 600 kg. The cement industry burning and not burning hazardous waste was assigned an emission factor of up to 4160 µg/t cement and 320 µg/t cement respectively. UNEP assigned in 1999 an emission factor of 2600 μg TEQ/t and 200 μg TEQ/t for hazardous waste burning and non-hazardous waste burning cement kilns respectively (1999). Other examples can be found from Italy (Caserini and Monguzzi, 2002), Russia (Kucherenko et al., 2001a; 2001b) and Taiwan (Chen, 2004). These emissions factors lead to cement industry contribution estimates ranging from 5%, and up to a worst case scenario estimate of 59% of total emissions by Brzuzy and Hites (1996). The most recent inventories do not longer differentiate if the kiln uses hazardous or non hazardous waste. The UNEP Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases (UNEP, 2005) has suggested three classes of default emission factors for cement production, differentiating between kiln type and the APCD temperature only. An emission factor of 5 µg TEQ/ton is assigned to vertical shaft kilns and wet kilns with APCD temperature over 300 oC; 0.6 µg TEQ/ton is assigned to wet kilns with APCD Kåre Helge Karstensen [email protected] Page 151 of 420 temperature between 200 oC and 300 oC, and 0.05 µg TEQ/ton is assigned to all dry kilns and wet kilns where dust collector temperatures is held below 200 o C. The European PCDD/PCDF inventory was based on a flat emission factor of 0.15 µg TEQ/t cement, not differentiating between kiln technologies or temperature in the APCD (Quaβ et al., 2004). More recent inventories are usually based on real measurements, resulting in significantly lower emission factors and a release contribution estimates, constituting from about 0.5% or less of total emissions. Fabrellas et al. (2002; 2004) used 0.014464 µg ITEQ/ton cement in the Spanish inventory; 0.2 μg TEQ/ton were used for the Newly Independent States and the Baltic countries (Kakareka, 2002; Kakareka and Kukharchyk, 2002); 0.025-1.2 μg I-TEQ/ton cement was used in the UK, covering also wet kilns burning a mix of fossil and waste derived fuel (Eduljee, 1996; Eduljee and Dyke, 1996; Alcock et al., 1999). In the absence of real measurements, the Hong Kong Environmental Protection Department (2000) assumed an exit gas concentration of 0.1 ng I-TEQ/m3, a flow rate of 7000 m3/min and an operation of 7680 hours of per year for their cement plant, leading to a contribution estimate of 0.96-1.39 percent of total emissions. The latest and most comprehensive investigations illustrate the gap between earlier literature data and real measurements. The average PCDD/PCDF flue gas concentration in European kilns is approximately 0.02 ng TEQ/m3, representing hundreds of recent measurements. Assuming an average exhaust-gas volume of 2300 Nm3/ton clinker (IPPC, 2001) and a clinker/cement ratio of 0.8 would give an emission factor of 0.037 µg TEQ/ton cement. The worldwide measurements performed by Holcim showed an average emission factor of 0.104 μg TEQ, 0.073 μg TEQ and 0.058 μg TEQ pr ton clinker, representing a clinker production of 35.1, 46.7 and 57.6 million ton respectively (Lang, 2004). Taiheiyo Cement measured the emission factor to be 0.03 µg TEQ/ton, representing 23.6 million tons of cement in 2001 (Taiheiyo, 2003). Kåre Helge Karstensen [email protected] Page 152 of 420 8. Potential risks to human health While it has been demonstrated that hazardous waste co-processing can be accomplished in an environmentally sound manner, improper design or operation may pose a potential threat to community and worker health and should be evaluated. Although cement kilns have all the desirable properties for efficient thermal destruction of many hazardous wastes, most cement kilns were not designed for this purpose and require modification of the fuel injection system, as well as construction of waste receiving facilities. These facility modifications should be carefully designed, and monitored to assure that environmental risks are minimized. 8.1 Introductory risk assessment in planning AFR activities A screening evaluation should be made to assess transportation, storage and handling, kiln emission and health risk, as an interactive part of the planning and design process. It would also be useful to evaluate the risk of clinker contamination at this stage. Subsequent to the facility modification and test burn, a more quantitative risk assessment may be conducted to determine the potential for adverse health impacts within the community and the kiln employees. The screening level risk assessment may be conducted as part of the planning process to assess the suitability of co-processing hazardous wastes in the specific kiln of interest. This assessment may provide an analysis of the risks associated with one specific kiln, or may be used to select among several kilns for the one most suitable for conversion and modification for hazardous waste co-processing. Four major types of risk should be assessed at this stage: 1. Transportation; 2. Storage and handling; Kåre Helge Karstensen [email protected] Page 153 of 420 3. Kiln emission and health risk and 4. Clinker contamination risk. The first three of these risks can be evaluated in terms of three separate components: 1) risk of toxic material release, 2) risk of human exposure, and 3) risk of adverse health effect. All types of risk regarding the co-processing of hazardous wastes require knowledge of the chemical properties of the waste and of the by-products from waste combustion. This knowledge allows one to calculate the expected fate and transport of pollutants in the environment. The accidental release of toxic materials to the environment during transportation of the hazardous material to the cement kiln should be evaluated. This evaluation is useful in the selection of alternative transportation scenarios to minimize risk of exposure in the event of an accident. Example alternatives are: 1) waste generators each transport their own material to the kiln; 2) a waste generators transport waste to a central facility which then transports waste to the kiln; 3) a professional waste transport operation collects waste from each generator and transports it to the kiln along a specified route. Option three will generally represent the lowest risk of exposure because the number of transport routes can be minimised, and skilled and knowledgeable drivers can be provided by the professional collection service. A second type of risk which should be evaluated is that of a spill or leakage of toxic material during storage and handling. This is primarily an occupational risk, although a major spill or leak could affect the community. This type of risk can be minimized through careful design and construction of the waste handling tanks, piping and values, and through thorough worker training programs and safety audits. The most visible risk, and the one of which the public is most aware, is the health risk from the by-products of waste co-processing in the kiln. This type of risk involves both routine and accidental emissions. The inhalation risk from routine emissions can be estimated Kåre Helge Karstensen [email protected] Page 154 of 420 using emission factors from similarly operating kilns in an atmospheric dispersion model using the local meteorological and topographical features. Humans may be exposed to chemicals from cement production facilities in emissions, byproducts of the manufacturing process, or the finished product. Exposure to the hazardous waste used as fuel may also occur during transportation of fuels to the facility. Persons exposed to high concentrations of facility emissions or process solids can experience adverse health effects. Typically, high concentrations are found only in the workplace, generally in countries other than the U.S., and not in locations where public health would be affected. High occupational exposures are nonetheless useful for elucidating some of the potential human health effects from cement production when adequate public studies are unavailable. Subsequent to the test burn, actual emission data and combustion parameters should be available for a more quantitative risk analysis. At that time it is advisable to conduct a more kiln-specific quantitative risk assessment of community exposure. Stack emission source data from the test burn could be used in atmospheric dispersion and food chain models to estimate community exposure through inhalation and ingestion. Several studies of risk associated with hazardous waste incineration suggests that under optimum operating conditions, inhalation risks are insignificant (Pleus and Kelly, 1996, Schuhmacher, 2002; Schuhmacher, et al., 2004; Tam and Neumann, 2004). However, it is useful to demonstrate this through risk assessment calculations specific to the kiln of interest. 8.2 Cement operations Despite the decades of operations and extensive public exposure to cement plant emissions in the US, neither clinical nor epidemiological studies have been performed that examine the effects on public health of a cement production facility burning either conventional or hazardous waste fuel. Evidence of problems with local public health has not been sufficient to cause concern or to trigger public health studies, and no major health agency has considered cement plants to be a threat to public health. This lack of concern may result in part from the low rate of occupational illness in the cement industry (i.e. 24.8 incidences per 10,000 workers), which is less than one-fourth the average incidence rate for Kåre Helge Karstensen [email protected] Page 155 of 420 any type manufacturing (i.e. 108.3 incidences per 10,000 workers). These occupational illness rates, as well as many others, are listed in the table below. The available studies on cement plants in other countries conclude that lack of emission controls can result in extremely high concentrations of particulates in ambient air. Exposure of local communities to these emissions has resulted in increased cases of respiratory diseases, skin diseases, eye irritation, and gastrointestinal tract diseases (Borka, 1986; Krishnamurthy and Rajachidambaram, 1986; Mishra and Tiwari, 1986; Anda, 1987). Since the 1970s, the increasingly strict controls on emissions from cement plants have considerably reduced the potential for public exposure to hazardous emissions. With the recent increase in the use of hazardous waste as a supplemental fuel in cement kilns, the issues for public health has become whether the chemicals emitted from cement plants burning hazardous waste might now be a threat to public health. This concern is largely based on the supposition that such plants emit much greater amounts of potentially toxic chemicals than those using only conventional fuel. This issue is addressed by reviewing the available information on the potential health threats from cement plants supplementing their fuel with hazardous waste and from those burning only conventional fuel. Three major sources of exposure are evaluated in this review (Mantus, 1992): - Stack emissions from the cement plant - CKD, the byproduct of the manufacturing process - Cement, the final product. As mentioned previously, another potential source of exposure to hazardous waste fuel at cement plants may be transportation of the fuel to the facility. This source is evaluated by reviewing statistics on spills and accidents of hazardous materials transportation. For each major source of exposure, the potential effects to human health are discussed below relative to both burning hazardous waste and burning conventional fuel. Potential Kåre Helge Karstensen [email protected] Page 156 of 420 exposures are also viewed in light of recent U.S. EPA regulations (i.e. the BIF rule) that further reduce emissions from cement kilns. Table 15 Occupational illness rates, 1989 a (Mantus, 1992) Meat products 689.4 Drug manufacture 60 Ship and boat building, repair 411.1 Chemicals and allied products 57.4 Motor vehicle and equipment manufacture 373.1 Paper and allied products 53.0 Plumbing and heating products manufacture 346.5 Petroleum refining 52.0 Household appliances manufacture 275.3 Guided missile, space vehicles, parts manufacture 49.5 Footwear manufacture 274.7 Photographic equipment and supplies 48.7 Leather tanning and finishing 239.9 Soaps, cleaners and toilet goods 37.4 Hats, caps and millinery 196.5 Computer and office equipment 37.3 Men’s and boy’s furnishings 185.1 Watches, clocks, watchcases, and parts manufacture 37.3 Engine and turbine manufacture 174.3 Agricultural chemicals 36.9 Metal forgings and stampings 172.4 Painting and paper hanging 32.4 Preserved fruits and vegetables 145.6 Costume jewelry and notions 28.3 Toys and sporting goods manufacture Concrete, gypsum, and plaster 144.7 products manufacture b 24.8 Office furniture manufacture 132.4 Newspaper printing and publication 22.3 Pens, pencils, office and art supplies 121.3 Residential building construction 17.8 Musical instrument manufacture 104.9 Services 16.7 Iron and steel foundries 100.5 Transportation and public utilities 16.0 Forestry 86.7 Women’s and misses’ outerwear 15.9 Greeting cards printing and publication 79.2 Cut stone and stone products 14.9 Bakery products 75.6 Retail trade 7.7 Girls’ and children’s outerwear 68.9 Finance, insurance and real estate 6.1 Tire and inner tube manufacture 68.1 Asphalt paving and roofing materials 5.5 Coal mining 62.6 a Incidence rates per 10,000 full-time workers. b This category includes manufacture of ready-mix concrete and Portland cement. Source: U.S. Department of Labor (1991). Kåre Helge Karstensen [email protected] Page 157 of 420 8.2.1 Cement plant emissions Humans may be exposed to cement plant emissions from both the stack and from fugitive emissions. The constituents in emissions from cement plant stacks that are human health concern can be divided into three broad categories: organic chemicals, metals, and particulates. The organic chemicals include unburned compounds present in the waste, thermal decomposition products, and compounds newly created from the burning process. In general, ten metals are of concern. Four are regulated as carcinogens-arsenic, beryllium, cadmium, and hexavalent chromium; six are regulated as noncarcinogens-antimony, barium, lead, mercury, silver, and thallium. Particulates are of concern for two reasons. Excessive inhalation of dust particles in general can be harmful to health, and toxic metals and organic chemicals adsorbed to particulate surfaces may be released when they contact skin or lung tissue. However, in the U.S., emissions from cement plants are passed through APCDs that remove the vast majority of the particulates, thus mitigating exposure to the high levels of particulates associated with adverse effects. Once released from the stack, emissions are diluted by ambient air and may be transported as a plume away from the facility. Any potential health effects to the public are directly related to the amount of exposure after transport away from the stack. The meteorological conditions at the facility, such as wind speed and direction, and the local terrain are major factors that affect the direction of transport, the amount of dilution, and shape of the emitted plume. As the plume migrates away from the facility, it continues to disperse, and emitted compounds become further diluted in ambient air. Concentrations to which the public may be exposure are dependent on the extent of dilution and on the deposition of gases and particulates on soils and surface water by gravity, wind, and precipitation. These modes of dispersion and deposition are illustrated in the figure. The components remaining in the air after dilution and deposition are the major source of direct exposure to compounds from the facility. Chemicals in the remaining gases and suspended particulates may be inhaled, or they may come in direct contact with skin. Kåre Helge Karstensen [email protected] Page 158 of 420 Figure 11 Modes of Dispersion and Deposition for Facility Stack Emissions (Mantus, 1992) Contact with emitted compounds may also occur through ingestion of water or of food grown in soils on which contaminants were deposited. Ingestion is considered an indirect route of exposure. Another indirect route of exposure is inhalation of resuspended dusts. This exposure occurs when constituents that have been transported away from a facility are deposited on local soils and then resuspended in the air by wind erosion, where contact follows by inhalation. Resuspended dusts from stack emissions in these cases do not contribute substantially to public exposure (Clement, 1988). The public health threat is low largely because the particles have been diluted with soil material, the organic chemicals have been degraded or volatilized, and both organic chemicals and metals may have leached to deeper soils. Despite the large quantity of metals present in the production of cement, cement kilns contribute relatively small quantities of metals to public exposure in the U.S. compared with other sources. For example, cement kilns contribute about 0.1% to the atmospheric chromium emissions in the U.S., of which 0.2% is estimated to be in the most toxic hexavalent form Kåre Helge Karstensen [email protected] Page 159 of 420 (ATSDR, 1987). In contrast, combustion of coal and oil from all sources accounts for 66% of the atmospheric chromium, or about 660 times greater than the contribution from cement kilns. Similarly, cement kilns contribute approximately 0.2% to the atmospheric lead in the U.S. as compared with the 89.4% from gasoline combustion (ATSDR, 1990), or 446 times greater than the contribution from cement kilns. 8.2.2 Fugitive emissions Fugitive emissions arise from sources other than the stack and are usually associated with normal plant operations, storage, upsets, or leaks at the facility. Fugitive emissions associated with the actual kiln contain essentially the same chemical constituents as stack emissions; however, they may contain more particulates than do stack emissions, since fugitive emissions do not pass through the APCDs. Fugitive emissions associated with storage and transfer of the hazardous waste fuel to the kiln would contain the same components as the waste. The population exposed to fugitive emissions at cement plants consists primarily of workers at the facility rather than the general public. Fugitive emissions occur at lower elevations and have larger particle sizes than stack emissions, resulting in dispersion over a smaller ground area. Offsite transport and exposure to the general public are thereby minimized, as is the potential for adverse health effects. Any nonstack emissions that manage to escape a facility are dispersed in the environment by the same factors that govern dispersion of stack emissions (i.e. local climate, geography, and chemical properties of the emissions). 8.2.3 Regulated risks to human health The potential for current stack emissions from cement plants to adversely affect public health is governed partly by the recently enacted BIF rule (Mantus, 1992). The BIF rule regulates emissions from cement kiln stacks on the basis of potential risk to public health. The limits set in the BIF rule are described as risk-based since they start from an acceptable Kåre Helge Karstensen [email protected] Page 160 of 420 risk limit and work backward to maximum allowable emissions. By contrast, a risk assessment starts with emissions and works forward to quantify the risks to health without a predetermined outcome. Through the use of risk-based exposure limits, the BIF rule attempts to prevent exposures of the public to high levels of emissions from cement plants that could cause long-term illness or cancer. Even though higher emissions from cement plants may have existed prior to regulations, adverse health effects associated with the emissions have not been documented. Thus, reduced exposure under the new BIF rule is expected to result in still lower potential for adverse health effects. For selected POHCs in hazardous waste, the U.S. EPA determined for the BIF rule that with a 99.99% DRE, exposure for a lifetime to the maximum concentrations in emissions generally would result in a risk of developing cancer of 1 in 1,000,000 or less (U.S. EPA, 1991). This level of risk is equal to the U.S. EPA’s most conservative definition of “acceptable” risk and is well below other types of federally regulated risk. The BIF rule further states that a 99.99% DRE will “ensure that constituents in the waste are not emitted at levels that could pose significant risk in virtually all scenarios” (U.S. EPA, 1991). The DRE required for “dioxin-listed” wastes under the BIF rule (and for PCBs under TSCA), is 99.9999%. These requirements limit exposure to such compounds to levels well below regulatory thresholds of public health concern. Because of these requirements, the U.S. EPA has started that emissions of PICs “do not pose significant risks when BIFs and incinerators are operated under good combustion conditions” (U.S. EPA, 1991). The BIF rule also regulates carcinogenic metal emissions on the basis of protecting public health. According to the rule, emissions of BIF-regulated metals form cement kilns are limited so that lifelong exposure to the maximum amounts of all BIF metals in ambient air through all pathways of possible exposure from a facility results in a risk of contracting cancer no grater than 1 in 100,000. For noncarcinogenic metals, the BIF standards are intended to prevent adverse health effects to the public even under maximum exposure to all possible exposure routes (U.S. EPA, 1991). Of the BIF-regulated metals, thallium may be of particular concern for releases from cement kilns. Although some forms of thallium are considered highly toxic, with dermal contact being the primary route of entering the body, little is known about potential health Kåre Helge Karstensen [email protected] Page 161 of 420 effects from chronic low exposures (Kazantis, 1986). The high volatility of thallium can result in less bonding in clinker, resulting in less removal of thallium to the process solids and its subsequent enhancement in the dust phases in the kiln (Sprung, 1985; Kirchner, 1987). Such elevated levels, which can be avoided by periodically removing CKD from the process, have been shown in the past to lead to excessive thallium emissions from cement kilns (Bambauer and Schäfer, 1984). For those kilns burning hazardous waste as a fuel, the emission of thallium is regulated under the BIF rules, requiring that public health impacts be avoided. In summary, cement plants that meet the regulations described in the BIF rule are operating under conditions identified by the U.S. EPA as associated with risks below those of regulatory concern (Mantus, 1992). 8.2.4 Health assessments of burning hazardous waste and conventional fuel The potential risk to the health of residents living near cement plants has been estimated in a few recent studies. These studies are especially useful to evaluate potential differences in exposure and associated risks between the use of conventional fuel and the use of hazardous waste for a portion of the fuel in cement kilns. In two major studies involving both a dry and a wet process cement kiln (Garg, 1990a, b), the U.S. EPA found that the amounts of PICs, dioxins, and furans emitted while burning hazardous waste were similar to the amounts emitted when only conventional fuel was burned. The U.S. EPA (Garg, 1990b) also examined potential public health effects due to emissions from burning conventional fuel (i.e. a mixture of coal and diesel) and conventional fuel mixed with hazardous waste in the wet process kiln. Under the conservative assumptions that a member of the public breathed dioxin emissions from the plant for a lifetime, the U.S. EPA estimated that risk of developing cancer when conventional fuel was burned was 2 in 1,000,000, and essentially the same – 2 to 4 in 1,000,000 – when hazardous waste was mixed with the conventional fuel. Kåre Helge Karstensen [email protected] Page 162 of 420 A similar assessment of health risks was performed for a cement kiln in California. The investigators estimated plausible exposures for the inhalation route as well as from ingestion of soil, crops, and fish exposed to emissions deposited downwind of the site (Stein and Lowe, 1990). Estimated risks of developing cancer from metals and a number of organic compounds were equal for both hazardous waste fuel and conventional fuel, at 2 to 3 in 1,000,000. These risks are virtually the same as those estimated by the U.S. EPA (Garg, 1990 b). More importantly, the investigators found that the estimated health risks actually decreased for the plant as the conventional fuel (i.e. petroleum coke) was increasingly replaced by hazardous waste fuel at amounts of 16% and 37% of the volume. Many of compounds present in the petroleum coke were not present in the hazardous waste fuel, resulting in an overall decrease in emission of hazardous constituents and risks. Further evaluation of the potential difference in health effects between cement production facilities burning hazardous waste and those burning only conventional fuel may be made with the available data on metal emissions in the CRI database. As shown earlier the average amounts of most metals currently emitted from kilns burning hazardous waste are not significantly different from the amounts emitted from kilns burning only conventional fuel. Emissions for the two exceptions to this trend, lead and mercury, were two to three times higher for kilns burning hazardous waste as a supplemental fuel. On the basis of this finding, the major concern for public health is whether the increases in lead and mercury emissions are sufficient to affect the health of people residing near cement plants. However, no health or epidemiology studies have been reported on cement kiln emissions. In the absence of such studies, one way to evaluate the increased emissions is to compare them to similar emissions from a specific cement kiln for which potential public health risks have been estimated. Comparison of the average lead and mercury emissions with those from the cement kiln in California discussed above shows that they fall within a range of 0.75 to 1.5 times their concentrations in emissions from the California kiln. At the emission rates for the California kiln, the downwind concentrations of lead and mercury were estimated to be 2 orders of magnitude (mercury) to 4 orders of magnitude (lead) below their respective health criteria (Stein and Lowe, 1990). By extrapolation, one would expect that an increase in emissions of mercury and lead by a factor of 2 to 3 from kilns burning hazardous waste would still result in average offsite concentrations well below public health concerns, possible by 2 to 4 orders of magnitude. Kåre Helge Karstensen [email protected] Page 163 of 420 On the basis of this analysis, the potential health effects due to metals exposure from kilns burning only conventional fuel or a mixture of conventional and hazardous waste fuel appear to be essentially the same (Mantus, 1992). 8.2.5 “Acceptable” risk In general, the studies discussed above indicate that the public’s risk of developing cancer from cement kiln emissions, whether burning hazardous waste or conventional fuel, is less than a few in a million. The U.S. EPA and other regulatory agencies (e.g. U.S. Food and Drug Administration, California Department of Health Services) usually consider health risks near or below 1 in 1,000,000 to be de minimus, or below the level of concern for regulation by the government (Travis et al., 1987; Kelly and Cardon, 1991). At this level, the incremental risk of developing cancer equates to an increased change of 0.0003% after accounting for the approximately 33% change of developing cancer in the U.S. from all sources. Risk levels less than 1 in 1,000,000 have typically not been regulated, and even levels up to 1 in 10,000 are seldom regulated. De manifestis risks, or risks that are of regulatory concern, have generally been considered to be a few in a thousand for developing cancer (Travis et al., 1987). Risks from cement kilns burning hazardous waste are thus considerably below levels of “acceptable” risk by most regulatory standards, although the ultimate determination of acceptability is a value judgment and not a scientific decision. In summary, analysis of current cement kiln emissions demonstrates that concentrations of emitted chemicals from facilities co-processing hazardous waste as a supplemental fuel are not substantially different from those burning conventional fuel. Since the threat to public health from conventional fuel sources has been accepted by the U.S. EPA as negligible and within acceptable limits, it follows that the similar exposures from properly operated kilns co-processing hazardous waste under current conditions would also result in negligible health effects (Mantus, 1992; Pleus and Kelly, 1996, Schuhmacher, 2002; Schuhmacher, et al., 2004; Tam and Neumann, 2004). Kåre Helge Karstensen [email protected] Page 164 of 420 9. BAT/BEP for co-processing hazardous wastes in cement kilns The following text is excerpts from the Stockholm Convention expert group on BAT/BEP - Cement Kilns firing Hazardous Waste, submitted February 2006 to the Stockholm Secretariat. The following paragraphs summarize best available techniques and best environmental practices for cement kilns firing hazardous waste. 9.1 General measures for management Legal aspects: Appropriate legislative and regulatory framework has to be in place to ensure enforcement and to guarantee a high level of environmental protection. All relevant authorities have to be involved during the permitting process, and in this regard, among other actions, the cement plant operator must: a) establish credibility through open, consistent, and continuous communication with authorities; b) provide necessary information to ensure that authorities are able to evaluate the processing of hazardous waste and; c) install community advisory panels early in the planning process. Environmental aspects: The use of hazardous wastes as alternative fuel does not significantly change the emissions from a cement kiln stack. However, fuels containing pollutants for which the cement process does not have sufficient retention capability (like mercury) shall not be used. Kåre Helge Karstensen [email protected] Page 165 of 420 Emission monitoring is obligatory in order to demonstrate compliance with existing laws, regulations, and agreements, with mechanisms for ensuring the reliability of the initial quality control of the process input materials. Operational aspects: Only hazardous waste from trustworthy parties throughout the supply chain will be accepted, with the traceability of the waste ensured prior to reception by the facility, with unsuitable waste refused. Materials transport, handling and storage must be effectively monitored, in full compliance with existing regulatory requirements. Health and Safety aspects: Site suitability avoids risks associated with location (proximity to populations of concerns, impact of releases, logistics, transport), infrastructure (technical solutions for vapours, odours, infiltration into environmental media, etc.). Adequate documentation and information are mandatory, providing an informed basis for openness and transparency about health and safety measures and standards, and ensuring as well that employees and authorities have such information well before starting any use of hazardous waste derived alternative fuel in a cement kiln facility. Communication issues and social responsibility: In the interest of openness and transparency, the planned cement kiln operator must provide all necessary information to allow stakeholders to understand the purpose of the use of hazardous waste in a cement kiln, the context, the function of the parties involved and decision-making procedures, Kåre Helge Karstensen [email protected] Page 166 of 420 In summary the following general management aspects should be taken into account: • General infrastructure, paving, ventilation; • General control and monitoring of basic performance parameters; • Control and abatement of gross air emissions (NOx, SO2, particles, metals); • Development of environmental monitoring (establishing standard monitoring protocols); • Development of audit and reporting systems; • Implementation of specific permit and audit systems for use of alternative fuels; • Demonstration by emission monitoring that a new facility can achieve a given emission limit value; • Occupational health and safety provisions: Cement kilns feeding alternative fuels need to have appropriate practices to protect workers handling those materials during the feeding process; • Sufficient qualification and training of staff. 9.2 Specific measures For new plants and major upgrades, best available techniques for the production of cement clinker are considered to be a dry process kiln with multistage preheating and precalcination. For existing installations, partial (and perhaps considerable) reconstruction is needed. Indirect measures for control of chemicals listed in Annex C of the Stockholm Convention have a minor impact in specific cases, but are an important element of integrated emission control. Kåre Helge Karstensen [email protected] Page 167 of 420 Process optimization • Quick cooling of kiln exhaust gases lower than 200° C. The critical range of temperature is usually passed through quickly in the clinker process; • Characterize a good operation and use this as a basis to improve other operational performance. Having characterized a good kiln, establish reference data by adding controlled doses of waste, and look at changes and required controls and practice to control emissions; • Management of the kiln process to achieve stable operating conditions, which may be achieved by applying process control optimization (including computer-based automatic control systems) and use of modern, gravimetric solid fuel feed systems; • Minimizing fuel energy use by means of: preheating and precalcination as far as possible, considering the existing kiln system configuration; use of modern clinker coolers, enabling maximum heat recovery; and heat recovery from waste gas; Control of chemicals listed in Annex C: Indirect measures for control of chemicals listed in Annex C have a minor impact in specific cases, but are an important element of integrated emission control. Such measures are generally applicable and are of simple technical construction. Hazardous waste preparation • Pretreatment of hazardous waste, with the objective of providing a more homogeneous alternative fuel and more stable combustion conditions, may include drying, Kåre Helge Karstensen [email protected] Page 168 of 420 shredding, mixing or grinding depending on the type of waste. Important is to give attendance to • Well-maintained and appropriate storage and handling of the alternative fuel; Input controls • Consistent long-term supply of alternative fuels (supplies of a month or more) is required to maintain stable conditions during operation; • Careful selection and control of substances (sulphur, nitrogen, chlorine, metals and volatile organic compounds); entering the kiln • Continuous supply of fossil fuel and alternative fuel with specification of heavy metals, chlorine (limitation, product/process dependent), sulphur; • Feeding of waste through the main burner or the secondary burner in precalciner/preheater kilns (ensure temperature > 900o C); • No waste feed as part of raw mix, if it includes organics; • No waste feed during start-up and shutdown. Control of chemicals listed in Annex C: Indirect measures for control of such chemicals have a minor impact in specific cases, but are an important element of integrated emission control. Such measures are generally applicable and are of simple technical construction. Formation of chemicals listed in Annex C is possible within relevant temperature ranges. Stabilization of process parameters • Regularity in fuel characteristics (both alternative and fossil); Kåre Helge Karstensen [email protected] Page 169 of 420 • Regular dosage; • Excess oxygen; • Monitoring of CO. Control of chemicals listed in Annex C: Indirect measures for control of such chemicals have a minor impact in specific cases, but are an important element of integrated emission control. Such measures are generally applicable and help ensure stable operating conditions. Process modification • The off-gas dust should be fed back into the kiln to the maximum extent practicable, in order to reduce issues related to disposal and emissions. Dust that cannot be recycled should be managed in a manner demonstrated to be safe. Control of chemicals listed in Annex C: Indirect measures for control of such chemicals have a minor impact in specific cases, but are an important element of integrated emission control. In general, the primary measures mentioned above are sufficient to achieve an emission level below 0.1 ng TEQ/Nm3 in flue gases for new and existing installations. If all of these options do not lead to a performance lower than 0.1 ng TEQ/Nm3 secondary measures may be considered, as described below. Secondary measures The secondary measures cited below are installed at cement kilns for other pollution control purposes, but they show a simultaneous effect on emissions of chemicals listed in Annex C. Further improvement of dust abatement and recirculation of dust. Kåre Helge Karstensen [email protected] Page 170 of 420 Control of chemicals listed in Annex C: Efficiency may decrease with decreasing temperature of dust precipitation; general applicability; medium technical construction; capture of chemicals listed in Annex C bound to particles. Activated carbon filter This measure has high removal efficiency for trace pollutants (> 90%). Pollutants such as sulphur dioxide (SO2), organic compounds, metals, ammonia (NH3), ammonium (NH4+) compounds, hydrogen chloride (HCl), hydrogen fluoride (HF) and residual dust (after an electrostatic precipitator or fabric filter) may be removed from the exhaust gases by adsorption on activated carbon. The only activated carbon filter installed at a cement works in Europe is that at Siggenthal, Switzerland. The Siggenthal kiln is a four-stage cyclone preheater kiln with a capacity of 2,000 tons of clinker per day. Measurements show high removal efficiencies for SO2, metals and PCDD/PCDF (European Commission 2001). Control of chemicals listed in Annex C: General applicability; demanding technical construction. Selective catalytic reduction In general, selective catalytic reduction installations are applied for NOx control. The process reduces NO and NO2 to N2 with the help of NH3 and a catalyst at a temperature range of about 300°-400° C, which would imply heating of the exhaust gases. Up to now selective catalytic reduction has only been tested on preheater and semi-dry (Lepol) kiln systems, but it might be applicable to other kiln systems as well (European Commission 2001). Its high cost could make this solution economically unviable. The first full-scale plant (Solnhofer Zementwerke) has been in operation since the end of 1999 (IPTS 2004). Control of chemicals listed in Annex C: Deman¬ding technical construction; expected improvement in control of chemicals listed in Annex C by efficient catalysts. Kåre Helge Karstensen [email protected] Page 171 of 420 9.3 Performance requirements based on best available techniques Performance requirements based on best available techniques for control of PCDD/PCDF in flue gases should be < 0.1 ng TEQ/Nm3. Emission levels shall be corrected to 273 K, 101.3 kPa, 10% O2 and dry gas. Monitoring To control kiln process, continuous measurements are recommended for the following parameters: • Pressure; • Temperature; • O2 content; • NOx; • CO, and possibly when the SOx concentration is high; • SO2 (a technique is being developed to optimize CO with NOx and SO2). To accurately quantify the emissions, continuous measurements are recommended for the following parameters (these may need to be measured again if their levels can change after the point where they are measured to be used for control): • Exhaust volume (can be calculated but the process is regarded by some as complicated); • Humidity; • Temperature at particulate matter control device inlet; • Particulate matter; • O2; • NOx; • SO2; Kåre Helge Karstensen [email protected] Page 172 of 420 • CO. Regular periodical monitoring is appropriate for the following substances: • metals and their compounds; • Total organic carbon; • HCl; • HF; • NH3; • PCDD/PCDF. Measurements of the following substances may be required occasionally under special operating conditions: • Destruction and removal efficiency, in case of disposal of persistent organic pollutants in cement kilns; • Benzene, toluene, xylene; • Polycyclic aromatic hydrocarbons; • Other organic pollutants (for example, chlorobenzenes, PCB including coplanar congeners, chloronaphthalenes). It is especially important to measure metals when wastes with higher metal content are used as raw materials or fuels. Kåre Helge Karstensen [email protected] Page 173 of 420 10. Conclusion Many emerging economies do not have a proper hazardous waste management infrastructure in place. The development of a proper hazardous waste management infrastructure is not only required to protect human health and the environment but it is also necessary to sustain further development of their economies. Rapid industrial growth leads to increased levels of waste and hazardous waste generation often long time before proper disposal means are available. Environmentally sound disposal of hazardous chemicals is costly if export or new disposal facilities are considered and may not be affordable to many countries. The joining of the cement industry to the waste management needs, under well managed and controlled co-processing in cement kilns, can provide a viable, economical, sustainable and environmentally sound option for treating many hazardous and non-hazardous industrial wastes. Proper rules and regulations are however needed. Co-processing of wastes in cement kilns has been practised around the world for the last thirty years and shown to be an environmentally sound and cost-efficient treatment option. Both the EU and the US acknowledge the benefits of cement kilns for hazardous waste treatment but has imposed stringent regulation and permitting conditions to secure protection of health and environmental. A modern rotary dry cement kiln has many inherent features, which makes it ideal for hazardous waste treatment; such as high temperatures, long residence time, surplus oxygen during and after combustion, good turbulence and mixing conditions, thermal inertia, counter currently dry scrubbing of the exit gas by alkaline raw material, fixation of heavy metals in the clinker structure, no generation of by-products such as slag, ashes or liquid residues and complete recovery of energy and raw material components in the waste. Co-processing of AFRs and hazardous wastes in cement kilns will however usually constitute one tool in a complete toolbox, complementary with other treatment options, usually consisting of physical/chemical treatment, various incineration options and landfill. 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Van den Berg, M., Birnbaum, L.S., Bosveld, A.T.C., Brunstrom, B., Cook, P., Feeley,M., Giesy, J.P., Hanberg, A., Hasegawa, R., Kennedy, S.W., Kubiak, T., Larsen, J.C., van Leeuwen, F.X.R., Liem, A.K.D., Nolt,C., Peterson, R.E., Poellinger, L., Safe, S.H., Schrenk, D., Tillit, D., Tysklind, M., Younes, M., Wærn, F., Zacharewski, T., 1998. "Toxic Equivalency Factors (TEFs) for PCBs, PCDDs, PCDFs for Humans and Wildlife". Environmental Health Perspectives 106 (12), 775–792. Kåre Helge Karstensen [email protected] Page 214 of 420 Van der Sloot, H. A., 1991. Systematic leaching behavior of trace elements from construction materials and waste materials. In Waste Materials in Construction. Eds. J. J. J. M. Goumans, H. A. van der Sloot and T. G. Aalbers, pp. 19-36. Elsevier, Amsterdam. Van Loo, W., 2004. European PCDD/PCDF data from the cement industry. CEMBUREAU - The European Cement Association, 55, rue d'Arlon - B-1040 Brussels. http://www.cembureau.be. WBCSD, 2005. 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Kåre Helge Karstensen [email protected] Page 217 of 420 Annex 1 A review of the literature – general co-processing of AFR This chapter presents abstracts or excerpts of articles on general co-processing of waste materials in the cement industry. The abstracts presented should be identical to the original but is not nescesaraly presented in a chronological order. Using alternative fuels and the advantages of process modeling in cement manufacturing Kääntee et al. (2004): “Energy costs and environmental standards encouraged cement manufacturers world-wide to evaluate to what extent conventional fuels can be replaced by alternative fuels, i.e., processed waste materials. Clinker burning is well suited for various alternative fuels. In order select a suitable alternative fuel, a commercial modeling tool (ASPEN PLUS®) is used to model the four-stage preheater kiln system of full-scale cement plant (clinker production ca 2900 tons/day), using petcoke as fuel. The goal is to optimize process control and alternative fuel consumption, while maintaining clinker product quality. Calculations with varying amounts of different fuels are compared with a reference case. The dependence of process performance on the amount of combustion air is clearly demonstrated and the energy demand of the process could be predicted for varying fuel mixes”. Use of alternative fuels in the Polish cement industry Mokrzycki, Uliasz-Bocheńczyk and Sarna (2003): “Alternative fuels are made up of mixtures of different wastes, such as industrial, municipal and hazardous wastes. These fuels need to have an appropriate chemical energy content which depends on the type of components and their organic content. An industry that is particularly well suited to the employment of alternative fuels is the cement industry. There is a number of factors that promote the use of alternative fuels in cement kilns. Of these factors, the most notable are: the high temperatures developed, the appropriate kiln length, the long period of time the fuel Kåre Helge Karstensen [email protected] Page 218 of 420 stays inside the kiln and the alkaline environment inside the kiln. There are a number of countries that use their own alternative fuels in cement plants. These fuels have different trade names and they differ in the amounts and the quality of the selected municipal and industrial waste fractions used. The fuels used should fall within the extreme values of parameters such as: minimum heating value, maximum humidity content, and maximum content of heavy and toxic metals. Cement plants in Poland also use alternative fuels. Within the Lafarge Group, the cement plants owned by Lafarge Poland Ltd. have initiated activities directed at promoting the wider use of alternative fuels. There are number of wastes that can be incinerated as fuel in cement plants. Some that can be mentioned are: selected combustible fractions of municipal wastes, liquid crude-oil derived wastes, car tires, waste products derived from paint and varnish production, expired medicines from the pharmaceutical industry and others. The experience gained by the cement plants of Lafarge Cement Poland Ltd confirms that such activities are economically and ecologically beneficial. The incineration of alternative fuels in cement plant is a safe method for the utilization of waste that is ecologically friendly and profitable for the industrial plants and society alike”. Research on alternative fuels for the cement industry Mokrzycki and Uliasz-Bocheńczyk (2003): “One of the main methods for utilizing waste is its use as an energy source. Waste is only suitable for use as a fuel if it has a chemical energy content. This energy content depends most of all on the size of the (organic) combustible fraction and on the moisture content. To better employ the chemical energy contained in wastes, alternative fuels have been developed which are mixtures of different wastes. Some of these alternative fuels are: RDF, BRAM, SIBRCOM, INBRE, PAKOM, etc. Research carried out for a number of years in cement plants all over the world have clearly shown the advantages of waste utilization in clinker processes and cement production. The decisive factors promoting the use of cement kilns for the utilization of wastes are: the high incineration temperature, the large area of the furnace, the significant length of the kiln and the alkaline environmental inside the kiln”. Kåre Helge Karstensen [email protected] Page 219 of 420 Waste management and environmental protection by the use of alternative fuels in the cement production - experience from Germany - Bolwerk (2001): “The cement industry is net-shaped connected to the environment. The production process requires energy and that leads to emissions. Brown coal and hard coal are the predominant sources of energy in Germany. At present, there are many cement factories in Germany which use, or are planning to use, up to 75% secondary fuels (tyres, waste plastic, liquid/solid), in the production of cement.” “Cement plants differ in specialized waste burning constructions. They cannot be considered as a waste disposal plant for all kind of waste. Waste for utilization is a possibility, because their chemical composition is comparable with fuels and raw materials which are normally used. Past experiences have shown that the cement industry can play an important part in the utilization of secondary fuels. Key factors include favourable conditions inside rotary tube kilns, optimized process and safety technology, improved exhaust gas cleaning systems and a comprehensive control of the input substances.” Efficiency of destruction of waste used in the co-incineration in the rotary kilns Ottoboni et al. (1998): “This work presents a study about the efficiency of destruction of industrial waste, used in the co-incineration in rotary kilns of the cement industry, considering the principle of the chemistry equilibrium and the kinetic of the reactions. As an example, it has analyzed the burn of one hazardous waste which has in its composition toluene, xylene and dicloroethane. The temperatures of the transformation and the time of the reaction to the formation of sub-products which will originate CO2, H2O and HCl, are evaluated. Thus, the formation of the pollutants in the kiln is preliminary estimated and the different forms to control the emissions is also discussed”. Kåre Helge Karstensen [email protected] Page 220 of 420 Waste incineration in cement plants: constraints and development opportunities (a French-German comparison) Setbon (1997): “Is it possible to reconcile economic and ecological concerns? This article examines, through a French-German comparison, the case of obtaining a calorific value for waste used as substitute fuels in cement kilns. On the one hand, this new strategy for obtaining needed inputs offers to the cement industry an economic opportunity for lowering production costs (the main determinant of competitivity in this sector). On the other hand, the controlled incineration of wastes allows the cement industry to present an “environmentally friendly” image (savings of primary energy inputs, reductions in solid waste disposal requirements). Commercial decisions to invest in waste incineration options therefore must take account of a variety of supply cost, regulatory and social factors that render uncertain the economic viability and social legitimacy of the choice”. The economics of tire remanufacturing Ferrer (1997): “The world market for tires is described to identify the current material flow from raw materials to tires and the used tire disposal problem. Then, I describe the value-adding operations in the tire production process and in the tire rethreading process. Once rethreading is identified as the only recovery alternative that maximizes tires utilization, I explain why heat generation is the only recovery alternative, when rethreading is not technically feasible. The economic values of heat generation in electric plants and in cement kilns are discussed. The paper culminates with the case of rethreading, the tire remanufacturing process and the recommendation of a simple decision rule for selecting the number of times a tire should be rethreaded to maximize its utilization”. Kåre Helge Karstensen [email protected] Page 221 of 420 Thermal residue disposal in cement works – comparison with other methods of waste treatment Kreft (1995): “The law governing wastes gives priority to avoiding waste before it is recycled or treated in some other way. This sets the objectives for a modern waste economy with the ultimate aim of causing the least possible emission when dumping and landfilling unavoidable residues. Incineration of wastes plays a special part in this process as it goes a long way towards fulfilling the set objectives. In the future there will be no more of the traditional dumping and landfilling of household refuse. A review is given of the refuse treatment schemes which are currently in use and the results that they are achieving. When waste treatment is divided into the areas of combustion, landfilling of residuals, and flue gas cleaning then the following differences become apparent: - Combustion in cement rotary kilns take place at substantially higher temperatures than when burning in a refuse incineration plant, and the residence time of the flue gases is also significantly higher. This means that toxic compounds are destroyed more effectively in cement kilns than in a refuse incineration plant. The residuals produced in refuse incineration plants, such as slag and ash, do not occur when refuse is burnt in cement kilns because these mineral residuals become constituents of the cement. Their chemical compositions are similar to that of raw meal and do not affect the cement quality, while residuals from a refuse incineration plant have to be dumped and landfilled. On the other hand, flue gas cleaning in a cement works takes place in the process itself through contact between the flue gases and the raw meal, during which the acid gas constituents and heavy metals are deposited and to a great extent are retained in the cement. The flue gas cleaning systems installed are confined to dust removal, in which the dust which is removed also contains deposited residue components. The flue gas cleaning system installed in a refuse incineration plant is technically much more sophisticated, but also provides more effective separation. As a consequence it follows that symbiosis of the advantages of the two concepts is bound to produce a better scheme – combustion in a rotary cement kiln with the advantages of high temperatures and residence times while avoiding residuals, and integration of an extended flue gas cleaning system into the plant design for a cement kiln”. Kåre Helge Karstensen [email protected] Page 222 of 420 Experience with specialized control techniques when using secondary materials Greger (1994): “The use of new and unknown raw materials and fuels, especially the use of secondary material, requires a guarantee of a first class product quality, exclusion of any additional environmental pollution, a process technology which is not impaired by the use of secondary materials, preservation of the safety of the employees, and acceptability with clients, neighbors, authorities and staff. Evidence that these requirements and the official conditions which frequently go beyond them have been fulfilled is, among other things, making it necessary to use test methods which are new to cement works. Organic analysis, especially the use of gas chromatography, is a new type of problem for a cement laboratory. Used initially for regular checking of the PCB content in secondary fuels required as part of the plant licensing for thermal disposal of combustible liquid wastes, GC analysis is also suitable for qualitative and quantitative measurement of extracts form solid samples, exhaust gas constituents, organic total carbon, and grinding aids in cements. Regular measurement of trace elements in secondary fuels, also an official condition in licensing, requires the establishment of an extended analytical technique with X-ray fluorescence. This makes it possible to collect extensive data for trace elements in raw materials, fuels, clinker and dusts facilitate balances of heavy metals over fairly long time periods”. Burning of solid waste in cement kilns Hansen (1993): “The use of pumpable waste in cement kilns is widely practical in the United States. In 1991, 1.3 million tons were used in kilns replacing over 1 million tons of fossil fuel. Due to the environmental damage being caused by the disposal of solid wastes in landfills, there has been increasing incentive to manage these wastes by means other than landfills. Recycling or recovery of value from wastes rather than landfilling has gained popularity in the US. However, up to now, the only practical management practice has been disposal by thermal treatment. Since thermal treatment without any recovery of value is extremely costly and there is limited capacity for safe thermal treatment, many materials that have significant environmental risk continue to go to landfills”. Kåre Helge Karstensen [email protected] Page 223 of 420 “The development of a practical method for the use of solid waste as a replacement for fossil fuel in cement kilns not only provides an alternative to the environmental problem of landfills, but also reduces the environmental impact of the production of the fossil fuel it replaces. For the special category of wastes where thermal destruction is mandated, the replacement of fossil fuel results in the complete avoidance of the emissions that would have been created in a thermal treatment device. Further, the regulatory process that accompanies the management of wastes results in significant controls on the combustion device, controls that did not exist while using fossil fuel. As a result, the emissions of the newly controlled system using waste are often less than when the facility used fossil fuel only”. Waste-derived fuel as a supplementary energy source at the Woodstock Cement Plant Suderman, Nisbet and Hainsworth (1992): “The manufacture of cement is an energyintensive process. By burning waste fuels to recover their energy value, a typical cement kiln can burn 113 500 L of liquid waste per day, providing 20 to 25% of a kiln’s daily heat requirement. The total quantity of liquid industrial organic wastes generated in Ontario annually is over 1 000 000 tons”. “Lafarge Canada Incorporated initially considered the idea of using waste-derived fuels as a supplementary energy source in 1982. Following the successful completion of a preliminary evaluation program, the company embarked on a project to investigate the process and both the product and environmental impact of burning liquid industrial wastes in its cement kiln at Woodstock, Ontario. Over a 90-day period, all aspects of the test burn were monitored and documented, including fuel procurement and handling, fuel combustion and emissions monitoring, emergency response and, ultimately, closure of the test program. This information, along with the economic, environmental and energy-saving implications of the waste-derived fuel project, is documented in this report. In addition, Lafarge has documented the various steps that were taken in an effort to keep the local public informed and to gain their acceptance. The level of success and failure in the public information program is examined”. Kåre Helge Karstensen [email protected] Page 224 of 420 The reuse of petroleum and petrochemical waste in cement kilns Gossman (1992): “The integration of two seemingly diverse technologies, management of hazardous wastes and production of cement, appears to be having a profound effect on both industries: - Study after study has warned of severe consequences of shortfalls in the nation’s capability for hazardous waste management. Yet today, many types of wastes are in significant demand for use as supplemental fuel. - Cement manufacturing plants can evaluate different sources of new revenue for their facilities by providing waste management services. Usually, each new source of revenue also helps lower plant fuel or raw material costs in the never ending effort to remain competitive in a well established and mature market”. Replace coal by using refuse derived fuel, and reduce the fuel cost Thorndyke (1988): “St. Lawrence Cement is carrying out a feasibility study for a program to use refuse derived fuel (RDF) at the Mississauga plant. The RDF will partially replace the coal which is used at present as the kiln fuel. The primary objective of the program is to reduce the St. Lawrence Cement fuel costs, but other advantages of the program are that an alternative method to landfilling for the disposal of municipal solid waste is provided and the amount of coal purchased by the plant from the United States will be reduced”. “At the request of the St. Lawrence Cement, Ontario Research Foundation has prepared this report, in support of the feasibility study, to project and assess air emissions from the St. Lawrence Cement plant if the RDF program is implemented. This section of the report, Volume 1, describes the current plant operations and the effects on these operations when planned modifications to one of the kilns (Kiln #3) are completed and when RDF is used in the kilns in various combinations to partially replace coal. For both current and Kåre Helge Karstensen [email protected] Page 225 of 420 planned operations, stack gas volumetric flowrates and emission rates specific emission components are projected. In a second section of the report, Volume 2, these data are used in preliminary dispersion modeling for limited weather conditions to obtain component point of impingement concentrations which are then compared with the point of impingement standards and guidelines in Regulation 308 of the Ontario Environmental Protection Act. The air emissions assessment is concluded in Volume 2 by using more complex dispersion modeling which applies to all types of weather conditions, considers different averaging times and includes data for both local weather conditions and existing ambient air quality”. “There are three kilns at the St. Lawrence Cement plant. Two of these kilns, Kiln #1 and Kiln #2, are similar Rotary Kilns and use a conventional wet process for clinker production. The remaining kiln, Kiln #3, uses a dry process consisting of a Rotary Kiln and a combined Preheater / Precalciner. (In this report the Preheater / Precalciner is referred to in abbreviated form as the Precalciner) In Kiln #1 and Kiln #2, the coal is combusted in the Rotary Kiln with the raw meal where calcinations occurs, whereas in Kiln #3, about half the coal is combusted in the Precalciner (“precalcining zone”) and the remainder is combusted in the Rotary Kiln (“burning zone”). Most of the calcination occurs in the precalcining zone”. “For technical reasons, the amount of coal which can be replaced by RDF in a rotary cement kiln is limited and may be no more than about 20%, based on the higher heating content of the fuels. This is primarily because RDF has a lower heating value compared with coal and this will affect the flame temperature”. “The preferred option for burning RDF at the plant is to replace 20% of the coal used in all three kilns. However, several options for burning RDF have been investigated since there may be limitations on the amount of RDF which can be used in Kiln #3 (assuming RDF is added only to the burning zone of this kiln) and on the amount of RDF which is available. In addition to the preferred option, one of the options for burning a reduced amount of RDF is to add RDF only to the burning zone of Kiln #3 to replace 20% of the coal. Another option, in which the total amount of RDF used is about the same, is to replace 20% of the coal used in Kiln #1 and Kiln #2, and 10% of the coal used in kiln #3, added only to the burning zone of the Kiln #3. Projected emissions from these three options for burning RDF at the plant are presented in this report together with projected emissions for current operations and planned operations, (after modifications to Kiln #3 are completed), using coal as the only fuel”. Kåre Helge Karstensen [email protected] Page 226 of 420 “Air emissions from the three kilns pass through electrostatic precipitators to remove most of the particulate material and are then discharged to the atmosphere through a single, common Kiln Stack. Air emissions from the Coal Mill, where coal is pulverized and dried in preparation for use as a fuel, are also discharged through the same stack. Similarly, air emissions from the Aerofall Mill, which is used to grind primarily limestone, may also be discharged through the Kiln Stack. With planned modifications to Kiln #3, the capacity of the kiln will be increased and a substantial portion of the burning zone exhaust gases (up to 50%) may bypass the precalcining zone, and be directed to the Kiln Stack after being conditioned and passed through a baghause. The purpose of the Bypass is to remove alkali metals, primarily as metal chlorides, from the kiln system. Currently, a smaller portion of the burning zone exhaust gases (61%) bypass the precalcining zone. These gases are also conditioned but are passed through an electrostatic precipitator before being discharged to the atmosphere through a separate stack, the Bypass Stack. The modifications to Kiln #3 are currently under construction and will be completed independently of the RDF program”. “Based on information provided by St. Lawrence Cement and obtained from a number of other sources, a material balance was prepared for current kiln operations when coal alone is used as the fuel. Then, similar material balances were prepared to reflect the planned process modifications to Kiln #3 and the use of RDF in the three different combinations to partially replace coal. A comparison of the material balances showed that neither the flowrates nor the composition of the major gaseous components in the stack gases (carbon dioxide, nitrogen, oxygen and moisture) will change significantly with RDF usage, although there will be considerable changes when the Kiln #3 capacity increases and the Bypass System volume is increased to 50%. As a result, the dispersion characteristics of the Kiln Stack gases will not change significantly with the RDF program, provided that there are no other operating changes”. “Projected emission rates of Kiln Stack components (other than the major gaseous components) when the RDF program is implemented were obtained by a review of information from the following sources: - Actual emission tests carried out at Kiln #1, Kiln #3 and the Coal Mill during normal plant operations when coal alone is used as the fuel; Kåre Helge Karstensen [email protected] Page 227 of 420 - Analyses of raw meal, waste iron oxide, coal and RDF samples typical of the material presently used in the kilns or expected to be used in the kilns; - Literature survey of coal, RDF and municipal solid waste combustion”. “The following emission component groups were included in the environmental assessment: - Particulate material; - Acid gases; - Metals; - Inorganic elements; - Polychlorinated organics; - Polycyclic aromatic hydrocarbons”. “From an environmental perspective, these are the components which are generally considered to be the most important in flue gases discharged from coal and RDF combustion”. “Overall, it is concluded that with the planned plant operations and use of RDF, emission rates of some air emission components will increase. These components include polychlorinated organics and some metals. Even with these increases, however, it is not expected that environmental standards or guidelines for any of the emission components will be exceeded, as shown in Volume 2 of this report. In fact, all emissions are projected to be well below levels at which standards or guidelines may be exceeded”. The use of industrial sludges as raw materials in the cement industry Riganti, Fiumara and Odobez (1986): “Sludge arising from physico-chemical treatment of industrial waste waters can be used as a component of clinker meals in cement plants”. Kåre Helge Karstensen [email protected] Page 228 of 420 “The material on which the present experimental work is focused was obtained from industrial sludge poor in organic matter and rich in aluminum, iron and heavy-metal hydroxides. The metals are rendered inert by cement-based binders in full compliance with the current Italian provisions. The material was checked to verify that its component comply with the acceptability limits established by the users, and to assess the level of pollution produced at the processing site. The eluate obtained with CO2-treated water from the treated material does not show appreciable release of heavy-metals. Emission values at the chimney of the cement plant depend on the effectiveness of the gas filtering system. The addition of treated industrial sludge to kiln feed does not have an appreciable effect on the cement-plant chimney dust, and reduces operating cost, without affecting the properties of the product (clinker) and the plant’s operating stability”. Portland cement: constitution and processing. Part 1: cement manufacture Roy: “The manufacture and utilization of portland cement is an excellent illustration of the interdisciplinary nature of materials science. A series of two modules, of which this is the first, is designed to put the subject in perspective, beginning with the chemistry of formation of the anhydrous phases which make up cement from its raw material components, and outlining the steps, processes and mechanisms involved, whereby cement, the key ingredient in concrete is prepared”. How to install a waste system Smith: “When a waste-derived fuel (WDF) system is installed in a cement plant, it must satisfy a variety of needs. It must: - provide a means of disposal for unwanted material; - be compatible with the manufacture of cement; - meet federal, state and local regulations; - provide a reasonable return on investment for all involved”. Kåre Helge Karstensen [email protected] Page 229 of 420 “Since a WDF facility exists primarily to reduce the impact that hazardous material may have on the environment, it is essential that each facility be operated in a manner that minimizes leakage, spillage, evaporation, runoff and other detrimental occurrences that would adversely affect the environment. The concept and design of a WDF facility and its components are the critical aspects of an economical, environmentally acceptable system. It is the responsibility of the owner, engineer and contractor to design and build an operatorfriendly system and reduce any chance of environmental contamination”. “Most WDF facilities have six basic components: - transport vehicle unloading; - material handling/control; - waste material storage; - material processing; - fuel blanding; - fuel burning”. “Each of these components offers an opportunity for technical excellence in design and operation, and each offer a different potential for problems and liability issues. The proper combination of these components provides the basis for a successful facility”. “Transport vehicle unloading plays a major role in most WDF facilities. For instance, it is the bulk truck and railcar unloading areas that set the “feeling” for non-company individuals about the entire facility. If truck drivers have a clean facility in which they can easily unload, they will spread positive feedback to others. In an industry which often conjures up negative images, positive public relations can be helpful”. “It is important that unloading areas with adequate spill containment be provided for each type of material shipment that is received. Zones that are impervious to the material being handled and that are capable of impounding the entire content to the transport vehicle need to be established. Crack control must be a prime ingredient in the spill containment Kåre Helge Karstensen [email protected] Page 230 of 420 design, and concrete containments that hold liquids need to be steel-lined, since concrete is porous to many solvents”. Best available technology for environmental protection in the cement industry Solisio, et al.: “This paper deals with available technology applicable to the cement industry for the maximum limitation on the atmospheric emissions from steady sources. The main pollutants taken into account are represented by particulate, SOx and NOx” “The effectiveness of the policy atmospheric pollution control of a new italian factory designed according to the best available technology, has been assessed through theoretical and experimental techniques”. “The results are then presented and discussed in order to show an actual example of application of the so-called “Clean Technologies”, where the prevention of pollution is mainly achieved, instead of the usual criteria for the mere protection of the environment”. Current knowledge of use of waste fuel in cement kilns Hazelwood, Gartner, and Smith (1982): “This study was initiated to document current knowledge concerning the use of waste fuels in cement kilns. Technical as well as economic factors affecting the use of cement kilns to destroy waste materials are reviewed. The recommendations thoroughly understand the impacts of this disposal technique”. “A number of plants have used wastes of relatively low toxicity to supplement their fuel needs. In addition, research in Canada, Sweden, and the United States have successfully demonstrated extremely high destruction efficiencies in cement kilns when burning highly toxic organic wastes. These studies indicate that a significant potential exists for the expanding use of cement kilns to safety dispose of many types of hazardous wastes generated in the United States and Puerto Rico”. Kåre Helge Karstensen [email protected] Page 231 of 420 “The risks incurred in burning toxic wastes in cement kilns appear to be very low. Given proper controls, emissions of organic compounds are likely to be at or below analytical limits of detection. Particulate loadings will increase when burning halogenated wastes hence excess dust capture capacity may be required to effectively utilize this type of waste”. “The economics of using waste fuels appears to be quite favorable for both cement plants and waste suppliers. Disposal of hazardous wastes through incineration or landfilling is likely to be more costly to waste generators than utilized cement kilns. Cement plants using waste fuels could not potentially reduce production costs by up to several dollars per ton”. “This report was submitted in partial fulfillment of Contract No. 68-03-2586 by A.T. Kearney, Inc., under the sponsorship of the U.S. Environmental Protection Agency. This report covers the period August 1979 to March 1981”. Kåre Helge Karstensen [email protected] Page 232 of 420 Annex 2 A review of the literature –co-processing of hazardous wastes This chapter presents abstracts or excerpts of articles on co-processing of hazardous waste materials in the cement industry. The abstracts presented should be identical to the original but is not nescesaraly presented in a chronological order. Clean – up of persistent organic pollutants in the industrialized world Brunner (2007): “While the accumulation of Persistent Organic Pollutants (POPs) and related waste toxins is a continuing threat to life and agriculture in many parts of the developing countries, it is being addressed actively, and successfully, in many countries of the industrialized world. In the United States perhaps the beginning of public awareness of the danger of uncontrolled chemical releases and contaminations was through the confluence of two events: publication of the book Silent Spring by Rachel Carlson and the realization that the future of our national symbol, the Bald Eagle, is in doubt”. “Silent Spring, released in 1962, imagined a world without the chirping of insects or the singing of birds because of the poisonous effects of DDT and other synthetic chemicals on wildlife, eventually making their way up the food chain and becoming a danger to humankind. At the same time there was convincing evidence that the Bald Eagle was becoming an endangered species, and perhaps a lost one in most of America because of the effects of these same chemical discharges on the bird’s reproductive cycle”. “With a heightened public awareness that the slogan “making life better through chemistry” had a very, very dark side, Congress passed the Solid Waste Disposal Act in 1965, the first federal law to require safeguards and encourage environmentally sound methods for disposal of household, municipal, commercial, and industrial refuse. In 1070 major changes were made, and this legislation became the Resource Recovery Act. In 1976 the Resource Conservation and Recovery Act (RCRA) was enacted, which is the basis of the current environmental framework for the control of industrial and other discharges into the environment. Specifically its goals were, and are: Kåre Helge Karstensen [email protected] Page 233 of 420 - To protect human health and the environment from the potential of waste disposal; - To conserve energy and natural resources; - To reduce the amount of waste generated, including hazardous waste; - To ensure that wastes are managed in an environmentally sound manner”. “Major changes of this legislation occurred as experience with its application developed. The 1984 amendments are known as the Hazardous and Solid Waste Amendments, and established systems for controlling hazardous waste, solid (primarily nonhazardous) waste, toxic substances, and petroleum products stored in underground tanks”. “The accumulation of chemical discharges from past activities were seen as a related problem, and they are addressed in RCRA’s companion law, the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA, also known as Superfund). CERCLA addresses the cleanup of inactive and abandoned hazardous waste sites”. “While RCRA has originated with the concern for effective control of wastes and other uncontrolled discharges into the environment, a similar fear was growing over the realization that hundreds of new chemicals are being developed each year and that some of them may have their own undesirable consequences if and when they are discharged into the environment. This was the basis of the enactment of the Toxic Substances Control Act (TSCA) in 1976”. “The new law gave EPA specific authority, which it earlier lacked, to move against older and new chemical hazards, including the authority to ban production of certain chemicals. The two most pressing needs were first, global, addressing the effect of fluorocarbons on the ozone layer protecting the earth from harmful ultraviolet radiation and second, a more one, dealing with the problem of PCBs”. Kåre Helge Karstensen [email protected] Page 234 of 420 “Manufactured since 1929, PCBs are a family of chemicals with low flammability and low conductivity, characteristics which led to their widespread use as cooling liquids and dielectric fluids in transformers and capacitors. They had been hailed as an industrial boon because their use prevented widespread occurrence of transformer fires, which had been all too common with the transformer fluids previously”. “With the recognition that there were serious unintended consequences of another “miracle chemical”, DDT, the public had little doubt in accepting the fact that evidence linking PCBs to skin cancer, reproductive failures, gastric disorders, skin lesions and other serious effects in laboratory animals could also be linked to humans. As a result PCBs were banned through TSCA, and the disposal of existing stocks was tightly regulated”. “TSCA regulations require that materials containing over 500 parts per million (or mg per kg) of PCBs can only be disposed of safety using EPA-approved incinerators at extremely high temperatures (greater than 1,200°C) and demonstrating a PCB destruction efficiency of 99.9999%, 6 nine’s destruction, or more than 1 gram of PCBs exiting the stack per ton of PCBs charged”. “As a result of this legislation and subsequent EPA regulations, over 20 million kg of high-level PCB-containing oils, primarily from heavy-duty electrical equipment, have been taken out of service since 1978 and most of them have been safely destroyed, without further incident”. “What we now call POPs, Persistent Organic Pollutants, originated with these two chemicals. And their control, in the United States, goes back well over a quarter century, to RCRA, CERCLA and TSCA legislative activity”. “Looking at the current POPs inventory, which presently includes the following dirty dozen of compounds, their control in the United States is as follows: Aldrin – RCRA Hazardous Constituent; Chlordane – RCRA Hazardous Constituent; Kåre Helge Karstensen [email protected] Page 235 of 420 DDT – RCRA Hazardous Constituent; Dieldrin – RCRA Hazardous Constituent; Dioxins – Special RCRA Waste; Endrin – RCRA Hazardous Constituent; Furans – Special RCRA Waste; Hepatachlor – RCRA Hazardous Constituent; Hexachlorobenzene – RCRA Hazardous Constituent; Mirex – Not Listed; PCBs – TSCA; Toxaphene – RCRA Hazardous Constituent”. “All but Mirex are specifically listed as hazardous wastes under RCRA or controlled under TSCA. The PCBs, as noted above, must be incinerated if they are present in concentrations in excess of 500 ppm (or 500 milligram/liter), with limited exceptions for the application of innovative technologies. If a RCRA waste is to be incinerated, which is regulated by RCRA, and not mandated, dioxins and furans are subject to a 99.9999% destruction and removal efficiency (six nines), while the other RCRA wastes must have no less than 99.99% destruction and removal efficiency (four nines). In all cases there are other restrictions on the incineration of these, as well as other hazardous wastes which include removal of any acid gases that are generated, control of particulate matter and any products of incomplete combustion, as well as control of carbon monoxide and other gaseous discharges”. “These destruction requirements were not arbitrary but were developed over years of analysis of the impact of the level of discharges affecting the public health, specifically to defining the maximum exposed individual (MEI) and the effect on this hypothetical person. Kåre Helge Karstensen [email protected] Page 236 of 420 The MEI is an individual located at the off-site location where ambient pollutant concentrations created by a facility are highest, even if this location is not populated”. “The EPA’s definition of acceptable risk is an additional lifetime (70 year) individual cancer risk to the potential MEI of 1 in 100,000. (The public’s perception of acceptable risk usually approaches zero when it comes to incinerators, and is closer to 100% when smoking or sunbathing, although either of these two activities result in significantly more danger than 1 in 100,000 – the danger may be closer to 1 in 3 that such activity will result in cancer in a 70 year lifetime.)” “But their very definition, POPs are organic, and any organic materials are subject to destruction through the application of heat. They will be destroyed when their temperature is sufficiently high, and there is enough air (oxygen) present to burn their carbon (organic) or other burnable constituents. This can be in an incinerator specifically designed for the destruction of that compound, or it can be in another system that while designed for another use, such as a cement kiln, has the appropriate temperature-time characteristics for destruction of the particular organic (POPs) in question”. “Thermal destruction requires that the material be held at a high enough temperature for a sufficient period of time that it will dissociate and be destroyed, ultimately resulting in the conversion of hydrogen present to water and carbon present to carbon dioxide”. “DDT requires a lower temperature for destruction than PCBs. This relatively high temperature tolerance by PCBs compounds are one reason for its use in electrical equipment, as noted above. It has a relatively high resistance to burning under the conditions under which it is used”. “It is not necessary to build an incinerator to achieve the required temperature of destruction. Many industrial processes generate the conditions necessary for the disposal of many POPs and many of these industries exist in the developing world. For instance, cement kilns are ubiquitous, and they may be candidates for POPs disposal. Note the following characteristics of cement kilns, lime kilns and similar systems processing alkali materials when applied to the disposal of a hazardous or toxic waste stream: Kåre Helge Karstensen [email protected] Page 237 of 420 - Chlorinated waste streams, such as the POPs dirty dozen, are neutralized by the alkali present in the process clinker. - Conversely, the chlorinated component in a chlorinated waste fulfills the need for chlorine in the clinker to reduce its alkali content, particularly in the manufacture of certain types of cement. - Investment in capital equipment is minimal because the cement or lime kiln and associated equipment are already in place. - Organic wastes with a significant heating value such as waste oils will allow a fuel savings in the process kiln. Fuel costs can run as high as 65% of the operating cost of a process kiln. - Ash from the destruction of the waste is absorbed in the process clinker. Heavy metals will tend to be trapped in the clinker as trace and inconsequential contaminants, and their fraction is too low to affect product quality. - There is a huge thermal inertia within the kiln. The large mass of clinker within the kiln at any one time tends to eliminate the possibility of rapid swings in temperature or other changes in the process. The process requires thermal stability to ensure product quality, and effective burnout of organic wastes. - The cement process requires that the temperature in the kiln be maintained at 1,370°C to 1,540°C, and the kilns are very long, generally over 100 meters long, which represents a relatively long gas retention time at these high temperatures. This temperature-residence time relationship will destroy any of the twelve POPs. - Air emissions equipment is already in place within cement or lime process kiln for the collection of particulate, and requires no additional investment for firing POPs or other organics besides, perhaps, specialty monitoring equipment to assure the destruction of these toxics. Kåre Helge Karstensen [email protected] Page 238 of 420 - The process kiln operates under a negative pressure, or draft. This is a requirement for kilns used as hazardous waste incinerators, which must be maintained at a negative pressure to prevent fugitive emissions”. “While these factors would tend to promote the use of these systems for POPs destruction, there are a number of other considerations which must be addressed, namely: - The location of the waste feed must be carefully considered to ensure effective burnout of organics (POPs). - Excess chloride can harm product quality. The chloride content of the waste must be known, and generally be limited to less than 0.7% if firing into cement process kiln. - Conventional process kilns are run with very little operator attention. Toxic and hazardous waste streams require continuous operator attention, which must be taken into effect when determining the cost of POPs destruction. - The storage and feeding of POPs and related materials require extensive personnel procedures to maintain personnel safety, and this is another cost factor above that normally encountered with a process kiln”. “In the United States and in other parts of the industrialized world, the cement or lime process kiln has been found to be an effective system, cost wise and process wise, for the destruction of POPs contaminated wastes”. “Besides the cement kiln, whose characteristics are discussed above, other systems may or may not have the ability to effectively destroy a POPs waste, depending on the nature of that waste. Looking at the characteristics of DDT, which requires the lowest temperatures of destruction of the dirty dozen, and hexachlorobenzene (HCB), which is one of the more refractory of these materials, the effectiveness of other process equipment has been determined”. Kåre Helge Karstensen [email protected] Page 239 of 420 “Other industrial furnaces that may be considered for POPs destruction would include the following; Carbon black furnaces; Open hearth furnaces for steel production; Lead smelters; Lightweight aggregate kilns; Zinc roasters”. “As noted above, a separate incinerator may not have to be built for POPs destruction. Any of these or other types of industrial furnaces may have the ability for firing and destroying POPs and POPs contaminated materials”. “It has been found that POPs have accumulated at various sites over a period of years, and decades. In the United States addressing site clean-up is through the Superfund directives, which is part of CERCLA (the Comprehensive Environmental Response, Compensation, and Liability Act of 1980). This legislation developed a series of procedures to determine who the Potentially Responsible Party (PRP) is, or the entity or group of entities who have responsibility for clean-up of the site in question. CERCLA also invokes a set of procedures to determine if the site is a an urgent and dangerous threat to the public health, and established a National Priorities List (NPL) which requires that these sites be placed on this list and get immediate attention”. “Once a site is on the NPL a set of alternatives for the clean-up of that site would be evaluated and the preferred one chosen. The majority of clean-ups have been through one or a combination of the following actions and technologies: Clean-up Methods for Superfund Sites Activated Carbon Treatment Carbon adsorbs passing organic molecules. Granular activated carbon (GAC) is most common. Contaminant is trapped in carbon pores. Same as fish tank filter operation. Water Is Pumped through a vessel full of GAC and gives up Contaminants. Air Stripping Kåre Helge Karstensen [email protected] Page 240 of 420 Removes volatile organic compounds (VOCs) from groundwater or surface water. Volatile vapors are transferred from water into a passing air stream. Air/VOC mixture is then treated to remove or destroy the VOC’s. Years to remove the contaminants. Bioremediation Uses naturally occurring microorganisms to degrade harmful chemicals. Bacteria, fungi, or yeast is trilled into top Layer of soil or injected into wells. Treats in situ (in place). Effective on oil and creosote. Needs ideal conditions. Capping Cover buried waste to prevent contaminant movement. Synthetic fiber, heavy clays, concrete cap. Used with pump and treat & gas vents. Minimum design life of 20 years. Must be monitored for settlement, standing water, erosion, cracks, and other degradation. Excavation Removal of contaminated material from hazardous waste site. Waste is moved using heavy equipment to licensed disposal/treatment facility. Care must be taken not to spread toxins to the nearby community during removal and transport through the neighborhood. Site is then graded & revegetated. Immobilization Cementateous material and chemical bind the waste. Bound waste is immobilized. Solubility is reduced to keep toxins from leaching and spreading. Kåre Helge Karstensen [email protected] Page 241 of 420 A monolithic block is left in place. Vitrification uses high temperature to convert waste to a hard glass-like substance. In Situ Vitrification Wastes, soils, sludges are melted in place. Glassy, solid mass that resists leaching. Soil/sludge is electrically melted. Destroys organic pollutants with heat through pyrolysis. Hoods are placed over the processing area to trap and process escaping gasses. Needs certain types of soil. Leachate collection Results when surface or ground water seeps through solid waste. Highly complex mix of contaminants. Can contaminate surface & groundwater. Can spread contamination beyond the waste site into the neighborhood. Collected by drains. Remediate with pumping & treatment. Pump and treat Most common treatment for groundwater. Aquifer water pumped from well. Recovered water is treated. Removed contaminants go to a disposal site. Helps control contaminant migration. Treatment includes bioremediation, carbon adsorption, air stripping, UV oxidation. Soil washing Liquids/Water scrubs soils of toxins. Separates fine silt and clay particles from coarser sand and gravel. Kåre Helge Karstensen [email protected] Page 242 of 420 Toxins are usually bound to silt & clay. Wash liquids can contain detergents. Contaminated liquid is itself treated to remove silt & clay. Water, silt, clay returned to site or is sent to permitted treatment facility. Thermal desorption Relatively low temperature heating removes contaminants from soils and sludges. Contaminants with low boiling points vaporize and are captured by vapor extractors. Immediate destruction. Extractors condense vapor or remove it with activated carbon. Condensate is reused or shipped to a permitted treatment facility. Incineration Destroy organics like dioxin, PCB’s & other OPOs. Can treat soils, sludges. solids, & liquids. Immediate destruction. May produce hazardous ash. Emissions must be controlled. A source of supplemental (fossil) fuel is required. Difficulties In Siting. Plasma-arc Disposal Effective destruction of all organics. Generates non-leachable residual. Immediate destruction. Classified by the USEPA as high-temperature incineration. Little experience with technology. Extremely expensive”. “As of April 2006, the NLP included 1,244 sites and an additional 59 have been proposed and are in the process of being evaluated for inclusion on the site. Since its Kåre Helge Karstensen [email protected] Page 243 of 420 inception, 970 sites have been cleaned up and work on an additional 44 is in progress. Over half of these sites included at least one of the dirty dozen of POPs compounds. And approximately a quarter of the remediated sites have been through incineration”. “In Europe member countries have each dealt with contaminated sites with their own methods and procedures. Many site remediations have been through trucking contaminated material to an incinerator off-site. They make much more use of incineration technology in Europe, and in most cases incinerators are either owned by or operated in concert with governmental agencies. There is greater cooperation than in the United States where the relationship between owner/operator and regulator may be adversarial”. “The European Union has begun to take notice of the problem of POPs and contaminated sites about ten years ago. They have established directives where they are concerned with secondary issues associated with Superfund site clean-ups. In the US the issue is getting the site clean-up, and other issues will fall into the private sector. In the EU, these secondary issues, such as damage to persons or property due to site contamination is part of the clean-up directive. They are attempting to find the party liable for site clean-up and that party may also be liable for crop loss, or sickness, or livestock destruction, etc. In the US the responsible party is sought, but even if that party cannot be found, the clean-up will continue through Government action and sponsorship, hoping to recover cost at a later time”. “The average time for clean-up of a site on the NLP is 12 years from the time that it has been designated on the NLP. The years of that time is spent in litigation and engineering studies, and only two years in the actual physical clean-up of the site. And this is without the added responsibility of dealing with secondary liability. In the EU directives, where a greater effort is made to find the responsible party and where these secondary issues of damage to life and property is to be considered, the clean-up process may require significantly more than the twelve years experienced in the United States”. “The United States had begun to address POPs in the environment over 30 years ago and the EU has only recently formulated their approach. In both cases there is, today, a clear recognition of the potential danger of POPs alone or in accumulations, and steps are well underway to address these issues”. Kåre Helge Karstensen [email protected] Page 244 of 420 Environmentally Sound Destruction of Obsolete Pesticides in Developing Countries using Cement Kilns Karstensen et al. (2005): “The accumulation and inadequate management of obsolete pesticides and other hazardous chemicals constitutes a threat for health and environment, locally, regionally and globally. Estimates indicate that more than 500,000 tons of obsolete pesticides are accumulated globally, especially in developing countries. FAO has been addressing this issue and disposed of approximately 3000 tons of obsolete pesticides in Africa and the Near East since the beginning of the 1990s. These pesticide wastes have mainly been shipped to Europe for high-temperature combustion in dedicated incinerators, a treatment option usually not available in developing countries”. “High temperature cement kilns are however commonly available in most countries and have shown to constitute an affordable, environmentally sound and sustainable treatment option for many hazardous chemicals if adequate procedures are implemented. Cement kilns have been used for disposal of obsolete pesticides in developing countries earlier but no study has been able to verify the destruction efficiency in an unambiguous way. Lessons learned from earlier experiences were used to carry out a test burn with two obsolete insecticides in a cement kiln in Vietnam. The destruction efficiency was measured to be better than 99.9999969 % for Fenobucarb and better than 99.9999832 % for Fipronil and demonstrated that the hazardous chemicals had been destroyed in an irreversible and environmental sound manner without new formation of dioxins, furans, hexachlorobenzene or PCBs, a requirement of the Stockholm Convention on POPs”. Implementation of using solid and hazardous wastes as supplementary fuel in Australia Jones et al. (1994): “The use of cement kilns for managing solid and hazardous wastes is facilitated by the high temperature, long gas retention periods, natural alkaline environment, minimum amount of waste produced and high thermal capacity. The main benefits include energy recovery, conservation of fossil fuels, reduction in cement production costs and the use of already existing facilities”. Kåre Helge Karstensen [email protected] Page 245 of 420 “The test burns conducted in cement kilns worldwide have demonstrated very high destruction efficiencies for most stable organic compounds, with toxic contaminants barely above the background levels”. “There are several cement plants in the US and Europe presently using solid and hazardous wastes as supplementary fuel. The application of this technology in Australia has been ignored in the past. An international conference (Kilburn’92) on the role of cement kilns in waste management was held recently in Australia and has enhanced the implementation of this technology in Australia”. Information support for the incineration of chemical waste in cement kilns Glažar Kornhauser and Musar (1993): “A specialized information system on industrial (hazardous) waste management has been developed and applied in Slovenia. It is composed of (1) computerized waste registry, (2) reference database on waste water management, (3) related database on river water pollution, (4) a prediction of waste generation module, and (5) an expert system for determination and prevention of river water pollution. Incineration of hazardous waste in cement kilns was identified as an efficient solution for over 20% of chemical waste accumulated. A specialized database on analytical control for this incineration was created, with the files on sampling, sample preparation, waste characteristics, and methods for proximate, survey and directed analyses. The method of structuring information into systems for the recognition of relationships and patterns was applied, resulting in a model system for analytical control of waste incineration on cement kilns presented in Fig. 4. The vertical branches of the system give the succession order of analyses for (1) cement raw materials, (2) primary fuel, (3) waste blended as secondary fuel, (4) stack gas, (5) dust from electro filters, and (6) cement produced. The hierarchical organization enables recognition of key analyses and pathways, as well as of optional procedures”. Destruction of chlorofluorocarbons in a cement kiln Kåre Helge Karstensen [email protected] Page 246 of 420 Ueno et al. (1997): “One of the thermal oxidation technologies recommended by the United Nations Environment Programme (UNEP) is destruction of chlorofluorocarbons (CFCs) in a cement kiln. The destruction of CFC12, CFC11 and CFC113 was studied in a cement kiln plant in actual commercial operation. CFCs were completely destroyed in the kiln under normal operating conditions. Hydrogen fluoride and hydrogen chloride generated by CFC decomposition were absorbed by cement materials. No formation of toxic halogenated organic compounds, such as polychlorinated dibenzo-p-dioxins or dibenzofurans (PCDDs/PCDFs), was observed in the CFC incineration”. Information support for toxic waste management Kornhauser et al. (1997): ”Toxic waste and its management constitute a major contemporary challenge to science and society. Every day over one million tons of hazardous waste are generated worldwide – 90% of it in the industrialized countries. Many countries, particularly those in transition, are burdened by tens of millions of tons of accumulated hazardous wastes. Most of these countries do not have the necessary means for replacement of polluting technologies. Capital intensive solutions are rarely accessible. The only realistic hope for toxic waste management is to mobilize the main resource available, i.e. a welleducated population, for creating awareness, setting up pollution prevention and waste management capacities, and introducing knowledge-intensive approaches in solving toxic waste problems. In this effort, universities have an important role to play. Such a programme on toxic waste management has been undertaken by the International Centre for Chemical Studies in Ljubljana (Slovenia), in co-operation with UNESCO and the United Nations Development Programme (UNDP). The programme has included the development and application of computerized information support for toxic waste prevention and management. International databases are processed regularly for the needs of specific projects in this field. Specialized databases have been created, and are regularly updated, for toxic substances and toxic waste generating processes, as well as for waste management and prevention technologies (in particular, incineration of toxic waste in cement kilns and microencapsulation of toxic products such as pesticides, for pollution prevention)”. Kåre Helge Karstensen [email protected] Page 247 of 420 “Attention has also been given to policy instruments and incentives for toxic waste management”. Incineration of waste liquid fuel review of the literature Trevor Scholtz (1989): “The St. Lawrence Cement Incorporated Plant in Mississauga, Ontario frequently uses waste solvents containing chlorinated hydrocarbons to replace a portion of the coal fuel used in the wet kilns. The purpose in using solvents in the kilns is to produce low-alkali cements by removing alkali metal chlorides as waste product”. “Emissions testing conducted on a wet kiln burning waste solvents has shown that the emissions of polychlorinated dibenzo-p-dioxins (PCDD) are much higher than would be expected on the basis of tests conducted at other combustion facilities. While the estimated ambient levels are well within present acceptable limits, it is anticipated that future regulations will make these limits more stringent. For these reasons, this study of the published literature has been carried out in order to assemble information on the various formation mechanisms and routes which have been identified as contributors to emissions of PCDD as well as the closely-related polychlorinated dibenzofurans (PCDF)”. “Based on the results of the literature review, there are three possible causes for PCDD and PCDF emissions: (i) they are present in the feed materials and pass through the kiln unburned, (ii) they form from chloroorganic precursors which result from the incomplete destruction of the waste solvent, and (iii) they form in the post combustion zone from inorganic carbon and chlorine sources. Clearly, each of these routes is dependent on the mixing and combustion conditions in the kiln. Published studies of the heat transfer, turbulence and combustion in cement kilns indicate that the prerequisite conditions to support any one of the above three emission mechanisms may exist depending on the flame characteristics, extent of the atomization of the waste fuel and degree of control of the combustion. Based on the present test results at St. Lawrence Cement, it is not possible to identify the dominant rout(s) leading to the measured PCDD emissions”. Kåre Helge Karstensen [email protected] Page 248 of 420 “The present analysis of the results of the literature review, together with the results of tests conducted at St. Lawrence Cement has led to a recommended course of study which will more fully define the PCDD emission problem from the wet kilns, so that future efforts can be directed towards appropriate remedial action. The recommended study involves emission measurements with and without waste solvent use, as well as a more complete characterization of the temperature and flow in the kiln”. Metal spikes for incinerator and BIF compliance test and trial burn Weitzmann et al. (1995): “This paper presents a discussion of the various chemical and physical forms of metal compounds that may be used for spiking during the trial burn or compliance test for hazardous waste combustion systems. It discusses the factors which should be considered in selection the forms of the spiking metals for organic (hot, high Btu, or high heating value) waste streams, aqueous waste streams, and solids waste streams. The paper focuses on the organic waste streams and compares to the use of organic or metal dispersion to the use of organometal compounds or aqueous solutions of metal compounds as spikes for these types of feed streams. It is concluded that metal dispersions appear to form particulate which is in the appropriate micron range to tax the air pollution control system’s performance. Dispersions of all regulated metals are commercially available in the required quantities for each application and they are relatively easy to pump, and to meter. Dispersions can be formulated so that their heating values are high enough to maintain the required elevated combustion and flame temperatures, and they are representative of the most common types of metal-bearing wastes sent to incinerators. The dispersions can also be used to spike metal compounds into water-based waste streams”. Staying under the limit Krogbeumker (1994): “Cement production is characterized by an extremely highenergy combustion process. The fuels available are, on the one hand, natural fuels such as coal, heating oil and natural gas, and on the other hand, secondary fuels commonly known as Kåre Helge Karstensen [email protected] Page 249 of 420 “junk” or “waste” fuels derived from other industrial productions process and waste disposal processes”. “The provisions of the Federal Emission Protection Law stipulate that secondary fuels should be avoided unless they can be utilized properly and harmlessly in accordance with the waste disposal process schematic – or wherever avoidance or utilization is technically impossible or unacceptable – they can be disposed of as harmless waste without adversely affecting the wellbeing of the general public”. “The utilization possibilities vary greatly from case to case. For example, the energy content can be utilized in energy conversion processes such as those which take place in incineration plants or power stations, or also in matter conversion processes, as occur in the production of cement clinker. That would offer the additional advantage of the unburnable portion contributing completely and without waste as a secondary raw material to the formation of the clinker”. Fuel substitution in cement kilns: an overview in the context of the proposed EU directive on the incineration of hazardous waste Mc Intyre (1994): “It is the European Commission’s intention to bring cement and other production processes which recycle hazardous wastes as substitute fuels under the provisions of the proposed Directive on the Incineration of Hazardous Waste. The Commission has recognised that such processes are primarily operated for purposes other than incineration of wastes and that adjustments need to be made to certain aspects of the Directive to facilitate the regulation of such plants under auspices of the Directive”. “As regards emissions specifically, Annex II of the first Draft of the proposed Directive provided for plants using substitute fuels in a manner which recognised the operating conditions of such plants. Unfortunately subsequent Drafts have consistently failed to recognise that for certain energy intensive production processes covered by Annex II, such as cement plants, it is often emissions arising from raw materials rather than fuel that dictate the levels of some pollutants and particularly SO2, TOC and CO in exhaust gases. The Kåre Helge Karstensen [email protected] Page 250 of 420 favourable combustions in cement kilns (high temperature, long residence time, oxidising conditions) ensure that the level of emissions of these parameters is independent of whether hazardous wastes are burnt in kilns or not”. “In is recognised that in most kilns certain emissions (such as TOC, CO and SO2) attributable to raw materials in the cement manufacturing process are not amenable to the emission limits currently proposed. It is also recognised that specific CO concentrations in the exhaust gas from cement kilns are required by the combustion process. It is possible to take these factors into account in developing controls for burning hazardous waste in such way as to ensure that the cement industry will burn wastes safely without any increase in the emissions of dioxins and other similar substances of concern associated with waste incineration”. “The influence of raw materials on the level of kiln exhaust gas emissions is recognised in national legislation regulating the cement industry in EU-Member State and consideration should be given to adjusting the provisions of Annex II to account for this. To this end, Cembureau has proposed an amendment to the Draft Directive that would take account of normal process conditions and emissions while ensuring that cement plants burning hazardous waste as fuel would be subject to as stringent limits and controls as purpose-built incinerators for that portion of kiln emissions arising from the combustion of waste”. “Fuel substitution in cement kilns leads to a significant decrease in the emission of greenhouse gases and other products of fossil fuel combustion including combustion residues. It also satisfies the waste management hierarchy as laid out in current EU legislation”. “This ERM Review considers the above issues in the context of the development of the EU Draft Directive and presents the case for an amendment to the proposed Directive’s current text if the cement industry is to contribute to waste management strategies within the European Union”. Kåre Helge Karstensen [email protected] Page 251 of 420 The use of monochlorobenzene as a principal organic hazardous constituent for destruction efficiency determinations in cement kilns Seebach et al. (1992): “Extensive research and development efforts have been devoted over the past ten years to the task of developing a list of suitable Principal Organic Hazardous Constituents (POHCs) or POHC surrogates to determine Destruction Efficiencies (DEs) in hazardous waste combustion processes. There have been proponents of various types of scales for POHC destruction difficulty – those based on the heat of combustion, on the auto ignition temperature, or on various thermo chemical kinetic and/or thermo dynamic parameters. However, many workers agree that one of the best methods to select a POHC that will challenge the combustion system’s destructive capability is to recognize the likely “failure mode” of the organic under the conditions to which it will be subjected. Thus, for example, a compound such as sulphur hexafluoride or perchloroethylene might be selected if the principal concern were adequate temperature, while a compound like monochlorobenzene (MCB) might be selected if the system operated at modest excess oxygen levels, but at very high temperatures (such as, for example, cement kilns). After exhaustive work, Dellinger and co-workers (1, 2, 3) have developed a listing of thermal stability for 320 organic compounds. Both pyrolytic and oxidative modes of failure of these compounds have been considered in preparing this list”. “Monochlorobenzene (MCB) appears as POHC number 15 on this list (3). Most of the compounds above MCB in the list are highly toxic (such as HCN, cyanogens, and carcinogenic polyaromatic hydrocarbons), difficult to measure (such as acetonitrile), or notorious products of incomplete combustion (PICs) such as benzene. SF6 is an attractive possibility, since it is #4 on the list, very easy to measure in low concentrations, and non-toxic (4,5). However, if the failure mode of concern is one of low oxygen, rather than low temperature, its selection is subject to criticism, since SF6 will decompose given adequate temperature, irrespective of O2 concentration. Therefore, while it may be use for generating supporting data, SF6 should probably not be selected as the only POHC for a trial burn in cement kilns”. Kåre Helge Karstensen [email protected] Page 252 of 420 “MCB thus seems an attractive choice for regulatory agencies, as it quite stable under high excess O2 conditions, and even more stable at lower O2. Furthermore, MCB is easily obtained in quantities great enough to run as extended test, is not prohibitively expensive, and is of only moderate toxicity. However, as recent data demonstrate, it is generally not an appropriate choice for use in cement kilns. The purpose of this paper is to provide the data to support this conclusion”. Hazardous waste fuels and the cement kiln Gabbard and Gossman (1990): “The integration of two seemingly diverse technologies, management of hazardous wastes and production of cement, appears to be having a profound effect on both industries: - Study after study has been warning of severe consequences of shortfalls in the nation’s capability for hazardous waste management. Yet today, many types of liquid wastes are in significant demand for use as supplemental fuel. - Cement manufacturing plants can evaluate different sources of new revenue for their facilities by providing waste management services. Usually, each new sources of revenue also helps lower plant fuel or raw material costs in the never ending effort to remain competitive in a well-established and mature market”. “Because of this, the small generator of liquid hazardous wastes such as spent solvents and various paint process residues finds his fees for off-site waste disposal services have actually gone down or remained constant, rather than escalating massively as had been predicted”. “The large volume waste generating plant that properly segregate and manages spent solvents, paint residues, and similar good Btu value materials can also take advantage of this competitive situation among the waste management options available to the plant”. Kåre Helge Karstensen [email protected] Page 253 of 420 Types of risks associated with the combustion of hazardous waste in cement kiln Edgerton and Ravishankar (1989): “An overview of the types of risks associated with the combustion of hazardous waste in cement kilns and the methodologies for assessing these risks is presented. A preliminary screening level risk assessment should be conducted in the planning stages of kiln conversion for combustion of hazardous waste. This assessment should include consideration of transportation risk, storage and handling risk, kiln emission and health risk, and risk of clinker contamination. A more quantitative assessment of health risks should be conducted after the trial burn, using measured values for each specific kiln’s emission rates. Finally, a risk management program should be implemented to assure that environmental control and safety practices are observed”. Incineration of hazardous waste in cement kilns Benestad (1989): “Stack gas analyses from a Norwegian cement kiln were performed during the incineration of hazardous waste. The kiln was operated by a dry cement process. Two studies carried out in 1983 and 1987 measured the emission of particles, organic micro pollutants including PAH, PCB and PCDD, chlorine and heavy metals. Both studies concluded that the type of fuel incinerated does not influence the emission of organic micro pollutants. The destruction of PCB was at least 99.9999%. The investigations shows that the emission of particles, PAH and other cyclic organic hydrocarbons are more influenced by operation conditions than the fuel incinerated”. Trial burns: methods perspective Johnson (1989): “This paper addresses the status and technology of several of the key stack sampling analysis methods required for conducting a trial burn test of a hazardous waste incinerator. The methods upon which most of the discussion is focused are EPA Method 0010, EPA Method 0030, and the new Multiple Metal Train. These methods have been Kåre Helge Karstensen [email protected] Page 254 of 420 shown to be reliable when used by knowledgeable and experienced personnel. They are definitely more technically sophisticated, and the equipment requires more skill and care than the simpler devices employed in the early days of emission testing. The state of the art is continuing to change rapidly, and more detailed procedures are becoming available”. Waste solvent combustion sampling at kiln 1 for St. Lawrence Cement Thorndyke (1989): “The St. Lawrence Cement Incorporated plant in Mississauga, Ontario, uses a conventional dry kiln with a precalciner (Kiln #3) and two conventional wet kilns (Kiln #1 and Kiln #2) to produce cement clinker. Frequently, waste chlorinated solvents are added to the wet kilns to produce low alkali clinker by removing the alkali metals as metal chlorides. Coal is normally used as the kiln fuel but the waste chlorinated solvents replace a portion of the coal as a fuel when they are used”. “Using waste chlorinated solvents in this manner may cause toxic trace chlorinated organic compounds to be emitted in the kiln gases but amounts might be expected to be insignificant because of the high kiln temperatures, long kiln residence time and scrubbing action of the kiln raw materials”. “No trace chlorinated organic emission data, however, appears to be available for other cement plants when waste chlorinated solvents are used. Therefore, St. Lawrence Cement requested ORF to carry out an emission program at Kiln #1, when waste chlorinated solvents were being used, in order to determine emission data for the following groups of trace chlorinated organic compounds: - Polychlorinated dibenzo-p-dioxins (dioxins); - Polychlorinated dibenzofurans (furans); - Chlorobenzenes; - Chlorophenols; Kåre Helge Karstensen [email protected] Page 255 of 420 - Polychlorinated biphenyls (PCBs)”. “Three separate tests were completed between July 5 and July 7, 1988, by ORTECH using standard sampling and analytical procedures”. “A comparison of these results with emission data for various other combustion facilities in Ontario showed that Kiln #1 is a major emitter of dioxins and chlorophenols when waste chlorinated solvents are combusted, although emission rates would probably be much lower when coal alone is used as a fuel, based on emission results obtained for an Ontario Hydro coal-fired generating station”. “Emission rates of dioxins and furans at Kiln #1 are unusual compared with the other facilities in that furans emissions were very low compared with dioxin emissions and dioxin emissions were confined to a relatively smaller number of major isomers. This indicates that the dioxins were formed in the kiln during combustion from one or more specific compounds in the waste chlorinated solvents”. “Dispersion modeling, based on the dispersion equations in Regulation 308 of the Ontario Environmental Protection Act, indicated that the maximum ground level impingement concentration resulting from the use of waste chlorinated solvents in Kiln #1 was 4.7% of the allowable provincial provisional guidelines for combined dioxin and furan emissions, with Kiln #1 operating alone. The equivalent percentage was less than 0.1% for the other trace chlorinated organic compounds”. “It can be expected that with two or three kilns operating this percentage for combined dioxins and furans would increase or decrease depending on whether waste chlorinated solvents were also used in Kiln #2, but would still not exceed about 6.8% for the probable worst case when the two wet kilns only are operating and both using waste chlorinated solvents at the same rate that was used in the present program for Kiln #1”. Kåre Helge Karstensen [email protected] Page 256 of 420 Trial burns for hazardous waste incineration permits Burton (1989): “A trial burn for a cement kiln which is be used as a hazardous waste incinerator is designed to determine how effectively that kiln is able to operate under specifiable “worst cases”. To make this determination with minimum time and cost while achieving maximum information requires careful planning and attention to general experience with trial burns. It also requires paying close attention to the specifics of what has been learned around the world with regard to the use of cement kilns as hazardous waste incinerators. On the basis of this evidence, it can be concluded that cement kilns offer considerable potential for the effective treatment of organic hazardous waste”. Performance audit results for volatile POCH measurements during RCRA trial burn tests Jayanty, Sokol and Von Lehmden (1988): “Audit materials containing principal organic hazardous constituents (POHCs) have been developed by EPA for use by federal, state and local agencies or their contractors to assess the accuracy of measurement methods used during RCRA trial burn tests. Audit materials are currently available for 27 gaseous organics in five, six, seven, and nine-component mixture at parts-per-billion levels (7 to 10,000 ppb) in compressed gas cylinders in a balance gas of nitrogen. The criteria used for the selection of 27 gaseous organic compounds is described”. “Stability studies indicate that all of the organic tested (with the exception of ethylene oxide and propylene oxide below 10 ppb levels) are stable enough to be used as reliable audit materials”. “Subsequent to completion of the stability studies, 89 performance audits have been conducted with the audit materials to assess the accuracy of the Volatile Organic Sampling Train (VOST) and bag measurement methods during or prior to RCRA trial burn tests. A summary of the audits conducted for each POHC and the measurement system audited is Kåre Helge Karstensen [email protected] Page 257 of 420 shown in this paper. The audit results obtained with audit gases during RCRA trial burn tests are generally within ±50 percent of the audit concentrations”. Safety arrangements for the auxiliary combustion of waste oils containing PCB in rotary cement kilns Krogbeumker (1988): “In the Federal Republic of Germany about 500 000 tons of waste oils containing polychlorinated biphenyls (PCB) as contaminants become available each year. Therefore, with the backing of the relevant authorities, tests are being carried out under industrial conditions with a view to ascertaining whether such waste oils can be harmlessly fired in cement kilns. In several series tests in which up to 10 percent of the overall fuel energy requirement of the kiln is to be provided by waste oil with progressively increasing PCB content ranging from 50 to 1000 ppm it is to be investigated up to what PCB content it is with certainty possible to achieve pollutant-free combustion. For this purpose comprehensive safety precautions have been taken to ensure reliable combustion. From the available results it can be inferred that, with adequate atomization of the oil in the gas steam, the PCB can be completely or very largely burnt in the cement kiln”. RCRA trial burn considerations Cudahy and Busmann (1987): “The publication of the first RCRA incineration regulations in December 1978 brought industrial incineration from a qualitative study of black smoke, ash and carbon monoxide to a new and relatively unknown quantitative area of destruction and removal efficiency (DRE). The new RCRA DRE performance standard has been one of the most significant occurrences in the history of industrial incineration, because the regulations will eventually lead through research to a better understanding of the fundamental physical and chemical process taking place in the incineration process”. “It is now over eight years since the publication of the EPA’s first proposed set of hazardous waste incineration (HWI) regulations in December 1978. These proposed regulations, which included the concept of trial burn, were followed by interim final HWI Kåre Helge Karstensen [email protected] Page 258 of 420 regulations in January 1981, and interim final amendments in June 1982. The purpose of this paper is to discuss the RCRA trial burn program relative to current status, existing technical issues, and trial burn testing results”. Hazardous waste combustion in industrial processes: cement and lime kilns Mournighan and Branscome (1987): “This report summarizes the results of several studies relating to hazardous waste combustion in cement and lime kilns. The tests included in this study are four kilns tested by the U.S. Environmental Protection Agency, four kilns tested by State agencies or the kiln operator, two Canadian tests, and one Swedish test. The predominant types of wastes tested included chlorinated organic compounds, aromatic compounds, and metal-contaminated waste oil. The kiln types include lime kilns and cement kilns, which included the dry, wet, and preheated processes. Fabric filters and electrostatic precipitators (ESPs) were the pollution control devices used in these processes, and the primary fuels included coal, coke, coal/coke, fuel oil, and natural gas/coke”. “The parameters examined in this report were Destruction and Removal Efficiency (DRE) of the Principal Organic Hazardous Constituents, particulate and HCl emissions, metals and the effect of burning hazardous waste on SO2, NOx, and Co emissions. The primary conclusion of this study is that DRE’s of 99.99 percent or greater can be obtained in properly-operating calcining kilns. Particulate matter can increase when chlorinated wastes are burned in a kiln equipped with an electrostatic precipitator. Those kilns equipped with fabric filters showed no change in emissions”. Evaluation of hazardous waste incineration in a dry process cement kiln Higgins and Helmstetter: ”This report presents the preliminary results of a test program conducted by SYSTECH Corporation at the Marquette Cement Plant in Oglesby, Illinois. The objective of this program was to compare the emissions resulting from co-firing low chlorine, high BTU liquid waste and coal in a dry process cement kiln with the emissions resulting from firing coal only”. Kåre Helge Karstensen [email protected] Page 259 of 420 “The characteristics of the liquid waste burned during the test were examined by performance of standard analytical methods, with particular emphasis on organic composition. Destruction and removal efficiencies (DREs) were calculated for our principal organic hazardous constituents (POHCs) of the fuel: methylene chloride; methyl ethyl ketone; 1,1,1-trichloriethane; and toluene. Additional analyses were conducted on the stack gases to determine particulate loading, SO2, NOx, total gaseous nonmethane organics (TGNMO), HCl, and metals emissions. The kiln dust was also sampled and analyzed for metals and Extraction Procedure (EP) toxicity”. “The results of these tests indicate that the cement kiln may be an ideal method of disposal for low chlorine, high Btu liquid wastes. The burning of liquid wastes in the kiln did not lead to any significant increase in particulate loading, SO2, NOx, TGNMO, or HCl over the levels observed during baseline coal-only test periods. Among the metals examined, only lead was found to significantly increase in emission rate during the liquid waste firing. No significant differences were observed in the EP toxicity of the kiln dusts sampled during the liquid waste and baseline tests, and only the concentration of lead was found to significantly increase in the kiln dust. Within the detection limits of the test method employed, the four POHCs measured were completely destroyed in the kiln”. Trial burn verification program for hazardous waste incineration Ananth et al.: ”The trial burn protocol described in the EPA Guidance Manual for Evaluating Permit Applications for the Operation of Incinerator Units has been followed in a case study of the Cincinnati Metropolitan Sewer District’s (MSD) incineration facility. This paper summarizes trial burn protocol requirements and presents the results of the protocol verification tests carried out at the MSD incineration research facility”. Kåre Helge Karstensen [email protected] Page 260 of 420 Determination of the thermal stability of selected hazardous organic compounds Dellinger et al. (1984): “Laboratory determined thermal decomposition profiles and kinetic data for a list of 20 organic compounds are reported. All data were obtained in flowing air at mean gas-phase high-temperature zone residence times ranging from one to six seconds. The extrapolated temperatures required for 99.99% destruction of the parent compound at two seconds mean residence time, T99.99 (2), ranged from 600 C for 1, 1, 1trichloroethane to 950 C for acetonitrile. The possible chemical mechanism for destruction of hazardous organic compounds are examined and used to explain trends in the experimentally determined thermal decomposition data. It is proposed, through proper application of the principles of organic chemistry, kinetics, and physics that laboratory gas-phase thermal decomposition data generated under controlled conditions can be incorporated into models of full-scale incineration and serve as a viable ranking of waste incinerability”. Destruction of PCB’s in cement kilns Black and Swanson (1983): “Polychlorinated biphenyls (PCB’s) are a group of chlorinated compounds synthesized initially in 1881 and brought into widespread commercial production from 1929 until their ban in 1976 by the United States Congress. During the 1960’s PCB were identified as a worldwide environmental contaminant with a chronic toxicity of important risk for humans”. “PCB regulations of May 31. 1979 (40 CFR Part 761) mandate incineration of PCB’s in concentrations greater than 500 part per million by EPA prescribed incineration conditions. Cement kilns, due to their unique operating characteristics, fulfil PCB incineration conditions. However, cement kiln destruction of PCB’s has not come into public and local governmental acceptance even though the need for PCB destruction capacity in the United States is a high environmental priority”. “Polychlorinated biphenyls (PCB’s) consist of related compounds having the general chemical formula C12H10-(a+b)Cl(a+b). Thus, PCB’s are chlorine substituted derivatives of Kåre Helge Karstensen [email protected] Page 261 of 420 biphenyl in which the hydrogen atoms have replaced by 1 to 10 chlorine atoms. Up to 210 chlorinated biphenyl isomers are theoretically possible”. “PCB’s are formed by the chlorination of biphenyl in the presence of an iron catalyst. The chemical composition of the final product is dependent on the amount of chlorination and blending of the final product. Thus, the final product is a mixture of isomers with the greatest percentage of compounds corresponding in composition to the average percent of chlorine. The most commonly referred to PCB trade name is Aroclor. An Aroclor mixture is commonly referred to by a four digit number such as 1242, where the 12 indicates chlorobiphenyl and the 42 represents the weight percent of chlorine present in the mixture”. “Properties of commercial PCB’s range from clear mobile liquids and pale yellow viscous oils to light amber resins and opaque crystalline solids as the higher molecular weight chlorobiphenyls are formulated in greater percentage of the PCB mixture. Useful characteristics of PCB’s which led to their worldwide acceptance and use include exceptional dielectric properties, thermal stability, non-flammability, excellent adhesive properties, low solubility in water, non-drying and thermoplastic properties”. “The very properties that make PCB so stable in the adverse environment commercial usage also allow them to remain intact in the natural environment. Regulatory response to PCB environmental effects was enacted under the Toxic Substances Control Act (TSCA, Public Law 94-469) by the Congress of the United States on October 11. 1976. The PCB disposal rules (40 CFR Part 761) became effective the day after EPA began enforcement of a ban on PCB manufacture. The disposal rules require proper disposal by landfill or incineration”. “Incinerators must meet the requirements of Part 761.40 and be approved by the Regional EPA Administrator including proof of a 99.9999 percent destruction efficiency. Liquid PCB incinerators must maintain the introduced liquids for a two second dwell time at 1200 C (±100C) at three percent excess air or for a one and one-half second dwell time at 1600C (±100C) at two percent excess air. Incineration must destroy PCB’s so the mass emissions are no greater than 0.001 grams of PCB’s/kg of PCB’s introduced into the incinerator”. Kåre Helge Karstensen [email protected] Page 262 of 420 “Combustion efficiency equations are shown in Part 761.40 (a)(2) using carbon dioxide and carbon monoxide measurements in stack gases. However, cement kilns calcine carbonates enriching the stack gas with additional carbon dioxide making the combustion efficiency equation inappropriate”. “Monitoring is also required for the PCB feed rate to the incinerator, combustion temperature, and stack emissions of oxygen, carbon monoxide and carbon dioxide. Prior to approval of an incinerator for disposal of PCB’s, the Regional EPA Administrator may require a successful trial burn to control problems are rare”. Treatment of hazardous waste in cement kiln within a decentralized scheme: the Norwegian experience Viken and Waage (1983): “Cement kilns have proved excellent devices for treating pump able hazardous waste. In Norway, the cement industry has been strongly involved in hazardous waste management, and plays a key role in the implementation of Norway’s hazardous waste management plan. The cement industry cannot solve all the hazardous waste problems faced in most countries, but as an integral part of a national scheme it can, under certain conditions, provide a sound treatment alternative for many types of such wastes both from an environmental and economic point of view”. “The purpose of this article is to provide a brief overview of the hazardous waste problem in Norway, some important properties of the national scheme and the role of the cement kiln in solving the problems. Furthermore, some major environmental and economic features of using a cement kiln in such a context will be outlined”. Knowledge of the potential problems as well as the opportunities by burning hazardous waste in cement kilns Chadbourne and Helmstetter (1983): “The cement manufacturing process is one of the oldest in the world, having been in practice for over 2000 years. It is also one of the most Kåre Helge Karstensen [email protected] Page 263 of 420 energy intensive, with up to 65 percent of the cost of the product attributable to energy consumption. In addition to high energy demand, the process conditions include extremely high temperatures. Cement clinker forms when the correct mixture of raw materials is heated to 2650° F. This requires combustion temperatures exceeding 3000° F. under oxidizing conditions. To accomplish this, gas temperatures above 2000° F. occur for several seconds (typically five seconds), which is much longer than residence times in permitted hazardous waste incinerators. These conditions are extremely favourable to the destruction of organic compounds and have led to extensive investigation into the potential for burning hazardous waste in cement kilns. Cement kilns consuming hazardous wastes have been tested for air emissions under various operating conditions. The substantial body of information on the emissions and handling of hazardous wastes from these studies has demonstrated that effective destruction of wastes can be accomplished with the added benefits of energy conservation and no significant change in air emissions”. “General Portland Inc. (GP) and SYSTECH Corporation (SYSTECH), during three years of continuous use of hazardous waste as fuel in cement kilns, have obtained knowledge of the potential problems as well as the opportunities that accompany this practice. Our experience in successfully using waste as fuel has resulted in the following conclusions: - Select combustible liquid wastes can successfully be used as fuel in cement kilns. - Available wastes that are desirable as fuels are hazardous materials by virtue of their ignitability and toxicity. - Blended hazardous waste materials retain their hazardous properties and must be properly handled even when used as fuels. - Prudent occupational safety and health procedures for these materials when used as fuels are the same as procedures required during the manufacturer and processing of the original chemical products. - Co-firing hazardous wastes in cement kilns conserves fossil fuel without requiring the increase in emissions which occurs from traditional waste incineration. Kåre Helge Karstensen [email protected] Page 264 of 420 - Comprehensive permitting and waste fuel analyses are prudent and necessary to avoid potential hazards posed by waste fuel use. - Appropriate permit conditions include: o Comprehensive analysis on each waste shipment; o Records on waste analysis, transfer, storage and use; o Control of emissions from storage tanks; o Continuous monitoring of combustion units; o Automatic shutdowns; o Periodic emission sampling; o Adequate emergency equipment and training; o Impervious concrete storage areas; o Good drainage and storm water control; o Adequate site security”. Burning chemichal wastes as fuel in cement kilns Lauber (1982): “Hazardous wastes in the environment represent one of our most serious problems. Ever increasing quantities of toxic wastes have contaminated our land, air, and water. Lack of adequate hazardous waste disposal facilities is a critical problem. Landfilling toxic wastes is no longer considered safe. The tragedy of the Love Canal has demonstrated the need for proper hazardous waste disposal facilities. Kåre Helge Karstensen [email protected] The best organic Page 265 of 420 chemical waste disposal method is process incineration. Cement kilns have been used for burning toxic chemical industrial wastes in Canada, Michigan, New York, Sweden, etc. Existing cement kilns, when properly operated, can destroy most organic chemical wastes. Even the most complex chlorinated hydrocarbons, including PCB can be completely destroyed during normal cement kiln operations, with minimal emissions to the environment. Burning toxic chemical wastes in cement kilns, and other mineral industries, is mutually beneficial to both industry, who generates such wastes, and to society and government, who want to dispose properly of such wastes in a safe, environmentally acceptable manner. The added benefit of energy conservation is important, since large quantities of valuable fuel can be saved in the manufacture of cement when such techniques are employed”. Destruction of chlorinated hydrocarbons in a cement kiln Ahling (1979): “For most of the substances analyzed, the emissions are lower than analytical detection limits. This means that the emissions of methylene chloride and trichloroethylene present in the solvent waste are less than 50 and 2 mg/kg, respectively, of fed substance. The test conducted on PCB shows that the destruction is better than 99.999 98%, which means that the emission is less than 0.2 mg/kg of fed PCB. In the tests on chlorinated phenols, peaks were observed indicating that very small concentrations of heptaand octachlorodibenzo-p-dioxin may occur in the flue gases. Owing to the small amounts, no complete analytical verification was possible. The effects on cement production were studied in a long term experiment, which showed that no change in cement quality and no interruption in operations occurred up to a chlorine input of 0.7% of the clinker production. At a higher input, there were tendencies for ring formation”. Burning waste chlorinated hydrocarbons in a cement kiln at the St. Lawrence Cement Co., Mississauga, Ontario MacDonald et al. (1977): “An experimental program was carried out in 1975/76 at the St. Lawrence Cement Co., Mississauga, Ontario in which waste chlorinated hydrocarbons, containing up to about 46 weight percent chlorine, were burned in a rotary cement kiln. The Kåre Helge Karstensen [email protected] Page 266 of 420 chlorinated hydrocarbons were burned in three distinct phases of increasing difficulty of combustion. Materials burned included mixtures of ethylene dichloride, chlorotoluene and up to approximately 50 percent polychlorinated biphenyls (PCB)”. “These materials were destroyed in the cement kiln with at least 99.98 percent efficiency in all cases. Emissions of high molecular weight chlorinated hydrocarbons were not detected. Three light chlorinated hydrocarbons, dichloromethane, chloroform and carbon tetrachloride, were found in the emissions in the part per billion or lower range. The quantity of precipitator dust requiring disposal, as well as emissions of particulate matter, increased during the test”. “The chlorine input from the chlorinated hydrocarbon waste up to about 0.8 weight percent relative to clinker and this effectively reduced the alkali concentration of the clinker in direct stoichiometric proportion. A reduction in fossil fuels used while burning chlorinated hydrocarbons was noted”. Kåre Helge Karstensen [email protected] Page 267 of 420 Annex 3 A review of the literature – environmental and health effects This chapter presents abstracts or excerpts of articles on environmental and health effects of co-processing of waste materials in the cement industry. The abstracts presented should be identical to the original but is not nescesaraly presented in a chronological order. Formation, release and control of dioxins in cement kilns -a review Karstensen (2007): “Co-processing of hazardous wastes in cement kilns have for decades been thought to cause increased emissions of PCDD/PCDFs - a perception that has been evaluated in this study. Hundreds of PCDD/PCDF measurements conducted by the cement industry and others in the last few years, on emissions and solid materials, as well as recent test burns with hazardous wastes in developing countries do not support this perception. Newer data has been compared with older literature data and shows in particular that many emission factors have to be reconsidered. Early emission factors for cement kilns co-processing hazardous waste, which are still used in inventories, are shown to be too high compared with actual measurements. Less than ten years ago it was believed that the cement industry was the main contributor of PCDD/PCDFs to air; data collected in this study indicates however that the industry contributes with less than 1% of total emissions to air. “The Stockholm Convention on POPs presently ratified by 144 Parties, classifies cement kilns co-processing hazardous waste as a source category having the potential for comparatively high formation and release of PCDD/PCDFs. This classification is based on early investigations from the 1980s and 1990s where kilns co-processing hazardous waste had higher emissions compared to those that did not burn hazardous waste. However, the testing of these kilns was often done under worst case scenario conditions known to favour PCDD/PCDF formation”. “More than 2000 PCDD/PCDF cement kiln measurements have been evaluated in this study, representing most production technologies and waste feeding scenarios. They generally indicate that most modern cement kilns co-processing waste today can meet an emission level Kåre Helge Karstensen [email protected] Page 268 of 420 of 0.1 ng I-TEQ/m3, when well managed and operated. In these cases, proper and responsible use of waste including organic hazardous waste to replace parts of the fossil fuel does not seem to increase formation of PCDD/PCDFs”. “Modern preheater/precalciner kilns generally seems to have lower emissions than older wet-process cement kilns. It seems that the main factors stimulating formation of PCDD/PCDFs is the availability of organics in the raw material and the temperature of the air pollution control device. Feeding of materials containing elevated concentrations of organics as part of raw-material-mix should therefore be avoided and the exhaust gases should be cooled down quickly in wet cement kilns”. “PCDD/PCDFs could be detected in all types of solid samples analysed: raw meal, pellets and slurry; alternative raw materials as sand, chalk and different ashes; cement kiln dust, clinker and cement. The concentrations are however generally low, similar to soil and sediment.” Pollutants emitted by a cement plant: health risks for the population living in the neighbourhood Schuhmacher, Domingo and Garreta (2004): “The aim of this study was to investigate the health risks due to combustor emissions in the manufacturing of Portland cement for the population living in the neighbourhood of a cement kiln in Catalonia, Spain. Pollutants emitted to the atmosphere in the course of cement production were modelled. The ISC3-ST model was applied to estimate air dispersion of the contaminants emitted by the cement plant. Air concentrations of NO2, SO2, PM10, metals, and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), as well as the potential exposure in the vicinity of the facility, were assessed via models based on US EPA guidance documents. PCDD/F and metal concentrations were also modelled for soil and vegetation. Based on these concentrations, the levels of human exposure were calculated. Individual cancer and non cancer risks for the emissions of the cement kiln were assessed. Health effects due to NO2, SO2, and PM10 emissions were also evaluated. Risk assessment was performed as a deterministic analysis. The main individual risk in the population was evaluated in a central-tendency and a high-end Kåre Helge Karstensen [email protected] Page 269 of 420 approach. The results shows that the incremental individual risk due to emissions of the cement plant is very low not only with regard to health effects, but also in relation to toxicological and cancer risks produced by pollutants such as metals and PCDD/Fs emitted by the cement kiln”. Collecting air samplings for analyzing; to set a risk level for carcinogenic benchmark concentrations Tam and Neumann (2004): “Ambient air samples collected from five monitoring sites in Portland, OR during July 1999 to August 2000 were analyzed for 43 hazardous air pollutants (HAP). HAP concentrations were compared to carcinogenic and non-carcinogenic benchmark levels. Carcinogenic benchmark concentrations were set at a risk level of one-inone-million (1×10-6). Hazard ratios of 1.0 were used when comparing HAP concentrations to non-carcinogenic benchmarks. Emission sources (point, area, and mobile) were identified and a cumulative cancer risk and total hazard index were calculated for HAPs exceeding these health benchmark levels. Seventeen HAPs exceeded a cancer risk level of 1×10-6 at all five monitoring sites. Nineteen HAPs exceeded this level at one or more site. Carbon tetrachloride, 1,3-butadiene, formaldehyde, and 1,1,2,2-tetrachloroethane contributed more than 50 % to the upper-bound lifetime cumulative cancer risk of 2.47×10-4. Acrolein was the only non-carcinogenic HAP with hazard ratios that exceeded 1.0 at all five sites. Mobile sources contributed the greatest percentage (68%) of HAP emissions. Additional monitoring and health assessments for HAPs in Portland, OR are warranted, including addressing issues that may have overestimated or underestimated risks in this study. Abatement strategies for HAPs that exceeded should be implemented to reduce potential adverse health risks”. Effect of burning supplementary waste fuels on the pollutant emissions by cement plants: a statistical analysis of process data Prisciandaro, Mazziotti and Veglió (2003): “This paper shows how some statistical tools can be applied in the process analysis of real plant data, e.g. in the clinker production by using alternative fuels (shredded tires and waste oils) as alternative fuels in clinker kilns of Kåre Helge Karstensen [email protected] Page 270 of 420 two different cement plants. Statistical Students’s t-tests, stepwise linear regression models and factor analysis were employed in the data analysis to evaluate the effect on the atmospheric stack emission of these alternative fuel feeding. Moreover a quite large improvement in the knowledge of the process have been obtained by statistical analysis of the data process that very often suffer of internal correlation among the process variables under investigation. Experimental results statistically analyzed have shown encouraging results, if less than 20% of regular fuel is replaced with alternative one: in particular clinker characteristics were unmodified, and stack emissions (NOx, SO2 and CO mainly) were, in the case of tires, slightly incremented, but remaining almost always below the law imposed limits; in the case of waste oils, polluted gas emissions were even decreased. Some empirical equations relating the stack emissions with some process data have been also obtained to be used for process analysis purposes”. Cement manufacture and the environment, part I Oss and Padovani (2002): “Hydraulic (chiefly portland) cement is the binding agent in concrete and mortar and thus a key component of a country’s construction sector. Concrete is arguable the most abundant of all manufactured solid materials. Portland cement is made primarily from finely ground clinker, which itself is composed dominantly of hydraulically active calcium silicate minerals formed through high-temperature burning of limestone and other materials in a kiln. This process requires approximately 1.7 tons of raw materials per ton of clinker produced and yields about 1 ton of carbon dioxide (CO2) emissions, of which calcination of limestone and the combustion of fuels each contribute about half. The overall level of CO2 output makes the cement industry one of the top two manufacturing industry sources of greenhouse gases; however, in many countries, the cement industry’s contribution is a small fraction of that from fossil fuel combustion by power plants and motor vehicles. The nature of clinker and the enormous heat requirements of its manufacture allow the cement industry to consume a wide variety of waste raw materials and fuels, thus providing the opportunity to apply key concepts of industrial ecology, most notably the closing of loops through the use of by-products of other industries (industrial symbiosis)”. Kåre Helge Karstensen [email protected] Page 271 of 420 “In this article, the chemistry and technology of cement manufacture are summarized. In a forthcoming companion article (part II), some of the environmental challenges and opportunities facing the cement industry are described. Because of the size and scope of the U.S. cement industry, the analysis relies primarily on data and practices from the United States”. Cement manufacture and the environment, part II Oss and Padovani (2003): “Construction materials account for a significant proportion of nonfuel materials flows throughout the industrialized world. Hydraulic (chiefly portland) cement, the binding agent in concrete and most mortars, is an important construction material. Portland cement is made primarily from finely ground clinker, a manufactured intermediate product that is composed predominantly of hydraulically active calcium silicate minerals formed through high-temperature burning of limestone and other materials in a kiln. This process typically requires approximately 3 to 6 million Btu (3.2 to 6.3GJ) of energy and 1.7 tons of raw materials (chiefly limestone) per ton (t) of clinker produced and is accompanied by significant emissions of, in particular, carbon dioxide (CO2), but also nitrogen oxides, sulphur oxides, and particulates. The overall level of CO2 output, about 1 ton/ton clinker, is almost equally contributed by the calcination of limestone and the combustion of fuels and makes the cement industry one of the top two manufacturing industry sources of this greenhouse gas. The enormous demand for cement and the large energy and raw material requirements of its manufacture allow the cement industry to consume a wide variety of waste raw materials and fuels and provide the industry with significant opportunities to symbiotically utilize large quantities of by-products of other industries”. “This article, the second in a two part series, summarizes some of the environmental challenges and opportunities facing the cement manufacturing industry. In the companion article, the chemistry, technology, raw materials, and energy requirements of cement manufacture were summarized. Because of the size and scope of the U.S. cement industry, the article relies primarily on data and practice from the United States”. Kåre Helge Karstensen [email protected] Page 272 of 420 PCDD/F and metal concentrations in soil and herbage samples collected in the vicinity of a cement plant Schuhmacher (2002): “In May 2000, the levels of a number of metals (As, Cd, Pb, Hg, Zn, Co, Mn, Tl, Ni nad V) were determined in 16 soil and herbage samples collected in the vicinity of a cement plant from Sta. Margarida i els Monjos (Catalonia, Spain). Metal concentrations were also analyzed in air filters from three sampling stations placed near the facility. For most metals, concentrations were similar or even lower than previously reported values for other areas from Catalonia. On the other hand, the levels of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) were also determined in four soil and 16 herbage samples. Mean values were 0.37 and 0.16 ng I-TEQ/kg for soils and herbage, respectively, values which in comparison with data from other surveys are rather low. No significant differences between metal and PCDD/F concentrations in samples collected at distances lower or greater than 3.5 km of the facility were noted. The current results show that the cement plant has a low impact on the metal and PCDD/F levels in the environment under direct influence of the facility. These results should be of interest to assess future temporal variations in the levels of metals and PCDD/Fs in this area”. Field testing of particulate matter continuous emission monitors at the DOE Oak Ridge TSCA incinerator Dunn et al. (2002): “A field study to evaluate the performance of three commercially available particulate matter (PM) continuous emission monitors (CEMs) was conducted in 1999-2000 at the US Department of Energy (DOE) Toxic Substances Control Act (TSCA) Incinerator. This study offers unique features that are believed to enhance the collective US experience with PM CEMs. The TSCA Incinerator is permitted to treat PCB-contaminated RCRA hazardous low-level radioactive wastes. The air pollution control system utilizes MACT control technology and is comprised of a rapid quench, venturi scrubber, packed bed scrubber, and two ionizing wet scrubbers in series, which create a saturated flue gas that must be conditioned by the CEMs prior to measurement. The incinerator routinely treats a wide variety of wastes including high and low BTU organic liquids, aqueous, and solid wastes. Kåre Helge Karstensen [email protected] Page 273 of 420 The various possible combinations for treating liquid and solid wastes may present a challenge in establishing a single, acceptable correlation relationship for individual CEMs. The effect of low-level radioactive material present in the waste is a unique site-specific factor not evaluated in previous tests. The three systems chosen for evaluation were two beta gauge devices and a light scattering device. The performance of the CEMs was evaluated using the requirements in draft Environmental Protection Agency (EPA) Performance Specification 11 (PS11) and Procedure 2. The results of Reference Method 5i stack tests for establishing statistical correlations between the reference method data and the CEMs responses are discussed”. Carbon dioxide emissions from the global cement industry Worrel (2001): “The cement industry contributes about 5% to global anthropogenic CO2 emissions, making the cement industry an important sector for CO2-emission mitigation strategies. CO2 is emitted from the calcination process of limestone, from combustion of fuels in the kiln, as well as from power generation. In this paper, we review the total CO2 emissions from cement making, including process and energy-related emissions. Currently, most available data only includes the process emissions. We also discuss CO2 emission mitigation options for the cement industry. Estimated total carbon emissions from cement production in 1994 were 307 million metric tons of carbon (MtC), 160 MtC from process carbon emissions, and 147 MtC from energy use. Overall, the top 10 cement-producing countries in 1994 accounted for 63% of global carbon emissions from cement production. The average intensity carbon dioxide emissions from total global cement production is 222 kg of C/t of cement. Emission mitigation options include energy efficiency improvement, new processes, a shift to low carbon fuels, application of waste fuels, increased use of additives in cement making, and, eventually, alternative cements and CO2 removal from flue gases in clinker kilns”. Kåre Helge Karstensen [email protected] Page 274 of 420 Letter to the editor: comments on “The health effects of living near cement kilns; a symptom survey in Midlothian, Texas” Pichette (2000): “In an article published in Toxicology and Industrial Health, Volume 14, Number 6, pp. 829-842, Legator et al. present results of a symptom survey they conducted in the city of Midlothian, Texas. The Texas Natural Resource Conservation Commission (TNRCC) offers a commentary regarding the use of a symptom survey to evaluate the health status of the residents of Midlothian, and concerns regarding the limitations of the survey. The TNRCC was provided a unique opportunity to review the data collected during the survey and to participate in the oral deposition of Dr. Marvin Legator, the principal investigator, who discussed the results during a deposition related to an administrative hearing regarding permitting one of the three operating cement companies in Midlothian. The TNRCC is able to offer a perspective of this symptom survey that may not be apparent to the casual reader or peer reviewer. There are numerous issues that the TNRCC has identified in their review of the authors’ symptom survey; however, we limit our commentary to issues that are most salient”. Mass balance of toxic metals in cement and aggregate kilns co-fired with fossil and hazardous waste-derived fuels Eckert et al. (1999): “The co-firing of conventional fossil fuel with hazardous wastederived fuel (WDF) in cement and aggregate kilns has increased considerably since 1984. Data are compiled from compliance-test reports for cement and light-aggregate kilns at steady-state conditions. These data reveal that the major of each metal incorporated into the kiln dust and product (cement clinker or aggregate product). Distribution ratios, for kiln dust and emissions relative to the total kiln system, are calculated for the metals arsenic (As), beryllium (Be), cadmium (Cd), chromium (Cr), and lead (Pb). Calculations, which use these ratios, balance the input and output metal mass by assigning the remaining metal to the product. These balance calculations include kilns that recirculate kiln dust and those that do not. Comparing reported and calculated metal concentrations in the product (cement clinker or aggregate product) provides a qualitative method for evaluating metals balance. Most Kåre Helge Karstensen [email protected] Page 275 of 420 compliance data yield poor agreement between the input and output masses. Metal distributions in kilns that recirculate different portions of cement kiln dust (CKD) indicate an increased tendency to concentrate As and Cr into CKD with increased CKD recirculation. This effect likely results from the rather low volatility of As and Cr. Metal concentrations in CKD, which are computed for the co-firing of WDF and fossil fuel in the kilns, are distinctly higher than those based on burning fossil fuel alone. A moderate to strong correlation of CKD metal concentrations with fuel concentrations indicate a fundamental control of CKD composition by fuel composition. Metal concentrations calculated for the transient approach to steady-state conditions provide a theoretical representation of that process. Equilibration test data, from compliance reports, show an irregular approach to steady-state conditions. This variable accumulation and release behaviour appears typical of the transient part of the process, and may increase the uncertainty in assessing steady-state conditions”. The health effects of living near cement kilns; a symptom survey in Midlothian, Texas Legator et al. (1998): “Cement kilns are major sources of toxic air emissions. Regulations based on demonstrated concentrations of specific chemicals, and risk assessments with inherent limitations and uncertainties, are the current methods of preventing exposure to “unsafe” emission levels. Monitoring data are frequently incomplete. These limitations mandate that residents residing near cement kilns be evaluated for adverse health effects. This study reports findings from a symptom survey conducted in Midlothian, Texas, which adds to the limited but growing body of knowledge showing that persons living near cement kilns are experiencing increased respiratory effects. This cross-sectional study uses randomized sampling and an extensive health questionnaire, covering 12 physiological systems, to determine differences in reported health symptoms between the study community (Midlothian, Texas, n=58) and the reference community (Waxahachie, Texas, n=54). Findings indicate significant elevations in reported respiratory symptoms in the study community (p-value 0.002). Although the comparatively small sample size is a limitation, the fact that only “respiratory effects” were highly significant supports the efficacy of this investigation. Respiratory effects would be the major anticipated outcome from the known exposures under investigation. This specificity of response (i.e. elevation in respiratory symptoms only), indicates that “response bias” was not a significant factor in this study”. Kåre Helge Karstensen [email protected] Page 276 of 420 Heavy metal outputs from a cement kiln co-fired with hazardous waste fuels Guo and Eckert (1996): “Measured data from a kiln equilibration test are analyzed for heavy metal outputs from a cement kiln co-fired with hazardous waste fuels. Metal outputs from stack emissions, cement kiln dust and cement clinker are considered. Equations are derived for predicting all three metal outputs at any hazardous waste feed rate under steady state conditions. Through analysis of two steady state conditions, at the beginning and end of the equilibration test, essentially the same ratios of metal feed rates are found to be distributed to the kiln dust at either high or low metal feed rates. Applying the same distribution ratios in the derived equations, metal concentrations of wasted kiln dust are predicted when the kiln is not using hazardous waste. Measured concentrations of arsenic, beryllium, cadmium, chromium, and lead in wasted kiln dust, at the highest intended hazardous waste feed rates to the kiln, are 68, 10, 72, 18 and 68 times those predicted for feed rates with no hazardous waste. In addition, the intermediate, non-steady state segment of the equilibration test is analyzed. If metals are assumed not to accumulate in the kiln, the intermediate metal concentrations in cement clinker are predicted to be substantially higher than those at the final steady state”. Environmental challenges Evans (1998): “The cement business is generally perceived as an industry with many of the characteristics which tend to present a high profile in the environmental arena, such as: - Large factories which are often isolated from other industries and which are usually attached to a substantial quarry operation. - Large volumes of production which require large volumes of fuel to be burnt and which produce large volume of combustion products. Kåre Helge Karstensen [email protected] Page 277 of 420 - A cost base which necessitates on-going investigation of alternative fuel sources whilst maintaining the goal of continuous environmental improvement”. “It is against this background that the industry has invested, and will continue to invest, many millions of pounds and thousands of man hours into the continuous improvement of its environmental performance. This has included the successful implementation of environmental management systems accredited to ISO 14001, on all of Blue Circle’s UK cement plant sites”. Determining controls on element concentrations in cement kiln dust leachate Duchesne and Reardon (1998): “Cement kiln dust is a waste residue composed chiefly of oxidized, anhydrous, micro-sized particles generated as a by-product of the manufacture of Portland cement. When cement kiln dust is brought into contact with water, high concentrations of potassium, sulphate and caustic alkalinity are leached. Other constituents are leached to a lesser extent. The objective of this study was to leached determine whether the concentration of a given chemical constituent in a kiln dust leachate is controlled by the precipitation of a secondary mineral phase or whether its concentration depends on its initial availability to the leachate solution and its subsequent diffusive flux from hydrating particles with time. Differentiating between two distinctive styles of leaching behaviour is necessary to predict the chemical composition of kiln dust leachate under dynamic flow conditions in disposal environments. Evidence of solubility control was found for Si, Ca, Mg, Al, Zn, Ti, Sr, and Ba. The concentrations of Na, Cl, K, Mo, Cr and Se, however, were found to have no solubility control. Because of the observed lack of solubility control and the particularly high concentrations of Cr and Mo in kiln dust leachate, we tested two additives (at 10 mass%) to reduce their concentrations: (1) aluminium oxide to promote the precipitation of calcium aluminosulfates and the proxying of chromate and molybdate for sulphate in their structures; and (2) iron metal to promote the reduction of chromate and molybdate to lower valent and less soluble forms. Neither treatment had any effect on the concentration levels of Cr and Mo in solution”. Kåre Helge Karstensen [email protected] Page 278 of 420 Environmental relevance of the use of secondary constituents in cement production Schneider and Kuhlmann (1997): “Cement companies improve the cost-effectiveness of the production process by using secondary materials, and at the same time they make a positive contribution to the environmentally compatible utilization of these materials. From the overall ecological point of view the utilization of secondary materials on a cement works is in some ways significant superior to other methods of utilization or even disposal. The evaluation criteria for environmental compatibility are laid down in, among other places, the German Recycling and Wastes Act. This states that an evaluation should be based mainly on the expected emissions, the energy utilization, the residues generated and the effect on the product. All investigations indicate that the heavy metal concentrations in the exhaust gases from rotary kiln systems do not come into the environmentally relevant category. The contribution by a cement works to the surrounding ambient pollution levels lies significantly below environmentally relevant concentrations. The use of secondary materials conserves primary raw materials and fuels. A comparative ecobalance was drawn up based on the example of CO2 emissions when using plastic materials in a cement works. Initial results shows that utilization in the clinker burning process is particularly good value when compared with other methods. It is primarily the levels of trace elements in the feed materials which have the greatest effect on the product. However, all available investigations shows that the release of heavy metals from concrete components is not environmental relevant. When secondary fuels are used in the clinker burning process the resulting concrete can be re-used without any reservations. The investigations described in this article show that the cement process is eminently suitable for environmentally friendly utilization of secondary materials”. Health effects from hazardous waste incineration facilities: five case studies Pleus and Kelly (1996): “In 1990, Greenpeace released a report about waste incineration entitled, “Playing with Fire” (Costner and Thornton 1990). Chapter 5 of this report is a compilation of frequently cited allegations of health and environmental impacts of five facilities that incinerate hazardous waste. The authors describe them as “among the few cases where formal or informal health surveys have been conducted” (Costner and Thornton Kåre Helge Karstensen [email protected] Page 279 of 420 1990). If these reports are true, they would indicate an important limitation to the use of hazardous waste incineration because of the adverse effects to local residents”. “The purpose of this paper is to review the scientific basis of these five case studies. For each case, a complete description of Greenpeace’s five case studies from the “Playing with Fire” report is quoted under the heading, Allegation. This is followed by a description of the available information in each case, summarized under Source Investigation. In each case, no scientific basis for the allegations could be found”. Possibilities to reduce dioxin/furan and PCB emissions when using alternative combustibles in the cement industry Bolwerk (1992): “Due to many tests and constant operations it appeared in the past that a modern cement plant is to a high degree suitable for the environmentally friendly use of multifarious products”. “The energy which is by now brought into the cement process by burning fossil energy carriers can be substituted up to 50% by the use of energy-rich combustibles. Essential preconditions for environmentally sound residual product disposal are problem-free continuous operating of the installation even feeding of the substances via the kiln’s primary and a safety system which ensures that burning takes place only when specific operating parameters (e. g. temperature, quantity of raw meal, primary fuel) are observed”. “In addition, appropriate measures like a bypass must ensure that the increased chlorine input does not give rise to operational problems in the calcining and transitional zone (kiln-preheater zone). The conditions for the cement burning process – high temperatures, sufficient sojourn times, oxidizing atmosphere – in connection with an optimized process, security and observation technology guarantee that the emissions of dioxin and furan are below the limit values of0,1 TEQ/cubic meter (TEQ = toxicological equivalent) in force in Germany and that the PCB’s are destroyed with high efficiency”. Kåre Helge Karstensen [email protected] Page 280 of 420 A study of emissions, offsite concentrations, and health effects by burning hazardous waste in cement kilns Kelly and Beahler (1992): “Burning hazardous waste in cement kilns has been the focus of widespread controversy in the United States over the past two years. Many allegations of inherent lack of safety, inadequate emissions controls, and consequent impacts to health and environment have been levelled at these facilities, many of which have been burning hazardous waste as supplementary fuel for a decade or more. To date, none of these allegations have been verified thorough medical or regulatory investigations. All test results to date have shown no adverse health effects as a result of the fuel programs”. “Midlothian, Texas, about 30 miles from Dallas, is believed to be the site of the highest concentration of cement plants burning hazardous waste in the world. Three plants are within a three-mile radius of each other, of which two are currently permitted to burn hazardous waste fuels; a total of about 108,000 tons of hazardous waste fuel were used in each of 1990 and 1991. The third plan has applied for permission to burn hazardous waste and used tires as supplementary fuel under the newly-enacted federal Boiler and Industrial Furnace Rule of 1991. Midlothian is also the focus of some of the strongest allegations about adverse health effects: ranging from cancer, rashes, and birth defects, to “massive poisoning” in general”. “In response to allegations of adverse health impacts, the Texas Air Control Board (TACB) in 1990 launched a major study of the offsite exposure concentrations to approximately 118 chemicals and chemical compounds in the Midlothian area. Although the study focused on ambient air sampling, with approximately 5,021 chemical analyses of compounds in air, TACB staff also conducted analyses of a wide variety of other matrices in response to citizens’ requests, including asphalt, water, soil, hay, and other media. A total of 6,112 analyses in addition to an unquantified number of stack emissions analyses have been reported to date involving 145 chemicals and chemical compounds from all sources”. “The exposure study is the largest such investigation ever conducted of a community where hazardous waste fuels are burned in cement kilns. Including the stack tests from the Kåre Helge Karstensen [email protected] Page 281 of 420 cement plants, an estimated $2.5 million US have been expended to date investigating offsite exposure over the past 20 months and comparing the results to applicable health effects criteria. All available monitoring data and the most recent emissions data taken in the community through June 1992, by both TACB and by the cement industry, are complied in this report”. “The measured offsite concentrations were compared to applicable federal and state criteria by the Effects Evaluation Division of the TACB. At this writing, 99.33% of the analytical results were found to be below conservative federal or state screening levels (i.e. only 0.67% exceeded initial screening criteria), generally indicating “no adverse health effects” would be expected in the community (Willhite, 1992). The results are believed to have far-ranging implications for other communities where the burning of hazardous wastes in cement kilns is being considered, and represent a major turning point in the overall understanding of offsite impacts associated with burning hazardous wastes in cement kilns”. Sampling of trace constituents in the clean gas from rotary cement kilns Kuhlmann et al. (1991): “The German Clean Air Regulations (TA Luft) of 1986 sets limits to the concentrations of inorganic substances (trace elements) in dust form. It is also necessary to check whether, due to the physical conditions (pressure, temperature) under which the exhaust gases are discharged and at which a substantial proportion of the substances can be present as vapour or gas, the total of the vapour, gas and dust emissions also complies with the stipulated mass concentrations. The measurements of filter-passing constituents in the clean gas from rotary cement kilns shows that only mercury produces appreciable amounts in vapour or gas form which will therefore also have to be determined as part of the emission measurements. With the other trace elements investigated (As, Cd,Pb, Tl), either no filter-passing constituents were detected (As, Tl) or else they lay close to the detection limits of the method of measurement. Values of up to 0.009 mg/m3 (std. state, dry) where found with cadmium, and of up to 0.016 mg/m3 (std. state, dry) with lead. It therefore follows that, with the exception of mercury, there is no need for measurement of filter-passing constituents during normal emission measurements at cement plants in accordance with the German Clean Air Regulations when the limits as specified in these regulations have to be Kåre Helge Karstensen [email protected] Page 282 of 420 checked. The process parameters of the sampling system used by the Cement Industry’s Research Institute, consisting of dust probe as specified in VDI 2066 and separate probe for filter-passing exhaust gas constituents, are comparable with the values mentioned in the preliminary draft of the VDE Guidelines 3868. Comparison measurements with the two systems on a cement kiln system produce matching results”. Experiences regarding pollution control problems in connection with the production of cement Bolwerk (1986): “Based on the raw materials and combustibles, the reactions resulting from the burning of the cement clinker and the utilization of waste products (e. g. waste oils, sludge asphalt, tyres, household refuse), the reactions in the cement kiln plays an important role as far as the emission behaviour of such plants is concerned. The dust generated during the burning of clinker as well as the resultant gaseous and vaporous compounds of the alkali metals, sulphur, halogens and heavy metals create circulation processes in the kiln, which increase the concentration of the condensates. On the basis of existing balance measurements the maximum emission for the various kinds of trace elements can be estimated. The values determined in this way are normally below the limits in force in the Federal Republic of Germany. In order that the environment is carefully controlled it is above all important that environmental control bodies function well”. Detecting waste combustion emissions Johnson (1986): “The disposal of hazardous wastes, especially organic chemicals, by incineration has been the subject of rapidly increasing interest during the past several years. When such wastes are incinerated, their composition is not the only characteristic that must be determined. Other factors of at least equal importance must be ascertained”. “These include the varieties and concentrations of any air contaminants that may be emitted during the incineration process. The presence or absence of contaminants shows how Kåre Helge Karstensen [email protected] Page 283 of 420 well a unit is operating and whether it will perform well enough to meet environmental standards”. “Research on developing adequate methods of sampling and analysis of the emissions is in progress. These sampling methods are generally applicable not only to incineration but also to processes closely related to incineration, such as the cofiring of waste in industrial boilers and the burning of contaminated heating oil”. “Although this article briefly discusses methods for sampling inorganic hazardous compounds, its primary emphasis is on ways of sampling organic compounds likely to be designated as principal organic hazardous constituents (POHCs) for a trial burn. These methods employ equipment such as the modified method five train (MM5), which includes an XAD-2 sorbent module; the source assessment sampling system(SASS); the recently developed volatile organic sampling train (VOST); and assorted containers such as glass bulbs and plastic bags”. Kåre Helge Karstensen [email protected] Page 284 of 420 Annex 4 A review of the literature – guidelines This chapter presents abstracts of guidelines on co-processing of waste materials in the cement industry. The abstracts presented should be identical to the original but is not nescesaraly presented in a chronological order. The GTZ-Holcim Guidelines on Co-Processing Waste Materials in Cement Production The GTZ-Holcim Guidelines on Co-Processing Waste Materials in Cement Production was published in 2006. Executive Summary Different types of wastes have been successfully co-processed as alternative fuels and raw materials (AFR) in cement kilns in Europe, Japan, USA, Canada and Australia since the beginning of the 1970s. These Guidelines are meant to gather the lessons of that experience and offer it particularly to developing countries that need to improve approaches to waste management. Some developing countries will need capacity building help before launching AFR programs. The Guidelines, meant for all of the cement industry and all of its stakeholders, result from a public-private partnership between Deutsche Gesellschaft für Technische Zusammenarbeit GmbH (GTZ) (www.gtz.de) and Holcim Group Support Ltd. (→ www.holcim.com). These findings and recommendations are based on experiences from industrialized and developing countries, as well as from the public and private sectors. They are also based on initiatives of bilateral and multilateral organizations to improve waste Kåre Helge Karstensen [email protected] Page 285 of 420 management at national and local levels, as well as attempts by the cement industry to reduce environmental degradation resulting from cement production. They reflect international laws and conventions. The use of AFR can decrease the environmental impacts of wastes, safely dispose of hazardous wastes, decrease greenhouse gas emissions, decrease waste handling costs and save money in the cement industry. It will help in achieving the targets set in Agenda 21 of the “Earth Summit” in Rio de Janeiro (1992), the Johannesburg Declaration on Sustainable Development (2002) and the Millennium Development Goals. However, there are some basic rules and principles that should be observed. AFR use should respect the waste hierarchy, be integrated into waste management programs, support strategies for resource efficiency and not hamper waste reduction efforts. Following certain basic rules assures that the use of AFR does not have negative impacts on cement kiln emissions. Co-processing should not harm the quality of the cement produced. Countries considering co-processing need appropriate legislative and regulatory frameworks. National laws should define the basic principles under which co-processing takes place and define the requirements and standards for co-processing. Regulators and operators should conduct baseline tests with conventional fuels and materials so they can compare AFR results to these. Some wastes should never be co-processed; these range from unsorted municipal garbage and certain hospital wastes to explosives and radioactive waste. Other wastes will need pre-processing before they can be used, and approaches to AFR use should take account of the need to effectively regulate and manage these pre-processing plants. Following certain basic rules assures that the use of AFR does not change the emissions of a cement kiln stack. These include feeding alternative fuels into the most suitable zones of the kiln, feeding materials that contain a lot of volatile matter into the high temperature zone only, and avoiding materials that contain pollutants kilns cannot retain, such as mercury. Emissions must be monitored, some only once a year and others continuously. Environmental impact assessments (EIA) should be done to confirm compliance with Kåre Helge Karstensen [email protected] Page 286 of 420 environmental standards; risk assessments can identify any weaknesses in the system, and material flux and energy flow analyses help to optimize the use of resources. Cement plant operators using AFR shall ensure their traceability from reception up to final treatment. Transport of wastes and AFR must comply with regulations. Plants must have developed, implemented and communicated to employees adequate spill response and emergency plans. For start-up, shut-down and conditions in between, strategies for dealing with AFR must be documented and available to plant operators. Plants need well-planned and functioning quality control systems, as well as monitoring and auditing protocols. Risks can be minimized by properly locating plants in terms of environmental setting, proximity to populations and settlements, and the impact of logistics and transport. Plants will require good infrastructure in terms of technical solutions for vapors, odors, dust, infiltration into ground or surface waters, and fire protection. All aspects of using AFR must be well documented, as documentation and information are the basis for openness and transparency about health and safety measures, inside and outside the plant. Management and employees must be trained in handling and processing of AFR. Hazardous operations training for new workers and subcontractors should be completed before starting with co-processing. Periodic re-certification should be done for employees and subcontractors. Induction training should be included for all visitors and third parties. Understanding risks and how to mitigate them are keys to training. Training authorities is the basis for building credibility. Introducing AFR requires open communications with all stakeholders. Provide all the information stakeholders need to allow them to understand the purposes of co-processing, the context, the functions of parties involved, and decision-making procedures. Open discussions about good and bad experiences are part of transparency, leading to corrective actions. Be credible and consistent, cultivating a spirit of open dialogue and respect for differing cultures. Kåre Helge Karstensen [email protected] Page 287 of 420 In these Guidelines the bar has been kept high in terms of environmental, social and health and safety standards, but they are realistic and achievable. Ambitious targets are needed in order to achieve goals (e.g. the Millennium Development Goals). However, one cannot expect that the public sector in any country or each and every cement plant operator or waste handling company anywhere in the world can implement all the proposed standards straight away. To achieve the proposed standards, a stepwise and country specific (phasing) program or action plan is required, which ideally represents a consensus (reflecting the enhanced cooperation) between the public and private sector. As populations increase in the developing world, so do waste management problems, and so does the need for more cement and concrete for housing and the infrastructure of development. The properly managed use of wastes as fuels and raw materials in cement kilns can help manage wastes while contributing to the sustainable development of our world. Waste to recovered fuel - cost-benefit analysis GUA Gesellschaft für Umfassende Analysen GmbH (2001): “In the project “Waste to Recovered Fuel”, which is co-funded by the 5th Framework Programme of the European Commission and an industrial consortium representing all stakeholders, a cost-benefit analysis is undertaken in order to evaluate the overall effects of different recovery options for combustible waste on national welfare. The study is limited to energy recovery and fuel recovery (supplemented by organic recovery) compared to landfill disposal”. “The analysed system (ASy) includes all relevant processes required in integrated waste management systems (collection, sorting and recovery of recyclables, incineration, landfill, etc.). The processes of production and use of recovered fuel are also part of the analysed system”. “MSW generated in households as well as combustibles from commerce and industry which are presently disposed of in the European Union serve as input materials into the analysed system (“waste”). The products, which are leaving the analysed system such as Kåre Helge Karstensen [email protected] Page 288 of 420 secondary materials or energy derived from incineration/co-combustion, substitute equivalent products which would have been produced on a conventional (primary) basis instead (see SPPP). The operation of primary processes or the use of conventional fuels (coal, etc.) is saved correspondingly”. “In the cost-benefit analysis the business cost of the processes saved represent the value of the products leaving the analysed system. (For instance, electricity produced in a MSW (in ASY) saves the production of the same amount of electricity in a conventional power plant (in SPPP). In this case, the value of the electricity produced in the MSWI is represented in the business costs which would arise through the installation and operation of a conventional power plant in order to generate the same amount of electricity.) This value is subtracted from the summarised business costs of the process in the analysed system. The internal costs of the integrated resource and waste management system are reduced correspondingly”. “The external effects of the processes (emissions) are also considered in the costbenefit analysis. In order to integrate emissions into the cost-benefit analysis, however, the emissions (such as SO2, NOx, heavy metals etc.) need to be transferred into monetary units. This is done by applying the principle of averting costs. (Averting costs are defined as known process costs that would be needed to reduce the relevant emission to a certain environmental standard. The processes applied are the processes which can reduce the relevant emission most efficiently (e.g. investment in thermal insulation in order to reduce fuel consumption and corresponding CO2 emissions)). Saved emissions again reduce the external cost (environmental/society costs) of the whole system accordingly”. “The calculation of the cost-benefit balance - the result of the cost-benefit analysis is carried out for several scenarios. A scenario describes a specific combination of waste management methods applied in the analysed system. The cost-benefit balance (CBB) describes the difference between the baseline scenario and an analysed scenario. The input into both baseline scenario and analysed scenario needs to be the same”. “The baseline scenario represents a reference to which the analysed methods of waste management (analysed scenarios) are compared. The baseline scenario is outlined as follows: Kåre Helge Karstensen [email protected] Page 289 of 420 - Present state of material recycling of paper, plastics, metals, glass, and bio-waste from households separated in the model region investigated. - “State of the art” landfilling of the remaining MSW (grey waste) and of the combustibles from commerce and industry which are either incinerated with energy recovery or are upgraded to recovered fuel in the analysed scenarios”. “The incineration scenarios produce heat and/or electricity in a dedicated MSW incinerator. The scenarios differ by the type of conventional energy production substituted”. “The fuel recovery scenarios treat the different options of fuel preparation (production of fluff, soft pellets, and hard pellets) and the use of recovered fuel (RF) in one of four combustion processes - cement kiln; - fluidised bed combustion; - pulverised coal combustion; - gasification and combustion in a pulverised coal combustion plant”. “Residuals from fuel preparation are directed to waste incineration (with energy recovery)”. “In the cost-benefit analysis different structural conditions for integrated resource and waste management systems are considered by means of defining three “model regions”. The differences between the model regions are reflected in the waste generation rate per capita, the waste composition, the type of collection system installed, the level of recycling, the cost structures (investment cost, personnel cost) and the saleability of energy generated in an incinerator”. “The different waste composition as well as the different separate collection systems in the model regions influence the mass flow of the waste to further treatment processes. The Kåre Helge Karstensen [email protected] Page 290 of 420 mass flow is also influenced by the efficiency of the fuel preparation process regarding the separation of recovered fuels”. “The cost-benefit analysis demonstrates that it is beneficial for the national economy to direct residual waste to processes carrying out energy recovery. The level of the benefits achieved, however, depends very much on the particular circumstances given”. “High benefits can be achieved when the share of combustibles in residual waste (paper, plastics) is high and when the waste is directed to fuel preparation processes”. “In terms of the fuel preparation processes it is desirable to have a high productivity regarding the separation of combustibles and the production of recovered fuel respectively. The more fuel can be recovered from residual waste the more regular fuels can be saved and the more benefits for the national economy can be achieved consequently. In principle, highest benefits are achieved when a maximum of waste is diverted from landfill”. “Within the limitations of the computer model it is shown that the type of cocombustion facility, in which the recovered fuel is finally used, has only a minor effect on the cost-benefit balance”. “Residual waste directed to waste incineration is also beneficial for the national economy in all modelled cases except when the produced energy would substitute energy from fossil gas. Here, however, the extent of saleable energy (electricity, district heat, industrial heat) as well as the capacity of the waste incinerator, as shown by sensitivity analyses, play an important role. The highest benefits can be achieved if energy from coal fired power plants is substituted”. “Averaged over a number of scenarios and regional conditions investigated, the annual welfare economic benefit of energy recovery and fuel recovery compared to landfill that can be achieved for the national economy is in the order of 5 - 30 Euro/inhabitant. The study shows that the analysed scenarios can save 2 - 4 GJ/inhabitant (= 50 - 100 kg of oil equivalent). This corresponds to some 10% of the solid fuel consumption and 2 - 4% of total fossil fuel consumption in Europe. It is a significant contribution to the Kyoto targets”. Kåre Helge Karstensen [email protected] Page 291 of 420 Development of CCME National emission guidelines for cement kilns Klein and Rose (1998): “As part of an effort to reduce emissions of nitrogen oxides from stationary industrial sources, Environment Canada led a multi-stakeholder consultation to establish CCME national emission guidelines for cement kilns. This paper describes the rationale behind the consultation, and the provisions of the Guideline published in March 1998. A description is included of the cement industry, its NOx emissions and control technologies, as well as emissions of other pollutants and carbon dioxide. The Guideline is based on principles of pollution prevention and cost-effective NOx reductions, as well as the recognition of energy efficiency to minimize greenhouse gas emissions. The use of flyash/slag blended cement is encouraged as a credit to NOx emissions, as are the use of waste fuels and waste heat recovery as a sustainable development strategy. Provincial regulatory agencies may set more stringent emission limits to address local air quality problems”. Cement manufacturing. Pollution prevention and abatement Handbook 1998 : Toward cleaner production The World Bank Group (1998): “The preparation of cement involves mining; crushing, and grinding of raw materials (principally limestone and clay); calcining the materials in a rotary kiln; cooling the resulting clinker; mixing the clinker with gypsum; and milling, storing, and bagging the finished cement. The process generates a variety of wastes, including dust, which is captured and recycled to the process. The process is very energyintensive, and there are strong incentives for energy conservation. Gases from clinker cooler are used as secondary combustion air. The dry process, using preheaters and precalciners, is both economically and environmentally preferable to the wet process because the energy consumtion – 200 joules per kilogram (J/kg) – is approximately half that for the wet process”. “Certain solid waste products from other industries, such as pulverized fly ash (PFA) from power stations, slag, roasted pyrite residues, and foundry sand, can be used as additives in cement production”. Kåre Helge Karstensen [email protected] Page 292 of 420 “The generation of fine particulates is inherent in the process, but most are recovered and recycled. Approximately 10-20% of the kiln feed can be suspended in the kiln exhaust gases, captured, and returned to the feed. Other sources of dust emissions include the clinker cooler, crushers, grinders, and materials-handling equipment. When the raw materials have high alkali or chloride content, a portion of the collected dust must be disposed of as solid waste, to avoid alkali build-up. Leaching of the dust to remove the alkali is rarely practiced. Grinding mill operations also result in particulate emissions. Other materials-handling operations, such as conveyors, result in fugitive emissions”. “Ambient particulate levels (especially at sizes less than 10 microns) have been clearly demonstrated to be related to health impacts. Gases such as nitrogen oxides (NOx) and sulphur oxides (SOx) are formed from the combustion of the fuel (oil and coal) and oxidation of sulfur present in the raw materials, but the highly alkaline conditions in the kiln can absorb up to 90% of the sulfur oxides. Heavy metals may also be present in the raw materials and fuel used and are released in kiln gases. The principal aim of pollution control in this industry is to avoid increasing ambient levels of particulates by minimizing the loads emitted”. “Cement kilns, with their high flame temperatures, are sometimes used to burn waste oils, solvents, and other organic wastes. These practices can result in the release of toxic metals and organics. Cement plants are not normally designed to burn wastes, but if such burning is contemplated, technical and environmental acceptability needs to be demonstrated. To avoid the formation of toxic chlorinated organics from the burning of organic wastes, air pollution control devices for such plants should not be operated in the temperature range of 230-400°C. (For further details, see United States 1991.)” “The priority in the cement industry is to minimize the increases in ambient particulate levels by reducing the mass load emitted from the stacks, from fugitive emissions, and from other sources. Collection and recycling of dust in kiln gases is required to improve the efficiency of the operation and to reduce atmospheric emissions. Units that are well designed, well operated, and well maintained can normally achieve generation of less than 0.2 kilograms of dust per metric ton (kg/t) of clinker, using dust recovery systems. NOx emissions should be controlled by using proper kiln design, low- NOx burners, and an optimum level of excess air. NOx emissions from a dry kiln with preheater and precalciner are typically 1.5 kg/t of clinker, as against 4.5 kg/t for the wet process. The nitrogen oxide Kåre Helge Karstensen [email protected] Page 293 of 420 emissions can be reduced further, to 0.5 kg/t of clinker, by afterburning in a reducing atmosphere, and the energy of the gases can be recovered in a preheater/precalciner”. “For control of fugitive particulate emissions, ventilation systems should be used in conjunction with hoods and enclosures covering transfer points and conveyors. Drop distances should be minimized by the use of adjustable conveyors. Dusty areas such as roads should be wetted down to reduce dust generation. Appropriate stormwater and runoff control systems should be provide to minimize the quantities of suspended material carried off site”. “SOx emissions are best controlled by using low sulfur fuels and raw materials. The absorption capacity of the cement must be assessed to determine the quantity of sufur dioxide emitted, which may be up to about half the sulfur load on the kiln. Precalcining with lowNOx secondary firing can reduce nitrogen oxide emissions”. “Alkaline dust removed from the kiln gases is normally disposed of as solid waste. When solid wastes such as pulverized fly ash are used with feedstock, appropriate steps must be taken to avoid environmental problems from contaminants or trace elements”. “Stormwater systems and storage areas should be designed to minimize washoff of solids”. “Mechanical systems such as cyclones trap the larger particulates in kiln gases and act as preconditioners for downstream collection devices. Electrostatic precipitators (ESPs) and fabric filter systems (baghouses) are the principal options for collection and control (achieving over99% removal efficiency) of fine particulates. ESPs are sensitive to gas characteristics, such as temperature, and to variation in voltage; baghouses are generally regarded as more reliable. The overall costs of the two systems are similar. The choice of system will depend on flue gas characteristics and local considerations”. “Both ESPs and baghouses can achieve high levels of particulate removal from the kiln gas stream, but good operation and maintenance are essential for achieving design specifications. Two significant types of control problem can occur: (a) complete failure (or automatic shutoff) of systems related to plant shutdown and start-up, power failures, and the like, leading to the emission of very high levels of particulates for short periods of time; and Kåre Helge Karstensen [email protected] Page 294 of 420 (b) a gradual decrease in the removal efficiency of the system over time because of poor maintenance or improper operation. The limit content of raw materials can be used to control sulfur oxides”. “Emissions levels for the design and operation of each project must be established through the environmental assessment (EA) process on the basis of country legislation and the Pollution Prevention and Abatement Handbook, as applied to local conditions. The emissions levels selected must be justified in the EA and acceptable to the World Bank Group”. “The guidelines given below present emissions levels normally acceptable to the World Bank Group in making decisions regarding provision of World Bank Group assistance. Any deviations from these levels must be described in the World Bank Group project documentation. The emissions levels given here can be consistently achieved by well- designed, well-operated, and well-maintained pollution control systems”. “The guidelines are expressed as concentrations to facilitate monitoring. Dilution of air emissions or effluents to achieve these guidelines is unacceptable”. “All of the maximum levels should be achieved for at least 95% of the time that the plant or unit is operating, to be calculated as a proportion of annual operating hours”. Aire emission “A maximum emissions level of 50 milligrams per normal cubic meter (mg/Nm3), equivalent to a maximum of 0.2 kg/t of clinker, for particulates in stack gases under full-load conditions is to be achieved. This emissions level is based on values that are routinely achieved in well-run plants. Maximum emissions levels for sulfur oxides are 400 mg/Nm3, for nitrogen oxides, 600 mg/Nm3”. “Management’s capacity to maintain the necessary operational and maintenance standards should be carefully evaluated. If necessary, training for plant personnel should be provided under the project. The EA and the prefeasibility or feasibility study should examine the effects of fugitive and stack emissions (including dust, sulfur oxides, and nitrogen oxides) Kåre Helge Karstensen [email protected] Page 295 of 420 on ambient air quality and implement measures to maintain acceptable ambient air quality levels”. Liquid effluents “Normally, effluents requiring treatment originate from cooling operations or as stormwater. Treated effluent discharges should have a pH in the range of 6-9. Cooling water should preferably be recycled. If this is not economical, the effluent should not increase the temperature of the receiving waters at the edge of the mixing zone (or 100 meters, where the mixing zone is not defined) by more than 3°C. If quantities of suspended solids in the effluent are high in relation to receiving waters, treatment may be required to reduce levels in the effluent to a maximum of 50 milligrams per liter (mg/l). Note that the effluent requirements are for direct discharge to surface waters”. Ambient noise “Noise abatement measures should be achieved. Measurements are to be taken at noise receptors located outside the project property boundary”. “Frequent sampling may be required during start-up and upset conditions. Once a record of consistent performance has been established, sampling for the parameters listed in this document should be as described below”. “Equipment for continuous monitoring of opacity levels (or particulates in the stack exhaust, whichever is cost-effective) should be installed. Measurement of the sulfur content of raw materials and fuel, and direct measurement of particulate SOx, and NOx levels at the plant boundary levels should be carried out at least annually. When operational upsets occur, the opacity of kiln and clinker cooler exhaust gases should be measured directly and corrective actions taken to maintain the opacity level of the stack gases below 10% (or an equivalent measurement)”. “The pH and temperature of the wastewater effluent should be monitored on a continuous basis. Suspended solids should be measured monthly if treatment is provided”. Kåre Helge Karstensen [email protected] Page 296 of 420 “Monitoring data should be analyzed and reviewed at regular intervals and compared with the operating standards so that any necessary corrective actions can be taken”. “Records of monitoring results should be kept in an acceptable format. The results should be reported to the responsible authorities and relevant parties, as required”. “The key production and control practices that will lead to compliance with emissions guidelines can be summarized as follows: Give preference to the dry process with preheaters and precalciners”. “Adopt the following pollution prevention measures to minimize air emissions: - Install equipment covers and filters for crushing, grinding, and milling operations; - Use enclosed adjustable conveyors to minimize drop distances; - Wet down intermediate and finished product storage piles; - Use low-NOx burners with the optimum level of excess air; - Use low sulfur in the kiln; - Operate control systems to achieve the required emissions levels”. “Develop a strong unit or division to undertake environmental management responsibilities”. Development of national guidelines for the use of hazardous and non-hazardous wastes in cement kilns in Canada Kåre Helge Karstensen [email protected] Page 297 of 420 Campbell and Mirza (1996): “In April, 1993, the Canadian Council of Ministers of the Environment (CCME) commissioned a study to develop national guidelines for the use of hazardous and non-hazardous wastes as supplementary fuels in cement kilns. The study was undertaken by Procot & Redfern Limited under the direction of the Wastes as Fuels Working Group which consists of provincial and federal regulators and industry representatives. The study culminated in the preparation of the guidelines for presentation to the Hazardous Waste Task Group of the CCME. This paper describes the CCME Working Group process, the draft guidelines development process for cement kilns using wastes as fuels in Canada, and presents the rationale for the proposed emission limits, operating standards and monitoring requirements”. Comparison of criteria pollutants for cement kilns burning coal and hazardous waste fuels Schreiber et al. (1996): “The Clean Air Act and Resource Conservation and Recovery Act have established pollutant emissions limitation for oxides, sulphur dioxide, carbon monoxide, hydrocarbons, particulates, dioxins/furans, and metals. The pollutant emissions data from Continental Cement Company were analyzed to observe changes in emissions resulting from changes in fuel sources and raw material compositions. The mass emissions rates were related on a toxicity equivalency basis to better compare emissions of chemicals of concern. An overall increase in toxicity of metals emissions from burning coal and HWDF as opposed to burning coal resulted. However, an overall decrease in toxicity of NOx, SO2, and 2,3,7,8 TCCDD TEQ emissions from burning coal and HWDF as opposed to burning coal also resulted. This decrease in emissions concentrations has a more favourable impact on pollutant emissions then the increase in metals emissions”. Kåre Helge Karstensen [email protected] Page 298 of 420 Annex 5 A review of the literature – objections to co-processing of wastes in cement kilns This chapter presents links and papers objectioning co-processing of waste materials in the cement industry. See for example the following links: http://www.downwindersatrisk.org/index.htm http://archive.greenpeace.org/toxics/documents/altdetoxCement.pdf http://www.foe.co.uk/pubsinfo/briefings/html/19971215145335.html http://www.wbcsd.ch/web/projects/cement/tf2/concern_over_plans.pdf http://www.ejnet.org/rachel/rhwn243.htm http://www.lerotic.de/cemex/indexE.htm http://www.ban.org/Library/burning_denmark.html http://www.ipen.org/ipepweb1/library/ipep_pdf_reports/7bye%20cement%20kilns%20in%20 belarus.pdf http://www.lrc.org.za/Articles/Articles_Detail.asp?art_ID=255 http://www.greenlink.org/public/hotissues/epawti.html http://www.notoxicburning.org/ www.groundwork.org.za Kåre Helge Karstensen [email protected] Page 299 of 420 Note from South Africa NGOs on ROD, 15/11-05 Civil society organisations have welcomed the decision by the North West Province to deny Holcim Cement permission to burn hazardous waste in their cement kiln in Dudfield, outside Lichtenberg (Ditsobotla Local Municipality District) in the North West Province. The decision is an important precedent. Earthlife Africa Johannesburg[1], with legal representation from the Legal Resources Centre (LRC) [2] office in Pretoria, submitted comment during the Environmental Impact Assessment and raised various concerns about the project. These concerns were considered favourable by government and the reasons for rejecting the Environmental Impact Report are as follows: • Cumulative impacts were not considered; • Reference to waste materials that would be burnt is “vague and wide”; • The Stockholm Convention on Persistent Organic Pollutants (POP’s) identifies cement kilns firing hazardous waste as a potential source of dioxins, furans and heavy metals; • No alternatives including the “no-go” option is discussed; and • The emission inventory was not based emission measurements or mass balance. [3] Louise du Plessis, of the LRC who acted on behalf of Earthlife Africa Johannesburg indicates that it is encouraging to see that the provincial department considered the matter so carefully and had the good judgement to implement the precautionary principle. Earthlife Africa Johannesburg spokesperson on this issue, Richard Worthington, indicates that, “Holcim's project is a classic case of opportunism dressed up as altruism: turning a blind eye to toxic emissions such as organochlorines (dioxins and furans), fudging the details of proposed "fuels" and claiming environmental benefits. Such projects seek to turn the polluter pays principle on its head - instead of industries accepting the costs of redesigning processes or products to avoid hazardous wastes, they now market their wastes as a commodity, which is presented as a "clean fuel" on the basis of avoiding one or more of the pollutants associated with coal (traditionally the dirtiest fuel). It is encouraging that such attempted slight-of-hand has been rejected by authorities.” Kåre Helge Karstensen [email protected] Page 300 of 420 Llewellyn Leonard, groundWork’s [4] Waste Coordinator, visited the local municipality in Lichtenberg in 2004, and in an address to the Mayor Mr. J. Bogatsu and his officials presented the health and environmental concerns of burning hazardous waste in cement kilns. This was followed up with a similar meeting with the National Union of Mineworkers who organise in the cement industry nationally. “It is only through careful and systematic building of our knowledge base on the dangers of hazardous waste incineration, that these proposals will be halted”, stressed Leonard. Various civil society organisations, including groundWork, Earthlife Africa, Wildlife and Environment Society of South Africa, the South Durban Community Environmental Alliance and Injiya ya Uri have consistently addressed their concerns on the burning of hazardous waste in cement kilns to the Ministry of Environment and Tourism, calling on the Ministry to develop clear policy guidelines through a consultative process to determine how hazardous waste is treated in South Africa. These organisations have worked together to challenge various proposals on the burning of hazardous waste [5]. Bashiru Abdul spokesperson for Agenda, an environmental justice NGO based in Dar es Salaam, Tanzania, who is presently in South Africa, stated that they were delighted at the victory news since this precedent set in South Africa would not allow for cement companies to set up similar processes in other African countries. There has been an international focus on these proposed developments by the Global Anti Incineration Alliance [6] Manny Colonzo, of Global Anti Incineration Alliance, welcomed the decision by government, and maintains that “the South African government’s decision puts them in a leadership position in ensuring that hazardous waste is not treated inappropriately.” See Record of decision. For more information call: • Llewellyn Leonard: groundWork – 082 4641383 • Louise du Plessis: Legal Resources Centre – 082 3460744 • Richard Worthington: Earthlife Africa – 082 4466392 Kåre Helge Karstensen [email protected] Page 301 of 420 Footnotes: [1] Earthlife Africa (ELA) is a membership driven organization of environmental and social justice activists, founded to mobilize civil society around environmental issues in relation to people. ELA Johannesburg (Jhb) branch was established in August 1988 as the first branch of the organization, which grew to many branches in the early nineties and is currently concentrated in three branches in South Africa and one in Namibia (www.earthlife.org.za) [2] The Legal Resources Centre is an independent, client-based, non-profit public interest law centre which uses law as an instrument of justice. It works for the development of a fully democratic society based on the principle of substantive equality, by providing legal services for the vulnerable and marginalised, including the poor, homeless, and landless people and communities of South Africa who suffer discrimination by reason of race, class, gender, disability or by reason of social, economic, and historical circumstances. (www.lrc.org.za) [3] Some of the core issues questioned by the LRC on the process: • Statements made by Holcim were seriously in dispute namely that the development they proposes is sustainable and at the least cost for future generations, the burning of waste is a renewable fuel source, the use of waste-derived fuels in a cement kiln instead of fossil fuel does not change emission levels ect. • The wastes to be used were not identified but only vaguely refer to. To analyse the impact of waste used as fuel in cement kiln it is crucial to identify the components of the waste stream. • The air pollution control measures. • Fabric filters are not effective for controlling emissions of dioxins. • Quench cooling of flue gas is effective for controlling emissions of dioxins, but Holcim is not employing this control measure. Kåre Helge Karstensen [email protected] Page 302 of 420 • Holcim underestimates the impact of dioxin emissions by ignoring the prevailing pathway for human intake which is through incorporation into the food chain, inhalation, which is the prevailing pathway for human intake of dioxin. • The presence of extensive crop cultivation in the vicinity of Holcim warrants a risk assessment of dioxin incorporation into South Africa’s food supply. • Holcim USA conducted a risk assessment of how its emissions of dioxin would incorporate into the local food supply. • Holcim provides inadequate information about how it would handle liquid wastes. • Holcim’s South Africa’s Air quality impact predictions are based on inapt assumptions about emission rates. • Holcim fails to provide an adequate basis for its assumptions about dioxin emission rates. • Holcim was wrong with statements that the potential for dioxin formation is not related to the type of fuel used. [4] groundWork is an environmental justice organisation working focusing on air pollution, waste and corporate abuse and works with community organisations living adjacent to petrochemical facilities in south Durban, Sasolburg, Secunda and Cape Town. (www.groundwork.org.za) Physicians' Statement In Support of Legislation Concerning Cement Plant Incineration of Hazardous Waste - House Bills 1007 and 1008 Being Sponsored by Representative Jesse Jones. January/February 1997. As local physicians practicing in communities "downwind" of a cement plant that burns hazardous wastes, we agree that prudent public health policy demands stricter standards for how and whether cement plants should be allowed to burn such wastes near heavily-populated Kåre Helge Karstensen [email protected] Page 303 of 420 areas. Perhaps we also need to ask if they should be allowed to burn these kinds of wastes at all. Too little is known about the continued long-term health consequences of exposures to the kinds of toxins released by the burning of hazardous waste - especially in a facility not originally built for waste disposal. We should always be very conservative about the kinds of substances we introduce into our bodies - whether it's a harmful drug or harmful air pollution. Many of us believe we have already seen patients' health adversely affected by the burning of hazardous waste in a cement plant and other local air pollution. The most recent science makes a convincing link between increasing air pollution levels and decreasing public health. It also concludes that there does not appear to be "safe" exposure levels for humans of some pollutants - pollutants emitted in large quantities when hazardous waste is commercially burned in cement plants. EPA scientists have recently stated that current air standards are not protective. One of the most important public health measures that can be taken by government is in helping to reduce exposure to harmful air pollution, pollution which results in more deaths every year in the U.S than auto accidents. We wholeheartedly support the legislation being sponsored by Representative Jones that would tighten the public health and safety standards for cement plants burning hazardous waste and create a buffer zone for the location of these plants in heavily-populated areas. In the name of sound public health policy, we urge all our state elected officials to also voice their strong support of Rep. Jones' bill. Arturo E. Aviles, M.D. Dallas Mark D. Towns, M.D. DeSoto Stephan Blount, D.C. Dallas, Duncanville Lee D. Walters, M.D. Duncanville James C. Buckner, D.C. Retired, Midlothian R. Wasserman, M.D. Dallas William P. Burch, D.D.S. Retired, DeSoto David Webb, M.D. DeSoto D.E. Christiansen, D.O. Duncanville Martin Williams, D.C. Cedar Hill Anthony D. Ellis, D.V.M. Cedar Hill Jay Gartner, M.D. Duncanville Charles M. Hamel, M.D. Arlington Munir E. Hazbun, M.D. Grand Prairie W.F. Howard, M.D. Dallas Jerry N. Kaumo, M.D. Dallas Frank Lane, M.D. Dallas Troy D. Lindsey, D.V.M. Cedar Hill Kåre Helge Karstensen [email protected] Page 304 of 420 Garrett Maxwell, M.D. Cedar Hill, DeSoto Thomas. A. Mitchell, M.D. DeSoto Joseph Pflanzer, M.D. DeSoto Donald Phillips, M.D. DeSoto Sharon Rictcher, M.D. Dallas William Sellars, M.D. DeSoto Richard Silver, M.D. Dallas John A Standefer, M.D. Duncanville Robert W. Sugerman, M.D. Dallas Burning Denmark's Good Name in Mozambique, by Jim Puckett In a neighborhood in Delhi, India stands an ominous rusting hulk of piping, conduit and conveyors - the Taj Mahal of inappropriate technology and aid. It was never used because Danish International Development Assistance (Danida), which helped fund and promote it, never did its basic homework. The agency failed to realize that in a low consumptive society with a very high rate of scavenging and recycling, the garbage that is left simply won’t burn. The vital lesson that the Delhi incinerator should have taught Danida about inappropriate technology transfer appears to have gone unlearned some 15 years later in Africa with another Danish incinerator project. At first glance, Danida’s plan might appear laudable. The agency proposes to deal with about 900 tonnes of deteriorating stockpiles of obsolete and aging pesticides in Mozambique by building a permanent hazardous waste station and retro-fitting a cement factory so that it can burn hazardous wastes. In fact, this project, like the Delhi debacle, is a product of northern arrogance and ignorance and is destined to cause more problems than it solves. Danida’s first mistake was its failure to consult with non-governmental organizations and local people. The agency’s website reads: “Denmark has a long-standing tradition of actively involving individuals, non-governmental organizations and associations and businesses formally and informally in formulating and implementing environmental policies.” Apparently, this “tradition” only applies to domestic activities. According to the translator hired for the only “hearing” that was held for this project, the burning of the hazardous wastes was not discussed at all, thus risks and alternatives were not discussed. No project Kåre Helge Karstensen [email protected] Page 305 of 420 documentation was made available in any language, not even the appallingly thin (32 pages) Environmental Impact Assessment. The level of awareness about the project in Mozambique was virtually nil until international and regional environmental justice groups brought noted Chemistry Professor and incineration expert Dr. Paul Connett of St. Lawrence University, New York to Maputo in August to warn of the project’s dangers. As a result of that visit, a new local advocacy group, Livaningo (meaning ‘bringing light’), was launched and is now struggling against powerful forces to fight the plan. Livaningo is, in fact, the hub of a global coalition of environmental groups working to change Danida’s plans in Mozambique. For many months the coalition has been engaged in a long letter exchange with Danish Development Minister Poul Nielson. (These letters are available at www.ban.org, library section). However, to date, that dialogue has produced little more than a record of steadfast intransigence on the part of Minister Nielson. Incineration of hazardous wastes in cement kilns actually produces the most toxic persistent organic pollutants (POPs) known - dioxins and furans - as inevitable by-products. These dangerous substances, along with heavy metal contaminants, find their way into both the cement product (clinker) and into cement kiln dusts, which are a common fallout problem around all cement factories. At the Cimentos de Mocambique cement kiln, workers were photographed this August, covered with such dust. Worldwide, cement kilns burning hazardous wastes are estimated to comprise 23 per cent of the current global source for dioxin. But all incinerators, including municipal solid waste burners, medical waste burners, cement kilns and high temperature incinerators, are known to produce dioxins and furans. These two compounds top the list of 12 substances that are targetted for international phase-out and elimination in the current negotiations for a new global POPs treaty under the auspices of the United Nations Environment Programme. The Nordics have taken the lead on this treaty. It makes little sense to advocate the elimination of POPs globally, while promoting new sources of the worst of them. Incinerators are not a solution for hazardous waste - they are part of the problem. Even historically-produced hazardous wastes, (such as obsolete pesticides) can now be dealt with using commercially available non-combustion alternatives that detoxify hazardous Kåre Helge Karstensen [email protected] Page 306 of 420 wastes without producing and spreading more into the atmosphere. When the environmental coalition provided the names of such companies to Minister Nielson, he replied that while these solutions might be interesting for future projects, they were not going to be considered for the Mozambique project. Danida has also turned a blind eye to the real threat of waste trafficking in Africa. Such a permanent hazardous waste facility will likely have a magnet effect for the powerful economic forces driving the international waste trade. While belated efforts have been made to receive assurances from Mozambique officials that the cement kiln would not burn imported hazardous wastes, no actual guarantees can ever exist. Indeed, according to DT 10/98, one Danida official confirmed that incinerating waste from neighbouring countries which implies importation - was part of the original intent of the project. Moreover, the Mozambique government recently gave authorization for the import of hazardous waste. Yet such deals were strictly outlawed in 1989 by the Lomé IV Convention. They also jeopardise the entry into force of the Basel Convention Ban - skillfully negotiated in 1994 by Danish Environment Minister Svend Auken - that bans the export of hazardous wastes from OECD to non-OECD countries. There is still a chance for Denmark to avoid a global NGO campaign attacking its projects and practices. Indeed, there is a great opportunity for Denmark to take the environmental high ground. Danida should first hold an open and transparent public forum on the risks and possible alternatives for burning hazardous wastes in Mozambique. Second, consistent with the Danish national policy to eliminate POPs worldwide, Danida should renounce any projects that promote new POPs sources (e.g. incinerators). Finally, Denmark should regain its role as environmental leader and promote the new wave of non-combustion hazardous waste destruction methods to destroy POPs stockpiles, starting with pesticides in Mozambique. Development Today: Nordic Outlook on Development Assistance, Business and the Environment -- 28 October 1998 -- Jim Puckett is Director of the Seattle-based Asia-Pacific Environmental Exchange (APEX) and Coordinator for the Basel Action Network (BAN), which seeks to implement the Basel Convention and end toxic trade. Kåre Helge Karstensen [email protected] Page 307 of 420 FAIR USE NOTICE. This document contains copyrighted material whose use has not been specifically authorized by the copyright owner. The Basel Action Network is making this article available in our efforts to advance understanding of ecological sustainability and environmental justice issues. We believe that this constitutes a `fair use' of the copyrighted material as provided for in section 107 of the US Copyright Law. If you wish to use this copyrighted material for purposes of your own that go beyond `fair use', you must obtain permission from the copyright owner. From NOTOXICBURNING.ORG: http://www.notoxicburning.org/ May 2007 Update The Montana Department of Environmental Quality has announced that it expects to release the Final Environmental Impact Statement (EIS) in June 2007. A record of decision on Holcim’s air quality permit will be published approximately 15 days later. We do not anticipate that there will be another opportunity for public comment. If the outcome is not satisfactory, the next step will be to appeal the decision to the Board of Environmental Review. We will only have 15 days after the record of decision to appeal so stay tuned... February 2007 Update EPA Do-Nothing Rule on Cement Kiln Mercury Pollution Ignores Court Order, Public Outcry Montanans Against Toxic Burning joins coalition of groups to challenge EPA's latest refusal to control toxic mercury emissions. Press Release November 2006 Update The public comment period on the long-awaited Draft Environmental Impact Statement (DEIS) and Draft Permit ended on September 28, 2006, and we now await the DEQ’s response to comments on those drafts and the departmental determination on the air quality permit. Kåre Helge Karstensen [email protected] Page 308 of 420 Burning whole scrap tires exposes people to hazardous dioxins. This is the biggest reason why doctors and other concerned citizens in our community are concerned about tire-burning at Holcim’s cement kiln: • Dioxin is among the most toxic substances ever identified, according to the National Academy of Sciences. Exposure to dioxin is linked with tumor development, birth defects, reproductive disorders, immune system disorders, and skin disorders among many other adverse health effects. • Studies by the U.S. Environmental Protection Agency (EPA) reveal that burning whole tires significantly increases emissions of cancer-causing dioxin. At Holcim’s Trident kiln, the DEQ anticipates that burning whole tires will increase dioxin emissions by 60 percent, well over federal limits that are intended to protect public health. Yet the DEQ decided to ignore this alarming jump in dioxin emissions when it prepared the health risk assessment required under Montana’s waste-burning laws. • Actual increases in dioxin emissions are likely to be even greater than anticipated by the DEQ. The DEQ is projecting emissions based solely on information from other plants, but it failed to gather any data from kilns with operations similar to what Holcim is proposing to do, that is, burn whole tires in a wet-process kiln. EPA studies show far greater increases in dioxin emissions when old "wet-process" kilns such as the Trident kiln burn whole tires. The DEQ is ignoring threats from toxic heavy metals. Lead smelter slag containing lead, arsenic, cadmium, chromium, and other toxic metals is already going into Holcim’s kiln. Last year, the DEQ agreed that pollution from slag is a major issue that must be addressed. Yet the DEQ has never attempted to find out what is coming out of Holcim’s stack. Based on this EIS, the public has no idea whether current pollution levels are safe, or what the impacts will be if Holcim adds tires to its mix. • Unaccountably, the DEQ is predicting that emissions from heavy metals and other hazardous air pollutants are going to decrease if Holcim receives its permit to burn 1.13 million whole scrap tires and 16,535 tons of lead smelter slag annually. Yet tires contain far more heavy metals than the coal they will be replacing in Holcim’s kiln, Kåre Helge Karstensen [email protected] Page 309 of 420 and EPA studies confirm that heavy metal emissions go up when cement kilns use tires as fuel. Similarly, lead smelter slag contains more heavy metals than the iron ore it is replacing in the cement mix. • The DEQ is relying on pollution controls to prevent heavy metals from escaping out Holcim’s stack, but the controls don’t work during the plant’s frequent "upsets." The Trident kiln regularly malfunctions, and burning tires is likely to make the current problems worse. Of the nine wet-process kilns burning whole tires in the U.S., seven are violating their pollution emissions limits. Three are classified as "high-priority violators" by EPA, including a Holcim cement plant in Ada, Oklahoma, which was fined $321,000 in 2005 for violating its pollution limits more than 1,000 times in one year. This record inspires little confidence that the Trident facility will effectively control emissions of hazardous air pollutants if it is allowed to burn tires. New rules target waste burners from Chemical & engineering news Chemical companies, commercial incinerators, environmental activists, cement kilns fight over air standards, by Jeff Johnson, C&EN Washington http://www.greenlink.org/public/hotissues/epawti.html GreenLink - Public - HotIssues - WTI C&EN on EPA Incineraor Regs/WTI May 15, 2000 Last September, after years of delay and discussion, the Environmental Protection Agency issued a final regulation that will subject several hundred facilities to a new regime of air pollution standards. Each year, the affected facilities burn a total of 3.3 million tons of hazardous waste. In all, 232 hazardous waste combustors at 172 facilities will be covered. These include 163 on-site process incinerators, 26 commercial incinerators, 33 cement kilns, and 10 aggregate kilns. Kåre Helge Karstensen [email protected] Page 310 of 420 EPA estimates the new rule will cut emissions of dioxins and furans by 70%, mercury by 55%, cadmium and lead by 88%, and particulates by 42%. The agency also estimates that releases of arsenic, beryllium, and chromium will be reduced by 75%. The regulation will require companies to install equipment that could include filters and other devices to capture particulates and metals; systems to quickly quench hot flue gases to curb dioxin formation; and monitors to continuously measure carbon monoxide, hydrocarbon emissions, and some operating parameters. Exactly what will be required, however, is left to the operators of covered facilities to determine, so long as they can show through compliance testing that they meet the emissions requirements. The largest single covered industry group is chemical companies, a number of which run onsite incinerators as part of their mix of techniques to handle hazardous waste. On-site incinerators burn about half the 3.3 million tons of waste incinerated each year. The largest chemical sectors that burn hazardous waste are industrial organic facilities and makers of pesticides and agricultural chemicals, according to EPA. Despite the years of debate, 17 parties--16 representing regulated companies and one from an environmental group--are suing over sections of the rule, EPA says. Their objections have been consolidated into one big suit, which is expected to be argued this fall in the U.S. Court of Appeals for the District of Columbia. The number of litigants will probably drop depending upon what can be wheedled out of EPA during more negotiations--because, although the rule is final, EPA is still talking and will re-propose portions of the rule, EPA and industry officials say. The new regulation is part of EPA's waste minimization and combustion strategy, announced in 1993, early in EPA Administrator Carol M. Browner's tenure. The goal of this strategy, say EPA officials, was to reduce reliance on hazardous waste incineration and to shift industry to processes that minimize hazardous waste generation. Applauding this view is Greenpeace's Rick Hind and other environmentalists, who would simply like incinerators shut down. "We are reducing hazardous waste now--waste Kåre Helge Karstensen [email protected] Page 311 of 420 minimization efforts are working," he says. "Our fear is that EPA will discourage this trend by going weak on incinerators and kilns." Hind wants toxic chemicals out of products and encourages what he calls a "revolution in the marketplace" as companies move to closed- loop industrial processes that produce no emissions or use nontoxic feedstock. Hind argues that even the best incinerators concentrate dioxins and metals in the ash, which winds up in a landfill. However, over the years, companies have come to integrate incinerators deeply into manufacturing processes, and a commercial economy has grown up based on burning hazardous wastes. Not long ago, EPA encouraged waste incineration. And therein lies part of the difficulty for this new regulation. Incinerators have many supporters, one of whom is Arthur M. Sterling, chemical engineering professor at Louisiana State University. "If run correctly, incineration is a very effective way to reduce volume," he says. "The alternative is landfilling and we are running out of space, and it is not permanent. There will be leaks. "The best alternative is process modifications to reduce waste," Sterling says. "People are working on that, but for some waste streams, incineration is the best choice." Sterling notes, however, that the public strongly dislikes incinerators, and he acknowledges that real problems have led to the disfavor. He also notes it is nearly impossible to site a new incinerator today. Sterling runs a pilot incinerator at LSU, and the negative climate has had a direct effect on his research--no grants. Once four researchers operated the unit, he says, and now he is the only one left. And rather than study ways to improve incineration performance, today the unit is used to generate gases and particulates that are used for health effects research. Although EPA estimates that only 1.5% of hazardous waste is incinerated, that still means millions of tons that can generate both fights and profits. In the byzantine world of hazardous waste regulation, money and business opportunities can be equal in importance to environmental protection. Consider kilns that use the waste for a fuel in the manufacture of aggregate and cement. They burn it along with fossil fuels, mostly Kåre Helge Karstensen [email protected] Page 312 of 420 coal. And they get paid to take it. The kilns charge much less than the amount commercial incinerators get to treat hazardous waste. Consequently, taking wastes that burn hot and fast is a good deal for a kiln and a generator: income for the kiln and cheaper disposal for the generator. Most commercial incinerators, however, don't like this arrangement, nor do people living near the kilns, who worry about air emissions and have been vocal opponents of the use of hazardous waste in kilns. Both groups have fought for years to end the practice and had hoped the new rule might help them. Along with trying to run cement kilns out of the hazardous waste business, commercial incinerator companies had hoped tough standards would drive work their way from chemical companies running on-site incinerators. Commercial incinerators have had a tough time during the past few years due to the success of waste minimization programs and too many commercial incinerators chasing too little waste. "Too many mouths to feed" is how Paul C. Evans puts it. Evans is an analyst with Environmental Information Ltd. in Minneapolis, which tracks the hazardous waste industry. Evans ticks off four commercial incinerators that have been mothballed in the past few years because of lack of business, but he thinks demand might be moving closer to commercial capacity. How the new rule will play out for future business, however, is a "million-dollar question," he says. Meanwhile, commercial incinerator operators will remain disappointed because the rule is unlikely to advance their long-held dream of more business. They can console themselves with the fact that the final standards are such that many of them will have to do little to comply. EPA estimates that the new controls will cost industry from $63 million to $73 million a year. More than three quarters of that will be paid by operators of cement kilns and on-site incinerators. Kåre Helge Karstensen [email protected] Page 313 of 420 EPA predicts that only one or two cement kilns that burn hazardous waste will return to burning only fossil fuels and that 13 on-site incinerators will shut down, probably small units. Annual cost for complying with new regulation: Facility Cost Commercial incinerators $7 million Commercial kilns $24 million On-site incinerators $35 million TOTAL $66 million Source: Environmental Protection Agency Altogether, from 14,000 to 42,000 tons of hazardous waste will be shifted to commercial incinerators, EPA estimates, less than 1% of the hazardous waste incinerated annually. Considering the amount of waste affected and the number of facilities covered, EPA's plan seems to leave most of the industry relatively unscathed. EPA estimates that average annual costs for compliance will be about $600,000 for cement kilns, $325,000 for aggregate kilns, and $250,000 for commercial and on-site incinerators. Looking at the higher price to burn a ton of hazardous waste, EPA estimates costs will go up between $5 and $15 per ton of waste burned. Assuming companies increase prices to incinerate, this works out to a 6 to 7% price increase for kilns, which charge about $150 a ton, and a 1% increase for incinerators, which charge about $700 per ton, according to EPA. The agency estimates that 7% of incinerators (mostly commercial), 21% of cement kilns, and no aggregate kilns will already meet the new standards. However, this new regulation and the sector it regulates are so complicated that industry experts are unsure what the costs will really be and which sectors are likely to face the biggest impact. Kåre Helge Karstensen [email protected] Page 314 of 420 Much could depend on EPA technical modifications that may change portions of the regulation, but the compliance date of September 2002 will remain the same. To set the new emissions standards, EPA used a mechanism in the 1990 Clean Air Act Amendments called "maximum achievable control technology," or MACT. MACT is a technology-based, standard-setting technique that uses emissions levels of the best operating 12% of an industrial sector to set national standards for all similar units. Congress' idea in including MACT in the Clean Air Act was to move past endless regulatory fights over new emissions standards that were based on health impacts. Instead, the assumption behind MACT is that if an eighth of the industry can do it, so can the rest. The law also gave EPA the option of moving beyond MACT's lowest limits, or "beyond the floor," if the agency can show that MACT standards are not protective, which it has done in some cases. EPA has used MACT in several industry sectors over the past decade, but nobody likes how EPA applied it here. The Cement Kiln Recycling Coalition, a trade association, is distraught about the standard for the semivolatile metals lead and cadmium. Don Davis, director of public affairs for the coalition, says that EPA, in moving beyond the floor for the kilns, has set the standard at a level not achieved by the top 12% of kilns. Moreover, he says the standard can be easily reached by incinerators and charges that EPA is favoring one industry over another. Chemical industry officials say the most difficult standard for chemical companies to meet will be the particulate emissions standard. The Chemical Manufacturers Association has sued EPA over this standard and others, but officials from the association would not comment on the regulation or suit. However, sources say EPA is planning to make a modification for particulates that may help some in the industry. Greg Rigo, an environmental engineer and air pollution expert with Rigo & Rigo Associates in Cleveland, predicts implementation will be difficult for chemical companies. Kåre Helge Karstensen [email protected] Page 315 of 420 "Incinerators are used for process safety, fume controls, and so forth," Rigo says. "They are tied directly into process lines. To make a modification, the line must be shut down, and no one wants to take millions of dollars of production off-line." But he says few incinerators will shut down, as does Melvin Keener, executive director of the Coalition for Responsible Waste Incineration, an incinerator trade association. Keener warns of confusion in the years ahead. He notes that industry groups have singled out more than 100 issues they want EPA to address and it is unclear now what deals can be struck and what may happen in court. He also notes that the regulation will be implemented in most cases by states, not EPA. Consequently, much may turn on what states do. The one environmental group suing EPA is the Sierra Club, which is represented by Earth Justice Legal Defense Fund. Attorney James Pew says EPA misused the MACT process. He says after EPA selected the technology of the top 12%, it then picked the worst level that could be achieved with that technology. "EPA didn't even come close to achieving what could be emitted by the top 12%," he says. "It defeated MACT's purpose." An EPA official defends picking the so-called worst of the best. "The law says maximum achievable control technology,"stresses EPA's David Hockey, who is project director for this regulation. "We picked emissions that could be achieved." Pew expects the technical debate on MACT to be a major focus of the lawsuit, as it has been all along. He says the large number of litigants is in fact an understatement of interest in the rule. "During rule making, there were rooms filled with industry lawyers and lobbyists, all of whom were berating EPA for the standard," Pew says. "To understand this, you have to look at the legal industry as much as the incineration business. There are a lot of players billing time on this process. And remember, if you are fighting regulations, delay is victory." Kåre Helge Karstensen [email protected] Page 316 of 420 There is one company in the U.S. that needs to do little to comply: Waste Technologies Industries (WTI), a commercial incinerator in East Liverpool,Ohio. Owned by Swiss company VonRoll and built a decade ago, WTI will meet or exceed all new emissions levels. "When we decided to build the plant 10 years ago, we knew U.S. regulations would move up to European standards so we decided to design the plant to meet those standards," says Fred Sigg, WTI general manager. "It was easier and cheaper to do it then." Sigg supports the new standards but wishes the dioxins level was tighter, noting that WTI emits less than half the new maximum. WTI adds activated carbon to capture dioxin and mercury emissions, something EPA considered but dropped as too expensive. "This isn't rocket science, but our plant is cleverly engineered, using technologies that have been around for decades," he says. Sigg doesn't mention it, but there is another reason for WTI's low emissions--its location. The plant is on a flood plain, a stone's throw from homes, and the top of its stack is but 300 yards from an elementary school that rests on a bluff above the plant. Almost from the ribbon cutting, WTI has faced a vocal, angry, and well-organized group of community activists who have tried to shut down the site. So far they have failed, but incinerator opponents are unlikely to be satisfied with standards WTI can meet without doing much. Still, WTI is among the world's cleanest, best run hazardous waste burners. How it navigates today's changing seas may hint at what lies ahead for other kilns and incinerators. © 2000 Green Environmental Coalition. All rights reserved worldwide. Cached documents copyright by their respective authors. Kåre Helge Karstensen [email protected] Page 317 of 420 Annex 6 Council Directive of 12 December 1991 on hazardous waste (91/689/EEC) The Hazardous Waste Directive is one of the oldest EU legislative acts on waste. Its provisions are indispensable for safeguarding a high level of environmental protection; and the differentiation it introduces between hazardous and non hazardous waste is along with the differentiation between recovery and disposal laid down in the Waste Framework Directive a key element of waste management policy. The elaboration of the Strategy on Prevention and Recycling on Waste includes an assessment of existing waste policies. In this regard the Hazardous Waste Directive will undergo a detailed examination. One objective of this review is to improve waste legislation by simplifying it. Therefore the strong connection between the provisions on waste and those exclusively applied to hazardous waste might justify their integration into one Directive. Council Directive of 12 December 1991 on hazardous waste (91/689/EEC) Having regard to the Treaty establishing the European Economic Community, and in particular Article 130s thereof, Having regard to the proposal from the Commission (1), Having regard to the opinion of the European Parliament (2), Having regard to the opinion of the Economic and Social Committee (3), Whereas Council Directive 78/319/EEC of 20 March 1978 on toxic and dangerous waste (4), established Community rules on the disposal of dangerous waste; whereas in order to take account of experience gained in the implementation of that Directive by the Member States, it is necessary to amend the rules and to replace Directive 78/319/EEC by this Directive; Kåre Helge Karstensen [email protected] Page 318 of 420 Whereas the Council resolution of 7 May 1990 on waste policy (5) and the action programme of the European Communities on the environment, which was the subject of the resolution of the Council of the European Communities and of the representatives of the Government of the Member States, meeting within the Council, of 19 October 1987 on the continuation and implementation of a European Community policy and action programme on the environment (1987 to 1992) (6), envisage Community measures to improve the conditions under which hazardous wastes are disposed of and managed; Whereas the general rules applying to waste management which are laid down by Council Directive 75/442/EEC of 15 July 1975 on waste (7), as amended by Directive 91/156/EEC (8), also apply to the management of hazardous waste; Whereas the correct management of hazardous waste necessitates additional, more stringent rules to take account of the special nature of such waste; Whereas it is necessary, in order to improve the effectiveness of the management of hazardous waste in the Community, to use a precise and uniform definition of hazardous waste based on experience; Whereas it is necessary to ensure that disposal and recovery of hazardous waste is monitored in the fullest manner possible; Whereas it must be possible rapidly to adapt the provisions of this Directive to scientific and technical progress; whereas the Committee set up by Directive 75/442/EEC must also empowered to adapt the provisions of this Directive to such progress, Article 1 1. The object of this Directive, drawn up pursuant to Article 2 (2) of Directive 75/442/EEC, is to approximate the laws of the Member States on the controlled management of hazardous waste. 2. Subject to this Directive, Directive 75/442/EEC shall apply to hazardous waste. Kåre Helge Karstensen [email protected] Page 319 of 420 3. The definition of ‘waste’ and of the other terms used in this Directive shall be those in Directive 75/442/EEC. 4. For the purpose of this Directive ‘hazardous waste’ means: - wastes featuring on a list to be drawn up in accordance with the procedure laid down in Article 18 of Directive 75/442/EEC on the basis of Annexes I and II to this Directive, not later than six months before the date of implementation of this Directive. These wastes must have one or more of the properties listed in Annex III. The list shall take into account the origin and composition of the waste and, where necessary, limit values of concentration. This list shall be periodically reviewed and if necessary by the same procedure, - any other waste which is considered by a Member State to display any of the properties listed in Annex III. Such cases shall be notified to the Commission and reviewed in accordance with the procedure laid down in Article 18 of Directive 75/442/EEC with a view to adaptation of the list. 5. Domestic waste shall be exempted from the provisions of this Directive. The Council shall establish, upon a proposal from the Commission, specific rules taking into consideration the particular nature of domestic waste not later than the end of 1992. Article 2 1. Member States shall take the necessary measures to require that on every site where tipping (discharge) of hazardous waste takes place the waste is recorded and identified. 2. Member States shall take the necessary measures to require that establishment and undertaking which dispose of, recover, collect or transport hazardous waste do not mix different categories of hazardous waste or mix hazardous waste with non-hazardous waste. Kåre Helge Karstensen [email protected] Page 320 of 420 3. By way of derogation from paragraph 2, the mixing of hazardous waste with other hazardous waste or with other waste, substances or materials may be permitted only where the conditions laid down in Article 4 of Directive 75/442/EEC are complied with and in particular for the purpose of improving safety during disposal or recovery. Such an operation shall be subject to the permit requirement imposed in Articles 9, 10 and 11 of Directive 75/442/EEC. 4. Where waste is already mixed with other waste, substances or materials, separation must be effected, where technically and economically feasible, and where necessary in order to comply with Article 4 of Directive 75/442/EEC. Article 3 1. The derogation referred to in Article 11 (1) (a) of Directive 75/442/ EEC from the permit requirement for establishments or undertakings which carry out their own waste disposal shall not apply to hazardous waste covered by this Directive. 2. In accordance with Article 11 (1) (b) of Directive 75/442/EEC, a Member State may waive Article 10 of that Directive for establishments or undertakings which recover waste covered by this Directive: - if the Member State adopts general rules listing the type and quantity of waste and laying down specific conditions (limit values for the content of hazardous substances in the waste, emission limit values, type of activity) and other necessary requirements for carrying out different forms of recovery, and - if the types or quantities of waste and methods of recovery are such that the conditions laid down in Article 4 of Directive 75/442/EEC are complied with. 3. The establishments or undertakings referred to in paragraph 2 shall be registered with the competent authorities. Kåre Helge Karstensen [email protected] Page 321 of 420 4. If a Member State intends to make use of the provisions of paragraph 2, the rules referred to in that paragraph shall be sent to the Commission not later than three months prior to their coming into force. The Commission shall consult the Member States. In the light of these consultations the Commission shall propose that the rules be finally agreed upon in accordance with the procedure laid down in Article 18 of Directive 75/442/EEC. Article 4 1. Article 13 of Directive 75/442/EEC shall also apply to producers of hazardous waste. 2. Article 14 of Directive 75/442/EEC shall also apply to producers of hazardous waste and to all establishments and undertakings transporting hazardous waste. 3. The records referred to in Article 14 of Directive 75/442/EEC must be preserved for at least three years except in the case of establishments and undertakings transporting hazardous waste which must keep such records for at least 12 months. Documentary evidence that the management operations have been carried out must be supplied at the request of the competent authorities or of a previous holder. Article 5 1. Member States shall take the necessary measures to ensure that, in the course of collection, transport and temporary storage, waste is properly packaged and labelled in accordance with the international and Community standards in force. 2. In the case of hazardous waste, inspections concerning collection and transport operations made on the basis of Article 13 of Directive 75/442/EEC shall cover more particularly the origin and destination of such waste. 3. Where hazardous waste is transferred, it shall be accompanied by an identification form containing the details specified in Section A of Annex I to Council Directive Kåre Helge Karstensen [email protected] Page 322 of 420 84/631/EEC of 6 December 1984 on the supervision and control within the European Community of the transfrontier shipment of hazardous waste (1), as last amended by Directive 86/279/EEC (2). Article 6 1. As provided in Article 7 of Directive 75/442/EEC, the competent authorities shall draw up, either separately or in the framework of their general waste management plans, plans for the management of hazardous waste and shall make these plans public. 2. The Commission shall compare these plans, and in particular the methods of disposal and recovery. It shall make this information available to the competent authorities of the Member States which ask for it. Article 7 In cases of emergency or grave danger, Member States shall take all necessary steps, including, where appropriate, temporary derogations from this Directive, to ensure that hazardous waste is so dealt with as not to constitute a threat to the population or the environment. The Member State shall inform the Commission of any such derogations. Article 8 1. In the context of the report provided for in Article 16 (1) of Directive 75/442/EEC, and on the basis of a questionnaire drawn up in accordance with that Article, the Member States shall send the Commission a report on the implementation of this Directive. 2. In addition to the consolidated report referred to in Article 16 (2) of Directive 75/442/EEC, the Commission shall report to the European Parliament and the Council every three years on the implementation of this Directive. Kåre Helge Karstensen [email protected] Page 323 of 420 3. In addition, by 12 December 1994, the Member States shall send the Commission the following information for every establishment or undertaking which carries out disposal and/or recovery of hazardous waste principally on behalf of third parties and which is likely to form part of the integrated network referred to in Article of Directive 75/442/ EEC: - name and address, - the method used to treat waste, - the types and quantities of waste which can be treated. Once a year, Member States shall inform the Commission of any changes in this information. The Commission shall make this information available on request to the competent authorities in the Member States. The format in which this information will be supplied to the Commission shall be agreed upon in accordance with the procedure laid down in Article 18 of Directive 75/442/EEC. Article 9 The amendments necessary for adapting the Annexes to this Directive to scientific and technical progress and for revising the list of wastes referred to in Article 1 (4) shall be adopted in accordance with the procedure laid down in Article 18 of Directive 74/442/EEC. Article 10 Kåre Helge Karstensen [email protected] Page 324 of 420 1. Member States shall bring into force the laws, regulations and administrative provisions necessary for them to comply with this Directive by 27 June 1995. They shall immediately inform the Commission thereof. 2. When Member States adopt these measures, they shall contain a reference to this Directive or shall be accompanied by such reference on the occasion of their official publication. The methods of making such a reference shall be laid down by the Member States. 3. Member States shall communicate to the Commission the texts of the main provisions of national law which they adopt in the field governed by this Directive. Article 11 Directive 78/319/EEC shall be repealed with effect from 27 June 1995. Article 12 This Directive is addressed to the Member States. Annex I Categories or generic types of hazardous waste listed according to their nature or the activity which generated them (*) (waste may be liquid, sludge or solid in form) Annex I. A. Wastes displaying any of the properties listed in Annex III and which consist of: Kåre Helge Karstensen [email protected] Page 325 of 420 1. anatomical substances; hospital and other clinical wastes; 2. pharmaceuticals, medicines and veterinary compounds; 3. wood preservatives; 4. biocides and phyto-pharmaceutical substances; 5. residue from substances employed as solvents; 6. halogenated organic substances not employed as solvents excluding inert polymerized materials; 7. tempering salts containing cyanides; 8. mineral oils and oily substances (e.g. cutting sludges, etc.); 9. oil/water, hydrocarbon/water mixtures, emulsions; 10. substances containing PCBs and/or PCTs (e.g. dielectrics etc.); 11. tarry materials arising from refining, distillation and any pyrolytic treatment (e.g. still bottoms, etc.); 12. inks, dyes, pigments, paints, lacquers, varnishes; 13. resins, latex, plasticizers, glues/adhesives; 14. chemical substances arising from research and development or teaching activities which are not identified and/or are new and whose effects on man and/or the environment are not known (e.g. laboratory residues, etc.); 15. pyrotechnics and other explosive materials; Kåre Helge Karstensen [email protected] Page 326 of 420 16. photographic chemicals and processing materials; 17. any material contaminated with any congener of polychlorinated dibenzo- furan; 18. any material contaminated with any congener of polychlorinated dibenzo-p- dioxin. Annex I.B. Wastes which contain any of the constituents listed in Annex II and having any of the properties listed in Annex III and consisting of: 19. animal or vegetable soaps, fats, waxes; 20. non-halogenated organic substances not employed as solvents; 21. inorganic substances without metals or metal compounds; 22. ashes and/or cinders; 23. soil, sand, clay including dredging spoils; 24. non-cyanidic tempering salts; 25. metallic dust, powder; 26. spent catalyst materials; 27. liquids or sludges containing metals or metal compounds; 28. residue from pollution control operations (e.g. baghouse dusts, etc.) except (29), (30) and (33); 29. scrubber sludges; Kåre Helge Karstensen [email protected] Page 327 of 420 30. sludges from water purification plants; 31. decarbonization residue; 32. ion-exchange column residue; 33. sewage sludges, untreated or unsuitable for use in agriculture; 34. residue from cleaning of tanks and/or equipment; 35. contaminated equipment; 36. contaminated containers (e.g. packaging, gas cylinders, etc.) whose contents included one or more of the constituents listed in Annex II; 37. batteries and other electrical cells; 38. vegetable oils; 39. materials resulting from selective waste collections from households and which exhibit any of the characteristics listed in Annex III; 40. any other wastes which contain any of the constituents listed in Annex II and any of the properties listed in Annex III. Annex II Constituents of the wastes in annex i.b. which render them hazardous when they have the properties described in Annex III (*) Kåre Helge Karstensen [email protected] Page 328 of 420 Wastes having as constituents: C1 beryllium; beryllium compounds; C2 vanadium compounds; C3 chromium (VI) compounds; C4 cobalt compounds; C5 nickel compounds; C6 copper compounds; C7 zinc compounds; C8 arsenic; arsenic compounds; C9 selenium; selenium compounds; C10 silver compounds; C11 cadmium; cadmium compounds; C12 tin compounds; C13 antimony; antimony compounds; C14 tellurium; tellurium compounds; C15 barium compounds; excluding barium sulfate; C16 mercury; mercury compounds; Kåre Helge Karstensen [email protected] Page 329 of 420 C17 thallium; thallium compounds; C18 lead; lead compounds; C19 inorganic sulphides; C20 inorganic fluorine compounds, excluding calcium fluoride; C21 inorganic cyanides; C22 the following alkaline or alkaline earth metals: lithium, sodium, potassium, calcium, magnesium in uncombined form; C23 acidic solutions or acids in solid form; C24 basic solutions or bases in solid form; C25 asbestos (dust and fibres); C26 phosphorus: phosphorus compounds, excluding mineral phosphates; C27 metal carbonyls; C28 peroxides; C29 chlorates; C30 perchlorates; C31 azides; C32 PCBs and/or PCTs; C33 pharmaceutical or veterinary compounds; Kåre Helge Karstensen [email protected] Page 330 of 420 C34 biocides and phyto-pharmaceutical substances (e.g. pesticides, etc.); C35 infectious substances; C36 creosotes; C37 isocyanates; thiocyanates; C38 organic cyanides (e.g. nitriles, etc.); C39 phenols; phenol compounds; C40 halogenated solvents; C41 organic solvents, excluding halogenated solvents; C42 organohalogen compounds, excluding inert polymerized materials and other substances referred to in this Annex; C43 aromatic compounds; polycyclic and heterocyclic organic compounds; C44 aliphatic amines; C45 aromatic amines C46 ethers; C47 substances of an explosive character, excluding those listed elsewhere in this Annex; C48 sulphur organic compounds; C49 any congener of polychlorinated dibenzo-furan; C50 any congener of polychlorinated dibenzo-p-dioxin; C51 hydrocarbons and their oxygen; nitrogen and/or sulphur compounds not otherwise taken into account in this Annex. Kåre Helge Karstensen [email protected] Page 331 of 420 Annex III Properties of wastes which render them hazardous H1 ‘Explosive’: substances and preparations which may explode under the effect of flame or which are more sensitive to shocks or friction than dinitrobenzene. H2 ‘Oxidizing’: substances and preparations which exhibit highly exothermic reactions when in contact with other substances, particularly flammable substances. H3-A ‘Highly flammable’: - liquid substances and preparations having a flash point below 21 ºC (including extremely flammable liquids), or - substances and preparations which may become hot and finally catch fire in contact with air at ambient temperature without any application of energy, or - solid substances and preparations which may readily catch fire after brief contact a source of ignition and which continue to burn or to be consumed after removal of the source of ignition, or - gaseous substances and preparations which are flammable in air at normal pressure, or - substances and preparations which, in contact with water or damp air, evolve highly flammable gases in dangerous quantities. H3-B ‘Flammable’: liquid substances and preparations having a flash point equal to or greater than 21 ºC and less than or equal to 55 ºC. Kåre Helge Karstensen [email protected] Page 332 of 420 H4 ‘Irritant’: non-corrosive substances and preparations which, through immediate, prolonged or repeated contact with the skin or mucous membrane, can cause inflammation. H5 ‘harmful’: substances and preparations which, if they are inhaled or ingested or if they penetrate the skin, may involve limited health risks. H6 ‘Toxic’: substances and preparations (including very toxic substances and preparations) which, if they are inhaled or ingested or if they penetrate the skin, may involve serious, acute or chronic health risks and even death. H7 ‘Carcinogenic’: substances and preparations which, if they are inhaled or ingested or if they penetrate the skin, may induce cancer or increase its incidence. H8 ‘Corrosive’: substances and preparations which may destroy living tissue on contacts. H9 ‘Infectious’: substances containing viable micro-organisms or their toxins which are known or reliably believed to cause disease in man or other living organisms. H10 ‘Teratogenic’: substances and preparations which, if they are inhaled or ingested or if the penetrate the skin, may induce non-hereditary congenital malformations or increase their incidence. H11 ‘Mutagenic’: substances and preparations which, if they are inhaled or ingested or if they penetrate the skin, may induce hereditary genetic defects or increase their incidence. H12 Substances and preparations which release toxic or very toxic gases in contact with water, air or an acid. H13 Substances and preparations capable by any means, after disposal, of yielding another substance, e.g. a leachate, which possesses any of the characteristics listed above. Kåre Helge Karstensen [email protected] Page 333 of 420 H14 ‘Ecotoxic’: substances and preparations which present or may present immediate or delayed risks for one or more sectors of the environment. Notes 1. Attribution of the hazard properties ‘toxic’ (and ‘very toxic’), ‘harmful’, ‘corrosive’ and ‘irritant’ is made on the basis of the criteria laid down by Annex VI, part I A and part II B, of Council Directive 67/548/EEC of 27 June 1967 of the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances (1), in the version as amended by Council Directive 79/831/EEC (2). 2. With regard to attribution of the properties ‘carcinogenic’, ‘teratogenic’ and ‘mutagenic’, and reflecting the most recent findings, additional criteria are contained in the Guide to the classification and labelling of dangerous substances and preparations of Annex VI (part II D) to Directive 67/548/EEC in the version as amended by Commission Directive 83/467/EEC (1). Test methods The test methods serve to give specific meaning to the definitions given in Annex III. The methods to be used are those described in Annex V to Directive 67/548/EEC, in the version as amended by Commission Directive 84/449/EEC (2), or by subsequent Commission Directives adapting Directive 67/548/EEC to technical progress. These methods are themselves based on the work and recommendations of the competent international bodies, in particular the OECD. Kåre Helge Karstensen [email protected] Page 334 of 420 Annex 7 Directive 2000/76/EC of the European Parliament and of the council of 4 December 2000 on the incineration of waste The European Parliament and the council of the European Union, Having regard to the Treaty establishing the European Community, and in particular Article 175(1) thereof, Having regard to the proposal from the Commission (1), Having regard to the Opinion of the Economic and Social Committee (2), Having regard to the Opinion of the Committee of the Regions (3), Acting in accordance with the procedure laid down in Article 251 of the Treaty (4), and in the light of the joint text approved by the Conciliation Committee on 11 October 2000, Whereas: (1) The fifth Environment Action Programme: Towards sustainability A European Community programme of policy and action in relation to the environment and sustainable development, supplemented by Decision No 2179/98/EC on its review (5), sets as an objective that critical loads and levels of certain pollutants such as nitrogen oxides (NO ), sulphur dioxide (SO ), heavy metals and dioxins should not be exceeded, while in terms of air quality the objective is that all people should be effectively protected against recognized health risks from air pollution. That Programme further sets as an objective a 90% reduction of dioxin emissions of identified sources by 2005 (1985 level) and at least 70% reduction from all pathways of cadmium (Cd), mercury (Hg) and lead (Pb) emissions in 1995. Kåre Helge Karstensen [email protected] Page 335 of 420 (2) The Protocol on persistent organic pollutants signed by the Community within the framework of the United Nations Economic Commission for Europe (UN-ECE) Convention on long-range transboundary air pollution sets legally binding limit values for the emission of dioxins and furans of 0,1 ng/m; TE (Toxicity Equivalents) for installations burning more than 3 tonnes per hour of municipal solid waste, 0,5 ng/m; TE for installations burning more than 1 tonne per hour of medical waste, and 0,2 ng/m; TE for installations burning more than 1 tonne per hour of hazardous waste. (3) The Protocol on Heavy Metals signed by the Community within the framework of the UN-ECE Convention on long-range transboundary air pollution sets legally binding limit values for the emission of particulate of 10 mg/m3 for hazardous and medical waste incineration and for the emission of mercury of 0,05 mg/m3 for hazardous waste incineration and 0,08 mg/m3 for municipal waste incineration. (4) The International Agency for Research on Cancer and the World Health Organisation indicate that some polycyclic aromatic hydrocarbons (PAHs) are carcinogenic. Therefore, Member States may set emission limit values for PAHs among other pollutants. (5) In accordance with the principles of subsidiarity and proportionality as set out in Article 5 of the Treaty, there is a need to take action at the level of the Community. The precautionary principle provides the basis for further measures. This Directive confines itself to minimum requirements for incineration and co-incineration plants. (6) Further, Article 174 provides that Community policy on the environment is to contribute to protecting human health. (7) Therefore, a high level of environmental protection and human health protection requires the setting and maintaining of stringent operational conditions, technical requirements and emission limit values for plants incinerating or co-incinerating waste within the Community. The limit values set should prevent or limit as far as practicable negative effects on the environment and the resulting risks to human health. Kåre Helge Karstensen [email protected] Page 336 of 420 (8) The Communication from the Commission on the review of the Community Strategy for waste management assigns prevention of waste the first priority, followed by reuse and recovery and finally by safe disposal of waste; in its Resolution of 24 February 1997 on a Community Strategy for waste management (6), the Council reiterated its conviction that waste prevention should be the first priority of any rational waste policy in relation to minimizing waste production and the hazardous properties of waste. (9) In its Resolution of 24 February 1997 the Council also underlines the importance of Community criteria concerning the use of waste, the need for appropriate emission standards to apply to incineration facilities, the need for monitoring measures to be envisaged for existing incineration plants, and the need for the Commission to consider amending Community legislation in relation to the incineration of waste with energy recovery in order to avoid large-scale movements of waste for incineration or co-incineration in the Community. (10) It is necessary to set strict rules for all plants incinerating or co-incinerating waste in order to avoid transboundary movements to plants operating at lower costs due to less stringent environmental standards. (11) The Communication from the Commission/energy for the future: renewable sources of energy/White paper for a Community strategy and action plan takes into consideration in particular the use of biomass for energy purposes. (12) Council Directive 96/61/EC (1) sets out an integrated approach to pollution prevention and control in which all the aspects of an installations environmental performance are considered in an integrated manner. Installations for the incineration of municipal waste with a capacity exceeding 3 tonnes per hour and installations for the disposal or recovery of hazardous waste with a capacity exceeding 10 tonnes per day are included within the scope of the said Directive. (13) Compliance with the emission limit values laid down by this Directive should be regarded as a necessary but not sufficient condition for compliance with the requirements of Directive 96/61/EC. Such compliance may involve more stringent Kåre Helge Karstensen [email protected] Page 337 of 420 emissions limit values for the pollutants envisaged by this Directive, emission limit values for other substances and other media, and other appropriate conditions. (14) Industrial experience in the implementation of techniques for the reduction of polluting emissions from incineration plants has been acquired over a period of ten years. (15) Council Directives 89/369/EEC (2) and 89/429/EEC (3) on the prevention and reduction of air pollution from municipal waste incineration plants have contributed to the reduction and control of atmospheric emissions from incineration plants. More stringent rules should now be adopted and those Directives should accordingly be repealed. (16) The distinction between hazardous and non-hazardous waste is based principally on the properties of waste prior to incineration or co-incineration but not on differences in emissions. The same emission limit values should apply to the incineration or coincineration of hazardous and non-hazardous waste but different techniques and conditions of incineration or co-incineration and different monitoring measures upon reception of waste should be retained. (17) Member States should take into account Council Directive 1999/30/EC of 22 April 1999 relating to limit values for sulphur dioxide, nitrogen dioxide and oxides of nitrogen, particulate matter and lead in ambient air (4) when implementing this Directive. (18) The incineration of hazardous waste with a content of more than 1% of halogenated organic substances, expressed as chlorine, has to comply with certain operational conditions in order to destroy as many organic pollutants such as dioxins as possible. (19) The incineration of waste which contains chlorine generates flue gas residues. Such residues should be managed in a way that minimizes their amount and harmfulness. (20) There may be grounds to provide for specified exemptions to the emission limit values for some pollutants during a specified time limit and subject to specific conditions. Kåre Helge Karstensen [email protected] Page 338 of 420 (21) Criteria for certain sorted combustible fraction of nonhazardous waste not suitable for recycling, should be developed in order to allow the authorization of the reduction of the frequency of periodical measurements. (22) A single text on the incineration of waste will improve legal clarity and enforceability. There should be a single directive for the incineration and co-incineration of hazardous and non-hazardous waste taking fully into account the substance and structure of Council Directive 94/67/EC of 16 December 1994 on the incineration of hazardous waste (5). Therefore Directive 94/67/EC should also be repealed. (23) Article 4 of Council Directive 75/442/EEC of 15 July 1975 on waste (6) requires Member States to take the necessary measures to ensure that waste is recovered or disposed of without endangering human health and without harming the environment. To this end, Articles 9 and 10 of that Directive provide that any plant or undertaking treating waste must obtain a permit from the competent authorities relating, inter alia, to the precautions to be taken. (24) The requirements for recovering the heat generated by the incineration or coincineration process and for minimizing and recycling residues resulting from the operation of incineration or co-incineration plants will assist in meeting the objectives of Article 3 on the waste hierarchy of Directive 75/442/EEC. (25) Incineration and co-incineration plants treating only animal waste regulated by Directive 90/667/EEC (1) are excluded from the scope of this Directive. The Commission intends to propose a revision to the requirements of Directive 90/667 with a view to providing for high environmental standards for the incineration and co incineration of animal waste. (26) The permit for an incineration or co-incineration plant shall also comply with any applicable requirements laid down in Directives 91/271/EEC (2), 96/61/EC, 96/62/EC (3), 76/464/EEC (4), and 1999/31/EC (5). Kåre Helge Karstensen [email protected] Page 339 of 420 (27) The co-incineration of waste in plants not primarily intended to incinerate waste should not be allowed to cause higher emissions of polluting substances in that part of the exhaust gas volume resulting from such co-incineration than those permitted for dedicated incineration plants and should therefore be subject to appropriate limitations. (28) High-standard measurement techniques are required to monitor emissions to ensure compliance with the emission limit values for the pollutants. (29) The introduction of emission limit values for the discharge of waste water from the cleaning of exhaust gases from incineration and co-incineration plants will limit a transfer of pollutants from the air into water. (30) Provisions should be laid down for cases where the emission limit values are exceeded as well as for technically unavoidable stoppages, disturbances or failures of the purification devices or the measurement devices. (31) In order to ensure transparency of the permitting process throughout the Community the public should have access to information with a view to allowing it to be involved in decisions to be taken following applications for new permits and their subsequent updates. The public should have access to reports on the functioning and monitoring of the plants burning more than three tonnes per hour in order to be informed of their potential effects on the environment and human health. (32) The Commission should present a report both to the European Parliament and the Council based on the experience of applying this Directive, the new scientific knowledge gained, the development of the state of technology, the progress achieved in emission control techniques, and on the experience made in waste management and operation of the plants and on the development of environmental requirements, with a view to proposing, as appropriate, to adapt the related provisions of this Directive. (33) The measures necessary for the implementation of this Directive are to be adopted in accordance with Council Decision 1999/468/EC of 28 June 1999 laying down the procedures for the exercise of implementing powers conferred on the Commission (6). Kåre Helge Karstensen [email protected] Page 340 of 420 (34) Member States should lay down rules on penalties applicable to infringements of the provisions of this Directive and ensure that they are implemented; those penalties should be effective, proportionate and dissuasive, have adopted this directive: Article 1 Objectives The aim of this Directive is to prevent or to limit as far as practicable negative effects on the environment, in particular pollution by emissions into air, soil, surface water and groundwater, and the resulting risks to human health, from the incineration and coincineration of waste. This aim shall be met by means of stringent operational conditions and technical requirements, through setting emission limit values for waste incineration and co-incineration plants within the Community and also through meeting the requirements of Directive 75/442/EEC. Article 2 Scope 1. This Directive covers incineration and co-incineration plants. 2. The following plants shall however be excluded from the scope of this Directive: (a) Plants treating only the following wastes: Kåre Helge Karstensen [email protected] Page 341 of 420 (i) vegetable waste from agriculture and forestry, (ii) vegetable waste from the food processing industry, if the heat generated is recovered, (iii) fibrous vegetable waste from virgin pulp production and from production of paper from pulp, if it is co-incinerated at the place of production and the heat generated is recovered, (iv) wood waste with the exception of wood waste which may contain halogenated organic compounds or heavy metals as a result of treatment with wood-preservatives or coating, and which includes in particular such wood waste originating from construction and demolition waste, (v) cork waste, (vi) radioactive waste, (vii) animal carcasses as regulated by Directive 90/667/EEC without prejudice to its future amendments, (viii) waste resulting from the exploration for, and the exploitation of, oil and gas resources from off-shore installations and incinerated on board the installation; (b) Experimental plants used for research, development and testing in order to improve the incineration process and which treat less than 50 tonnes of waste per year. Article 3 Definitions Kåre Helge Karstensen [email protected] Page 342 of 420 For the purposes of this Directive: 1. ‘waste’ means any solid or liquid waste as defined in Article 1(a) of Directive 75/442/EEC; 2. ‘hazardous waste’ means any solid or liquid waste as defined in Article 1(4) of Council Directive 91/689/EEC of 12 December 1991 on hazardous waste (1). For the following hazardous wastes, the specific requirements for hazardous waste in this Directive shall not apply: (a) combustible liquid wastes including waste oils as defined in Article 1 of Council Directive 75/439/EEC of 16 June 1975 on the disposal of waste oils (2) provided that they meet the following criteria: (i) the mass content of polychlorinated aromatic hydrocarbons, e.g. polychlorinated biphenyls (PCB) or pentachlorinated phenol (PCP) amounts to concentrations not higher than those set out in the relevant Community legislation; (ii) these wastes are not rendered hazardous by virtue of containing other constituents listed in Annex II to Directive 91/689/EEC in quantities or in concentrations which are inconsistent with the achievement of the objectives set out in Article 4 of Directive 75/442/EEC; and (iii) the net calorific value amounts to at least 30 MJ per kilogram, (b) any combustible liquid wastes which cannot cause, in the flue gas directly resulting from their combustion, emissions other than those from gasoil as defined in Article 1(1) of Directive 93/12/EEC (3) or a higher concentration of emissions than those resulting from the combustion of gasoil as so defined; 3. ‘mixed municipal waste’ means waste from households as well as commercial, industrial and institutional waste, which because of its nature and composition is similar to waste from households, but excluding fractions indicated in the Annex to Kåre Helge Karstensen [email protected] Page 343 of 420 Decision 94/3/EC (4) under heading 20 01 that are collected separately at source and excluding the other wastes indicated under heading 20 02 of that Annex; 4. ‘incineration plant’ means any stationary or mobile technical unit and equipment dedicated to the thermal treatment of wastes with or without recovery of the combustion heat generated. This includes the incineration by oxidation of waste as well as other thermal treatment processes such as pyrolysis, gasification or plasma processes in so far as the substances resulting from the treatment are subsequently incinerated. This definition covers the site and the entire incineration plant including all incineration lines, waste reception, storage, on site pretreatment facilities, waste-fuel and airsupply systems, boiler, facilities for the treatment of exhaust gases, on-site facilities for treatment or storage of residues and waste water, stack, devices and systems for controlling incineration operations, recording and monitoring incineration conditions; 5. ‘co-incineration plant’ means any stationary or mobile plant whose main purpose is the generation of energy or production of material products and: — which uses wastes as a regular or additional fuel; or — in which waste is thermally treated for the purpose of disposal. If co-incineration takes place in such a way that the main purpose of the plant is not the generation of energy or production of material products but rather the thermal treatment of waste, the plant shall be regarded as an incineration plant within the meaning of point 4. This definition covers the site and the entire plant including all co-incineration lines, waste reception, storage, on site pretreatment facilities, waste-, fuel and air-supply systems, boiler, facilities for the treatment of exhaust gases, on-site facilities for treatment or storage of residues and waste water, stack devices and systems for controlling incineration operations, recording and monitoring incineration conditions; Kåre Helge Karstensen [email protected] Page 344 of 420 6. ‘existing co-incineration or co-incineration plant’ means an incineration or coincineration plant: (a) which is in operation and has a permit in accordance with existing Community legislation before 28 December 2002, or, (b) which is authorized or registered for incineration or co-incineration and has a permit issued before 28 December 2002 in accordance with existing Community legislation, provided that the plant is put into operation not later than 28 December 2003, or (c) which, in the view of the competent authority, is the subject of a full request for a permit, before 28 December 2002, provided that the plant is put into operation not later than 28 December 2004; 7. ‘nominal capacity’ means the sum of the incineration capacities of the furnaces of which an incineration plant is composed, as specified by the constructor and confirmed by the operator, with due account being taken, in particular, of the calorific value of the waste, expressed as the quantity of waste incinerated per hour; 8. ‘emission’ means the direct or indirect release of substances, vibrations, heat or noise from individual or diffuse sources in the plant into the air, water or soil; 9. ‘emission limit values’ means the mass, expressed in terms of certain specific parameters, concentration and/or level of an emission, which may not be exceeded during one or more periods of time; 10. ‘dioxins and furans’ means all polychlorinated dibenzo-p-dioxins and dibenzofurans listed in Annex I; 11. ‘operator’ means any natural or legal person who operates or controls the plant or, where this is provided for in national legislation, to whom decisive economic power over the technical functioning of the plant has been delegated; Kåre Helge Karstensen [email protected] Page 345 of 420 12. ‘permit’ means a written decision (or several such decisions) delivered by the competent authority granting authorization to operate a plant, subject to certain conditions which guarantee that the plant complies with all the requirements of this Directive. A permit may cover one or more plants or parts of a plant on the same site operated by the same operator; 13. ‘residue’ means any liquid or solid material (including bottom ash and slag, fly ash and boiler dust, solid reaction products from gas treatment, sewage sludge from the treatment of waste waters, spent catalysts and spent activated carbon) defined as waste in Article 1(a) of Directive 75/442/EEC, which is generated by the incineration or coincineration process, the exhaust gas or waste water treatment or other processes within the incineration or co-incineration plant. Article 4 Application and permit 1. Without prejudice to Article 11 of Directive 75/442/EEC or to Article 3 of Directive 91/689/EEC, no incineration or co-incineration plant shall operate without a permit to carry out these activities. 2. Without prejudice to Directive 96/61/EC, the application for a permit for an incineration or co-incineration plant to the competent authority shall include a description of the measures which are envisaged to guarantee that: (a) the plant is designed, equipped and will be operated in such a manner that the requirements of this Directive are taking into account the categories of waste to be incinerated; (b) the heat generated during the incineration and co-incineration process is recovered as far as practicable e.g. through combined heat and power, the generating of process steam or district heating; Kåre Helge Karstensen [email protected] Page 346 of 420 (c) the residues will be minimized in their amount and harmfulness and recycled where appropriate; (d) the disposal of the residues which cannot be prevented, reduced or recycled will be carried out in conformity with national and Community legislation. 3. The permit shall be granted only if the application shows that the proposed measurement techniques for emissions into the air comply with Annex III and, as regards water, comply with Annex III paragraphs 1 and 2. 4. The permit granted by the competent authority for an incineration or co-incineration plant shall, in addition to complying with any applicable requirement laid down in Directives 91/271/EEC, 96/61/EC, 96/62/EC, 76/464/EEC and 1999/31/EC: (a) list explicitly the categories of waste which may be treated. The list shall use at least the categories of waste set up in the European Waste Catalogue (EWC), if possible, and contain information on the quantity of waste, where appropriate; (b) include the total waste incinerating or co-incinerating capacity of the plant; (c) specify the sampling and measurement procedures used to satisfy the obligations imposed for periodic measurements of each air and water pollutants. 5. The permit granted by the competent authority to an incineration or co-incineration plant using hazardous waste shall in addition to paragraph 4: (a) list the quantities of the different categories of hazardous waste which may be treated; (b) specify the minimum and maximum mass flows of those hazardous wastes, their lowest and maximum calorific values and their maximum contents of pollutants, e.g. PCB, PCP, chlorine, fluorine, sulphur, heavy metals. Kåre Helge Karstensen [email protected] Page 347 of 420 6. Without prejudice to the provisions of the Treaty, Member States may list the categories of waste to be mentioned in the permit which can be co-incinerated in defined categories of co-incineration plants. 7. Without prejudice to Directive 96/61/EC, the competent authority shall periodically reconsider and, where necessary, update permit conditions. 8. Where the operator of an incineration or co-incineration plant for non-hazardous waste is envisaging a change of operation which would involve the incineration or coincineration of hazardous waste, this shall be regarded as a substantial change within the meaning of Article 2(10)(b) of Directive 96/61/EC and Article 12(2) of that Directive shall apply. 9. If an incineration or co-incineration plant does not comply with the conditions of the permit, in particular with the emission limit values for air and water, the competent authority shall take action to enforce compliance. Article 5 Delivery and reception of waste 1. The operator of the incineration or co-incineration plant shall take all necessary precautions concerning the delivery and reception of waste in order to prevent or to limit as far as practicable negative effects on the environment, in particular the pollution of air, soil, surface water and groundwater as well as odours and noise, and direct risks to human health. These measures shall meet at least the requirements set out in paragraphs 3 and 4. 2. The operator shall determine the mass of each category of waste, if possible according to the EWC, prior to accepting the waste at the incineration or co-incineration plant. Kåre Helge Karstensen [email protected] Page 348 of 420 3. Prior to accepting hazardous waste at the incineration or co-incineration plant, the operator shall have available information about the waste for the purpose of verifying, inter alia, compliance with the permit requirements specified in Article 4(5). This information shall cover: (a) all the administrative information on the generating process contained in the documents mentioned in paragraph 4(a); (b) the physical, and as far as practicable, chemical composition of the waste and all other information necessary to evaluate its suitability for the intended incineration process; (c) the hazardous characteristics of the waste, the substances with which it cannot be mixed, and the precautions to be taken in handling the waste. 4. Prior to accepting hazardous waste at the incineration or co-incineration plant, at least the following reception procedures shall be carried out by the operator: (a) the checking of those documents required by Directive 91/689/EEC and, where applicable, those required by Council Regulation (EEC) No 259/93 of 1 February 1993 on the supervision, and control of shipments of waste within, into and out of the European Community (1) and by dangerous-goods transport regulations; (b) the taking of representative samples, unless inappropriate, e.g. for infectious clinical waste, as far as possible before unloading, to verify conformity with the information provided for in paragraph 3 by carrying out controls and to enable the competent authorities to identify the nature of the wastes treated. These samples shall be kept for at least one month after the incineration. 5. The competent authorities may grant exemptions from paragraphs 2, 3 and 4 for industrial plants and undertakings incinerating or co-incinerating only their own waste at the place of generation of the waste provided that the requirements of this Directive are met. Kåre Helge Karstensen [email protected] Page 349 of 420 Article 6 Operating conditions 1. Incineration plants shall be operated in order to achieve a level of incineration such that the slag and bottom ashes Total Organic Carbon (TOC) content is less than 3% or their loss on ignition is less than 5% of the dry weight of the material. If necessary appropriate techniques of waste pretreatment shall be used. Incineration plants shall be designed, equipped, built and operated in such a way that the gas resulting from the process is raised, after the last injection of combustion air, in a controlled and homogeneous fashion and even under the most unfavorable conditions, to a temperature of 850 °C, as measured near the inner wall or at another representative point of the combustion chamber as authorized by the competent authority, for two seconds. If hazardous wastes with a content of more than 1% of halogenated organic substances, expressed as chlorine, are incinerated, the temperature has to be raised to 1 100 °C for at least two seconds. Each line of the incineration plant shall be equipped with at least one auxiliary burner. This burner must be switched on automatically when the temperature of the combustion gases after the last injection of combustion air falls below 850 °C or 1 100 °C as the case may be. It shall also be used during plant start-up and shut-down operations in order to ensure that the temperature of 850 °C or 1 100 °C as the case may be is maintained at all times during these operations and as long as unburned waste is in the combustion chamber. During start-up and shut-down or when the temperature of the combustion gas falls below 850 °C or 1 100 °C as the case may be, the auxiliary burner shall not be fed with fuels which can cause higher emissions than those resulting from the burning of gasoil as defined in Article 1(1) of Council Directive 75/716/EEC, liquefied gas or natural gas. Kåre Helge Karstensen [email protected] Page 350 of 420 2. Co-incineration plants shall be designed, equipped, built and operated in such a way that the gas resulting from the co-incineration of waste is raised in a controlled and homogeneous fashion and even under the most unfavorable conditions, to a temperature of 850 °C for two seconds. If hazardous wastes with a content of more than 1% of halogenated organic substances, expressed as chlorine, are co-incinerated, the temperature has to be raised to 1 100 °C. 3. Incineration and co-incineration plants shall have and operate an automatic system to prevent waste feed: (a) at start-up, until the temperature of 850 °C or 1 100 °C as the case may be or the temperature specified according to paragraph 4 has been reached; (b) whenever the temperature of 850 °C or 1 100 °C as the case may be or the temperature specified according to paragraph 4 is not maintained; (c) whenever the continuous measurements required by this Directive show that any emission limit value is exceeded due to disturbances or failures of the purification devices. 4. Conditions different from those laid down in paragraph 1 and, as regards the temperature, paragraph 3 and specified in the permit for certain categories of waste or for certain thermal processes may be authorized by the competent authority, provided the requirements of this Directive are met. Member States may lay down rules governing these authorizations. The change of the operational conditions shall not cause more residues or residues with a higher content of organic pollutants compared to those residues which could be expected under the conditions laid down in paragraph 1. Conditions different from those laid down in paragraph 2 and, as regards the temperature, paragraph 3 and specified in the permit for certain categories of waste or for certain thermal processes may be authorized by the competent authority, provided the requirements of this Directive are met. Member States may lay down rules governing these authorizations. Such authorization shall be conditional upon at least Kåre Helge Karstensen [email protected] Page 351 of 420 the provisions for emission limit values set out in Annex V for total organic carbon and CO being complied with. In the case of co-incineration of their own waste at the place of its production in existing bark boilers within the pulp and paper industry, such authorization shall be conditional upon at least the provisions for emission limit values set out in Annex V for total organic carbon being complied with. All operating conditions determined under this paragraph and the results of verifications made shall be communicated by the Member State to the Commission as part of the information provided in accordance with the reporting requirements. 5. Incineration and co-incineration plants shall be designed, equipped, built and operated in such a way as to prevent emissions into the air giving rise to significant groundlevel air pollution; in particular, exhaust gases shall be discharged in a controlled fashion and in conformity with relevant Community air quality standards by means of a stack the height of which is calculated in such a way as to safeguard human health and the environment. 6. Any heat generated by the incineration or the co-incineration process shall be recovered as far as practicable. 7. Infectious clinical waste should be placed straight in the furnace, without first being mixed with other categories of waste and without direct handling. 8. The management of the incineration or the co-incineration plant shall be in the hands of a natural person who is competent to manage the plant. Article 7 Air emission limit values Kåre Helge Karstensen [email protected] Page 352 of 420 1. Incineration plants shall be designed, equipped, built and operated in such a way that the emission limit values set out in Annex V are not exceeded in the exhaust gas. 2. Co-incineration plants shall be designed, equipped, built and operated in such a way that the emission limit values determined according to or set out in Annex II are not exceeded in the exhaust gas. If in a co-incineration plant more than 40% of the resulting heat release comes from hazardous waste, the emission limit values set out in Annex V shall apply. 3. The results of the measurements made to verify compliance with the emission limit values shall be standardized with respect to the conditions laid down in Article 11. 4. In the case of co-incineration of untreated mixed municipal waste, the limit values will be determined according to Annex V, and Annex II will not apply. 5. Without prejudice to the provisions of the Treaty, Member States may set emission limit values for polycyclic aromatic hydrocarbons or other pollutants. Article 8 Water discharges from the cleaning of exhaust gases 1. Waste water from the cleaning of exhaust gases discharged from an incineration or coincineration plant shall be subject to a permit granted by the competent authorities. 2. Discharges to the aquatic environment of waste water resulting from the cleaning of exhaust gases shall be limited as far as practicable, at least in accordance with the emission limit values set in Annex IV. Kåre Helge Karstensen [email protected] Page 353 of 420 3. Subject to a specific provision in the permit, the waste water from the cleaning of exhaust gases may be discharged to the aquatic environment after separate treatment on condition that: (a) the requirements of relevant Community, national and local provisions are complied with in the form of emission limit values; and (b) the mass concentrations of the polluting substances referred to in Annex IV do not exceed the emission limit values laid down therein. 4. The emission limit values shall apply at the point where waste waters from the cleaning of exhaust gases containing the polluting substances referred to in Annex IV are discharged from the incineration or co-incineration plant. Where the waste water from the cleaning of exhaust gases is treated on site collectively with other on-site sources of waste water, the operator shall take the measurements referred to in Article 11: (a) on the waste water stream from the exhaust gas cleaning processes prior to its input into the collective waste water treatment plant; (b) on the other waste water stream or streams prior to its or their input into the collective waste water treatment plant; (c) at the point of final waste water discharge, after the treatment, from the incineration plant or co-incineration plant. The operator shall take appropriate mass balance calculations in order to determine the emission levels in the final waste water discharge that can be attributed to the waste water arising from the cleaning of exhaust gases in order to check compliance with the emission limit values set out in Annex IV for the waste water stream from the exhaust gas cleaning process. Kåre Helge Karstensen [email protected] Page 354 of 420 Under no circumstances shall dilution of waste water take place for the purpose of complying with the emission limit values set in Annex IV. 5. When waste waters from the cleaning of exhaust gases containing the polluting substances referred to in Annex IV are treated outside the incineration or coincineration plant at a treatment plant intended only for the treatment of this sort of waste water, the emission limit values of Annex IV are to be applied at the point where the waste waters leave the treatment plant. If this off-site treatment plant is not only dedicated to treat waste water from incineration, the operator shall take the appropriate mass balance calculations, as provided for under paragraph 4(a), (b) and (c), in order to determine the emission levels in the final waste water discharge that can be attributed to the waste water arising from the cleaning of exhaust gases in order to check compliance with the emission limit values set out in Annex IV for the waste water stream from the exhaust gas cleaning process. Under no circumstances shall dilution of waste water take place for the purpose of complying with the emission limit values set in Annex IV. 6. The permit shall: (a) establish emission limit values for the polluting substances referred to in Annex IV, in accordance with paragraph 2 and in order to meet the requirements referred to in paragraph 3(a); (b) set operational control parameters for waste water at least for pH, temperature and flow. 7. Incineration and co-incineration plant sites, including associated storage areas for wastes, shall be designed and in such a way as to prevent the unauthorized and accidental release of any polluting substances into soil, surface water and groundwater in accordance with the provisions provided for in relevant Community legislation. Moreover, storage capacity shall be provided for contaminated rainwater run-off from the incineration or co-incineration plant site or for contaminated water arising from spillage or fire-fighting operations. Kåre Helge Karstensen [email protected] Page 355 of 420 The storage capacity shall be adequate to ensure that such waters can be tested and treated before discharge where necessary. 8. Without prejudice to the provisions of the Treaty, Member States may set emission limit values for polycyclic aromatic hydrocarbons or other pollutants. Article 9 Residues Residues resulting from the operation of the incineration or co-incineration plant shall be minimized in their amount and harmfulness. Residues shall be recycled, where appropriate, directly in the plant or outside in accordance with relevant Community legislation. Transport and intermediate storage of dry residues in the form of dust, such as boiler dust and dry residues from the treatment of combustion gases, shall take place in such a way as to prevent dispersal in the environment e.g. in closed containers. Prior to determining the routes for the disposal or recycling of the residues from incineration and co-incineration plants, appropriate tests shall be carried out to establish the physical and chemical characteristics and the polluting potential of the different incineration residues. The analysis shall concern the total soluble fraction and heavy metals soluble fraction. Article 10 Control and monitoring Kåre Helge Karstensen [email protected] Page 356 of 420 1. Measurement equipment shall be installed and techniques used in order to monitor the parameters, conditions and mass concentrations relevant to the incineration or coincineration process. 2. The measurement requirements shall be laid down in the permit or in the conditions attached to the permit issued by the competent authority. 3. The appropriate installation and the functioning of the automated monitoring equipment for emissions into air and water shall be subject to control and to an annual surveillance test. Calibration has to be done by means of parallel measurements with the reference methods at least every three years. 4. The location of the sampling or measurement points shall be laid down by the competent authority. 5. Periodic measurements of the emissions into the air and water shall be carried out in accordance with Annex III, points 1 and 2. Article 11 Measurement requirements 1. Member States shall, either by specification in the conditions of the permit or by general binding rules, ensure that paragraphs 2 to 12 and 17, as regards air, and paragraphs 9 and 14 to 17, as regards water, are complied with. 2. The following measurements of air pollutants shall be carried out in accordance with Annex III at the incineration and co-incineration plant: (a) continuous measurements of the following substances: NOx , provided that emission limit values are set, CO, total dust, TOC, HCl, HF, SO2; Kåre Helge Karstensen [email protected] Page 357 of 420 (b) continuous measurements of the following process operation parameters: temperature near the inner wall or at another representative point of the combustion chamber as authorized by the competent authority, concentration of oxygen, pressure, temperature and water vapor content of the exhaust gas; (c) at least two measurements per year of heavy metals, dioxins and furans; one measurement at least every three months shall however be carried out for the first 12 months of operation. Member States may fix measurement periods where they have set emission limit values for polycyclic aromatic hydrocarbons or other pollutants. 3. The residence time as well as the minimum temperature and the oxygen content of the exhaust gases shall be subject to appropriate verification, at least once when the incineration or co-incineration plant is brought into service and under the most unfavorable operating conditions anticipated. 4. The continuous measurement of HF may be omitted if treatment stages for HCl are used which ensure that the emission limit value for HCl is not being exceeded. In this case the emissions of HF shall be subject to periodic measurements as laid down in paragraph 2(c). 5. The continuous measurement of the water vapor content shall not be required if the sampled exhaust gas is dried before the emissions are analyzed. 6. Periodic measurements as laid down in paragraph 2(c) of HCl, HF and SO2 instead of continuous measuring may be authorized in the by the competent authority in incineration or co-incineration plants, if the operator can prove that the emissions of those pollutants can under no circumstances be higher than the prescribed emission limit values. 7. The reduction of the frequency of the periodic measurements for heavy metals from twice a year to once every two years and for dioxins and furans from twice a year to once every year may be authorized in the permit by the competent authority provided that the emissions resulting from co-incineration or incineration are below 50% of the emission limit values determined according to Annex II or Annex V respectively and Kåre Helge Karstensen [email protected] Page 358 of 420 provided that criteria for the requirements to be met, developed in accordance with the procedure laid down in Article 17, are available. These criteria shall at least be based on the provisions of the second subparagraph, points (a) and (d). Until 1 January 2005 the reduction of the frequency may be authorized even if no such criteria are available provided that: (a) the waste to be co-incinerated or incinerated consists only of certain sorted combustible fractions of non-hazardous waste not suitable for recycling and presenting certain characteristics, and which is further specified on the basis of the assessment referred to in subparagraph (d); (b) national quality criteria, which have been reported to the Commission, are available for these wastes; (c) co-incineration and incineration of these wastes is in line with the relevant waste management plans referred to in Article 7 of Directive 75/442/EEC; (d) the operator can prove to the competent authority that the emissions are under all circumstances significantly below the emission limit values set out in Annex II or Annex V for heavy metals, dioxins and furans; this assessment shall be based on information on the quality of the waste concerned and measurements of the emissions of the said pollutants; (e) the quality criteria and the new period for the periodic measurements are specified in the permit; and (f) all decisions on the frequency of measurements referred to in this paragraph, supplemented with information on the amount and quality of the waste concerned, shall be communicated on a yearly basis to the Commission. 8. The results of the measurements made to verify compliance with the emission limit values shall be standardized at the following conditions and for oxygen according to the formula as referred to in Annex VI: Kåre Helge Karstensen [email protected] Page 359 of 420 (a) Temperature 273 K, pressure 101,3 kPa, 11% oxygen, dry gas, in exhaust gas of incineration plants; (b) Temperature 273 K, pressure 101,3 kPa, 3% oxygen, dry gas, in exhaust gas of incineration of waste oil as defined in Directive 75/439/EEC; (c) when the wastes are incinerated or co-incinerated in an oxygen-enriched atmosphere, the results of the measurements can be standardized at an oxygen content laid down by the competent authority reflecting the special circumstances of the individual case; (d) in the case of co-incineration, the results of the measurements shall be standardized at a total oxygen content as calculated in Annex II. When the emissions of pollutants are reduced by exhaust gas treatment in an incineration or co-incineration plant treating hazardous waste, the standardization with respect to the oxygen contents provided for in the first subparagraph shall be done only if the oxygen content measured over the same period as for the pollutant concerned exceeds the relevant standard oxygen content. 9. All measurement results shall be recorded, processed and presented in an appropriate fashion in order to enable the competent authorities to verify compliance with the permitted operating conditions and emission limit values laid down in this Directive in accordance with procedures to be decided upon by those authorities. 10. The emission limit values for air shall be regarded as being complied with if: (a) — none of the daily average values exceeds any of the emission limit values set out in Annex V(a) or Annex II; — 97% of the daily average value over the year does not exceed the emission limit value set out in Annex V(e) first indent; Kåre Helge Karstensen [email protected] Page 360 of 420 (b) either none of the half-hourly average values exceeds any of the emission limit values set out in Annex V(b), column A or, where relevant, 97% of the half-hourly average values over the year do not exceed any of the emission limit values set out in Annex V(b), column B; (c) none of the average values over the sample period set out for heavy metals and dioxins and furans exceeds the emission limit values set out in Annex V(c) and (d) or Annex II; (d) the provisions of Annex V(e), second indent or Annex II, are met. 11. The half-hourly average values and the 10-minute averages shall be determined within the effective operating time (excluding the start-up and shut-off periods if no waste is being incinerated) from the measured values after having subtracted the value of the confidence interval specified in point 3 of Annex III. The daily average values shall be determined from those validated average values. To obtain a valid daily average value no more than five half hourly average values in any day shall be discarded due to malfunction or maintenance of the continuous measurement system. No more than ten daily average values per year shall be discarded due to malfunction or maintenance of the continuous measurement system. 12. The average values over the sample period and the average values in the case of periodical measurements of HF, HCl and SO2 shall be determined in accordance with the requirements of Article 10(2) and (4) and Annex III. 13. The Commission, acting in accordance with the procedure laid down in Article 17, shall decide, as soon as appropriate measurement techniques are available within the Community, the date from which continuous measurements of the air emission limit values for heavy metals, dioxins and furans shall be carried out in accordance with Annex III. 14. The following measurements shall be carried out at the point of waste water discharge: Kåre Helge Karstensen [email protected] Page 361 of 420 (a) continuous measurements of the parameters referred to in Article 8(6)(b); (b) spot sample daily measurements of total suspended solids; Member States may alternatively provide for measurements of a flow proportional representative sample over a period of 24 hours; (c) at least monthly measurements of a flow proportional representative sample of the discharge over a period of 24 hours of the polluting substances referred to in Article 8(3) with respect to items 2 to 10 in Annex IV; (d) at least every six months measurements of dioxins and furans; however one measurement at least every three months shall be carried out for the first 12 months of operation. Member States may fix measurement periods where they have set emission limit values for polycyclic aromatic hydrocarbons or other pollutants. 15. The monitoring of the mass of pollutants in the treated waste water shall be done in conformity with Community legislation and laid down in the permit as well as the frequency of the measurements. 16. The emission limit values for water shall be regarded as being complied with if: (a) for total suspended solids (polluting substance number 1), 95% and 100% of the measured values do not exceed the respective emission limit values as set out in Annex IV; (b) for heavy metals (polluting substances number 2 to 10) no more than one measurement per year exceeds the emission limit values set out in Annex IV; or, if the Member State provides for more than 20 samples per year, no more than 5% of these samples exceed the emission limit values set out in Annex IV; (c) for dioxins and furans (polluting substance 11), the twice yearly measurements do not exceed the emission limit value set out in Annex IV. Kåre Helge Karstensen [email protected] Page 362 of 420 17. Should the measurements taken show that the emission limit values for air or water laid down in this Directive have been exceeded, the competent authorities shall be informed without delay. Article 12 Access to information and public participation 1. Without prejudice to Council Directive 90/313/EEC (1) and Directive 96/61/EC, applications for new permits for incineration and co-incineration plants shall be made available at one or more locations accessible to the public, such as local authority offices, for an appropriate period to enable it to comment on them before the competent authority reaches a decision. That decision, including at least a copy of the permit, and any subsequent updates, shall also be made available to the public. 2. For incineration or co-incineration plants with a nominal capacity of two tonnes or more per hour and notwithstanding Article 15(2) of Directive 96/61/EC, an annual report to be provided by the operator to the competent authority on the functioning and monitoring of the plant shall be made available to the public. This report shall, as a minimum requirement, give an account of the running of the process and the emissions into air and water compared with the emission standards in this Directive. A list of incineration or co-incineration plants with a nominal capacity of less than two tonnes per hour shall be drawn up by the competent authority and shall be made available to the public. Article 13 Abnormal operating conditions Kåre Helge Karstensen [email protected] Page 363 of 420 1. The competent authority shall lay down in the permit the maximum permissible period of any technically unavoidable stoppages, disturbances, or failures of the purification devices or the measurement devices, during which the concentrations in the discharges into the air and the purified waste water of the regulated substances may exceed the prescribed emission limit values. 2. In the case of a breakdown, the operator shall reduce or close down operations as soon as practicable until normal operations can be restored. 3. Without prejudice to Article 6(3)(c), the incineration plant or co-incineration plant or incineration line shall under no circumstances continue to incinerate waste for a period of more than four hours uninterrupted where emission limit values are exceeded; moreover, the cumulative duration of operation in such conditions over one year shall be less than 60 hours. The 60-hour duration applies to those lines of the entire plant which are linked to one single flue gas cleaning device. 4. The total dust content of the emissions into the air of an incineration plant shall under no circumstances exceed 150 mg/m3 expressed as a half-hourly average; moreover the air emission limit values for CO and TOC shall not be exceeded. All other conditions referred to in Article 6 shall be complied with. Article 14 Review clause Without prejudice to Directive 96/61/EC, the Commission shall submit a report to the European Parliament and the Council before 31 December 2008 based on experience of the application of this Directive, in particular for new plants, and on the progress achieved in emission control techniques and experience in waste management. Furthermore, the report shall be based on the development of the state of technology, of experience in the operation of the plants, of environmental requirements. This report will include a specific section on the x application of Annex II.1.1. and in particular on the economic and technical feasibility for Kåre Helge Karstensen [email protected] Page 364 of 420 existing cement kilns as referred to in the footnote to Annex II.1.1. of respecting the NO emission limit value for new cement kilns set out in that Annex. The report shall, as appropriate, be accompanied by proposals for revision of the related provisions of this Directive. However, the Commission shall, if appropriate, propose an amendment for Annex II.3 before the said report, if major waste streams are directed to types of co-incineration plants other than those dealt with in Annex II.1 and II.2. Article 15 Reporting The reports on the implementation of this Directive shall be established in accordance with the procedure laid down in Article 5 of Council Directive 91/692/EEC. The first report shall cover at least the first full three-year period after 28 December 2002 and comply with the periods referred to in Article 17 of Directive 94/67/EC and in Article 16(3) of Directive 96/61/EC. To this effect, the Commission shall elaborate the appropriate questionnaire in due time. Article 16 Future adaptation of the directive The Commission shall, in accordance with the procedure laid down in Article 17(2), amend Articles 10, 11 and 13 and Annexes I and III in order to adapt them to technical progress or new findings concerning the health benefits of emission reductions. Article 17 Kåre Helge Karstensen [email protected] Page 365 of 420 Regulatory committee 1. The Commission shall be assisted by a regulatory committee. 2. Where reference is made to this paragraph, Articles 5 and 7 of Decision 1999/468/EC shall apply, having regard to the provisions of Article 8 thereof. The period laid down in Article 5(6) of Decision 1999/468/EC shall be set at three months. 3. The committee shall adopt its own rules of procedure. Article 18 Repeal The following shall be repealed as from 28 December 2005: (a) Article 8(1) and the Annex to Directive 75/439/EEC; (b) Directive 89/369/EEC; (c) Directive 89/429/EEC; (d) Directive 94/67/EC. Article 19 Penalties The Member States shall determine penalties applicable to breaches of the national provisions adopted pursuant to this Directive. The penalties thus provided for shall be effective, proportionate and dissuasive. The Member States shall notify those provisions to Kåre Helge Karstensen [email protected] Page 366 of 420 the Commission by 28 December 2002 at the latest and shall notify it without delay of any subsequent amendment affecting them. Article 20 Transitional provisions 1. Without prejudice to the specific transitional provisions provided for in the Annexes to this Directive, the provisions of this Directive shall apply to existing plants as from 28 December 2005. 2. For new plants, i.e. plants not falling under the definition of ‘existing incineration or co-incineration plant’ in Article 3(6) or paragraph 3 of this Article, this Directive, instead of the Directives mentioned in Article 18, shall apply as from 28 December 2002. 3. Stationary or mobile plants whose purpose is the generation of energy or production of material products and which are in operation and have a permit in accordance with existing Community legislation where required and which start co-incinerating waste not later than 28 December 2004 are to be regarded as existing co-incineration plants. Article 21 Implementation 1. Member States shall bring into force the laws, regulations and administrative provisions necessary to comply with this Directive not later than 28 December 2002. They shall forthwith inform the Commission thereof. Kåre Helge Karstensen [email protected] Page 367 of 420 When Member States adopt those measures, they shall contain a reference to this Directive or be accompanied by such reference on the occasion of their official publication. The methods of making such reference shall be laid down by the Member States. 2. Member States shall communicate to the Commission the text of the provisions of domestic law which they adopt in the field governed by this Directive. Article 22 Entry into force This Directive shall enter into force on the day of its publication in the Official Journal of the European Communities. Article 23 Addressees This Directive is addressed to the Member States. Done at Brussels, 4 December 2000. For the European Parliament The President N. FONTAINE For the Council The President F. VÉDRINE Kåre Helge Karstensen [email protected] Page 368 of 420 ANNEX I Equivalence factors for dibenzo-p-dioxins and dibenzofurans For the determination of the total concentration (TE) of dioxins and furans, the mass concentrations of the following dibenzo-p-dioxins and dibenzofurans shall be multiplied by the following equivalence factors before summing: Toxic equivalence factor 2,3,7,8 1,2,3,7,8 — Tetrachlorodibenzodioxin (TCDD) — Pentachlorodibenzodioxin (PeCDD) 1 0,5 1,2,3,4,7,8 — Hexachlorodibenzodioxin (HxCDD) 0,1 1,2,3,6,7,8 — Hexachlorodibenzodioxin (HxCDD) 0,1 1,2,3,7,8,9 — Hexachlorodibenzodioxin (HxCDD) 0,1 1,2,3,4,6,7,8 — Heptachlorodibenzodioxin (HpCDD) 0,01 — Octachlorodibenzodioxin (OCDD) 0,001 2,3,7,8 — Tetrachlorodibenzofuran (TCDF) 0,1 2,3,4,7,8 — Pentachlorodibenzofuran (PeCDF) 0,5 1,2,3,7,8 — Pentachlorodibenzofuran (PeCDF) 0,05 1,2,3,4,7,8 — Hexachlorodibenzofuran (HxCDF) 0,1 1,2,3,6,7,8 — Hexachlorodibenzofuran (HxCDF) 0,1 1,2,3,7,8,9 — Hexachlorodibenzofuran (HxCDF) 0,1 2,3,4,6,7,8 — Hexachlorodibenzofuran (HxCDF) 0,1 1,2,3,4,6,7,8 — Heptachlorodibenzofuran (HpCDF) 0,01 1,2,3,4,7,8,9 — Heptachlorodibenzofuran (HpCDF) 0,01 — Octachlorodibenzofuran (OCDF) 0,001 ANNEX II Kåre Helge Karstensen [email protected] Page 369 of 420 Determination of air emission limit values for the co-incineration of waste The following formula (mixing rule) is to be applied whenever a specific total emission limit value ‘C’ has not been set out in a table in this Annex. The limit value for each relevant pollutant and carbon monoxide in the exhaust gas resulting from the co-incineration of waste shall be calculated as follows: Vwaste × C waste + Vproc × C proc Vwaste + Vproc1 Vwaste: =C exhaust gas volume resulting from the incineration of waste only determined from the waste with the lowest calorific value specified in the permit and standardized at the conditions given by this Directive. If the resulting heat release from the incineration of hazardous waste amounts to less than 10 % of the total heat released in the plant, Vwaste must be calculated from a (notional) quantity of waste that, being incinerated, would equal 10% heat release, the total heat release being fixed. Cwaste: emission limit values set for incineration plants in Annex V for the relevant pollutants and carbon monoxide. Vproc: exhaust gas volume resulting from the plant process including the combustion of the authorized fuels normally used in the plant (wastes excluded) determined on the basis of oxygen contents at which the emissions must be standardized as laid down in Community or national regulations. In the absence of regulations for this kind of plant, the real oxygen content in the exhaust gas without being thinned by addition of air unnecessary for the Kåre Helge Karstensen [email protected] Page 370 of 420 process must be used. The standardization at the other conditions is given in this Directive. Cproc: emission limit values as laid down in the tables of this annex for certain industrial sectors or in case of the absence of such a table or such values, emission limit values of the relevant pollutants and carbon monoxide in the flue gas of plants which comply with the national laws, regulations and administrative provisions for such plants while burning the normally authorized fuels (wastes excluded). In the absence of these measures the emission limit values laid down in the permit are used. In the absence of such permit values the real mass concentrations are used. C: total emission limit values and oxygen content as laid down in the tables of this annex for certain industrial sectors and certain pollutants or in case of the absence of such a table or such values total emission limit values for CO and the relevant pollutants replacing the emission limit values as laid down in specific Annexes of this Directive. The total oxygen content to replace the oxygen content for the standardization is calculated on the basis of the content above respecting the partial volumes. Member States may lay down rules governing the exemptions provided for in this Annex. II.1. Special provisions for cement kilns co-incinerating waste Daily average values (for continuous measurements) Sample periods and other measurement requirements as in Article 7. All values in mg/m3 (Dioxins and furans ng/m3). Half-hourly average values shall only be needed in view of calculating the daily average values. The results of the measurements made to verify compliance with the emission limit values shall be standardized at the following conditions: Temperature 273 K, pressure 101,3 kPa, 10% oxygen, dry gas. Kåre Helge Karstensen [email protected] Page 371 of 420 II.1.1. C — total emission limit values Pollutant C Total dust 30 HCI 10 HF 1 NOx for existing plants 800 NOx for new plants 500 (1) Pollutant C ( Cd + Tl 0,05 Hg 0,05 Sb + As + Pb + Cr + Co + Cu + Mn + Ni + V 0,5 1) For the implem entatio n of the NOx Dioxins and furans 0,1 emissio n limit values, cement kilns which are in operation and have a permit in accordance with existing Community legislation and which start co-incinerating waste after the date mentioned in Article 20(3) are not to be regarded as new plants. Until 1 January 2008, exemptions for NOx may be authorized by the competent authorities for existing wet process cement kilns or cement kilns which burn less than three tonnes of waste per hour, provided that the permit foresees a total emission limit value for NOx of not more than 1200 mg/m3. Kåre Helge Karstensen [email protected] Page 372 of 420 Until 1 January 2008, exemptions for dust may be authorized by the competent authority for cement kilns which burn less than three tonnes of waste per hour, provided that the permit foresees a total emission limit value of not more than 50 mg/m3. II.1.2. C — total emission limit values for SO2 and TOC Pollutant SO2 TOC C 50 10 Exemptions may be authorized by the competent authority in cases where TOC and SO2 do not result from the incineration of waste. II.1.3. Emission limit value for CO Emission limit values for CO can be set by the competent authority. II.2. Special provisions for combustion plants co-incinerating waste II.2.1. Daily average values Without prejudice to Directive 88/609/EEC and in the case where, for large combustion plants, more stringent emission limit values are set according to future Community legislation, the latter shall replace, for the plants and pollutants concerned, the emission limit values as laid down in the following tables (Cproc). In that case, the following tables shall be adapted to these more stringent emission limit values in accordance with the procedure laid down in Article 17 without delay. Kåre Helge Karstensen [email protected] Page 373 of 420 Half-hourly average values shall only be needed in view of calculating the daily average values. Cproc: Cproc for solid fuels expressed in mg/Nm3 (O2 content 6%): Pollutants < 50 MWth 50-100 MWth 100 to 300 MWth > 300 MWth SO2 850 850 to 200 200 general case or rate of (linear decrease from or rate of indigenous fuels desulphurisation 100 to 300 MWth) desulphurisation ≥ 90% or rate of ≥ 95% desulphurisation ≥ 92% NOx Dust 50 400 300 200 50 30 30 Until 1 January 2007 and without prejudice to relevant Community legislation, the emission limit value for NOx does not apply to plants only co-incinerating hazardous waste. Until 1 January 2008, exemptions for NOx and SO2 may be authorized by the competent authorities for existing co-incineration plants between 100 and 300 MWth using fluidized bed technology and burning solid fuels provided that the permit foresees a Cproc value of not more than 350 mg/Nm3 for NOx and not more than 850 to 400 mg/Nm3 (linear decrease from 100 to 300 MWth) for SO2. Cproc for biomass expressed in mg/Nm3 (O2 content 6%): . Kåre Helge Karstensen [email protected] Page 374 of 420 ‘Biomass’ means: products consisting of any whole or part of a vegetable matter from agriculture or forestry, which can be used for the purpose of recovering its energy content as well as wastes listed in Article 2(2)(a)(i) to (v). Pollutants < 50 MWth 50 to 100 MWth 100 to 300 MWth > 300 MWth SO2 200 200 200 NOx 350 300 300 50 30 30 Dust 50 Until 1 January 2008, exemptions for NOx may be authorized by the competent authorities for existing co-incineration plants between 100 and 300 MWth using fluidized bed technology and burning biomass provided that the permit foresees a Cproc value of not more than 350 mg/Nm3. Cproc for liquid fuels expressed in mg/Nm3 (O2 content 3%): Pollutants < 50 MWth SO2 50 to 100 MWth 100 to 300 MWth > 300 MWth 850 850 to 200 200 (linear decrease from 100 to 300 MWth) NOx Dust 50 400 300 200 50 30 30 Kåre Helge Karstensen [email protected] Page 375 of 420 II.2.2. C — total emission limit values C expressed in mg/Nm3 (O2 content 6%). All average values over the sample period of a minimum of 30 minutes and a maximum of 8 hours: Pollutant C Cd + Tl 0,05 Hg 0,05 Sb + As + Pb + Cr + Co + Cu + Mn + Ni + V 0,5 C expressed in ng/Nm3 (O2 content 6%). All average values measured over the sample period of a minimum of 6 hours and a maximum of 8 hours: Pollutant C Dioxins and furans 0,1 II.3. Special provisions for industrial sectors not covered under II.1 or II.2 co- incinerating waste II.3.1. C — total emission limit values: C expressed in ng/Nm3. All average values measured over the sample period of a minimum of 6 hours and a maximum of 8 hours: Kåre Helge Karstensen [email protected] Page 376 of 420 Pollutant C Dioxins and furans 0,1 C expressed in mg/Nm3. All average values over the sample period of a minimum of 30 minutes and a maximum of 8 hours: Pollutant C Cd + Tl 0,05 Hg 0,05 ANNEX III Measurement techniques 1. Measurements for the determination of concentrations of air and water polluting substances have to be carried out representatively. 2. Sampling and analysis of all pollutants including dioxins and furans as well as reference measurement methods to calibrate automated measurement systems shall be carried out as given by CEN-standards. If CEN standards are not available, ISO standards, national or international standards which will ensure the provision of data of an equivalent scientific quality shall apply. Kåre Helge Karstensen [email protected] Page 377 of 420 3. At the daily emission limit value level, the values of the 95% confidence intervals of a single measured result shall not exceed the following percentages of the emission limit values: Carbon monoxide: 10% Sulphur dioxide: 20% Nitrogen dioxide: 20% Total dust: 30% Total organic carbon: 30% Hydrogen chloride: 40% Hydrogen fluoride: 40%. ANNEX IV Emission limit values for discharges of waste water from the cleaning of exhaust gases Emission limit values expressed in mass concentrations for unfiltered samples Polluting substances 1. Total suspended solids as defined by Directive 91/271/EEC 95% 30mg / l 100% 45mg / l 2. Mercury and its compounds, expressed as mercury (Hg) 0,03 mg/l 3. Cadmium and its compounds, expressed as cadmium (Cd) 0,05 mg/l 4. Thallium and its compounds, expressed as thallium (Tl) 0,05 mg/l 5. Arsenic and its compounds, expressed as arsenic (As) 0,15 mg/l Kåre Helge Karstensen [email protected] Page 378 of 420 6. Lead and its compounds, expressed as lead (Pb) 0,2 mg/l 7. Chromium and its compounds, expressed as chromium (Cr) 0,5 mg/l 8. Copper and its compounds, expressed as copper (Cu) 0,5 mg/l 9. Nickel and its compounds, expressed as nickel (Ni) 0,5 mg/l 10. Zinc and its compounds, expressed as zinc (Zn) 1,5 mg/l 11. Dioxins and furans, defined as the sum of the individual dioxins and furans evaluated in accordance with Annex I 0,3 mg/l Until 1 January 2008, exemptions for total suspended solids may be authorized by the competent authority for existing incineration plants provided the permit foresees that 80% of the measured values do not exceed 30 mg/l and none of them exceed 45 mg/l. ANNEX V Air emission limit values (a) Daily average values Total dust 10 mg/m3 Gaseous and vaporous organic substances, expressed as total organic carbon 10 mg/m3 Hydrogen chloride (HCl) 10 mg/m3 Hydrogen fluoride (HF) 1 mg/m3 Sulphur dioxide (SO2) 50 mg/m3 Kåre Helge Karstensen [email protected] Page 379 of 420 Nitrogen monoxide (NO) and nitrogen dioxide (NO2) expressed as nitrogen dioxide for existing incineration plants with a nominal capacity exceeding 6 tonnes per hour or new incineration plants 200 mg/m3 (*) Nitrogen monoxide (NO) and nitrogen dioxide (NO2), expressed as nitrogen dioxide for existing incineration plants with a nominal capacity of 6 tonnes per hour or less 400 mg/m3 (*) (*) Until 1 January 2007 and without prejudice to relevant (Community) legislation the emission limit value for NOx does not apply to plants only incinerating hazardous waste. Exemptions for NOx may be authorized by the competent authority for existing incineration plants: — with a nominal capacity of 6 tonnes per hour, provided that the permit foresees the daily average values do not exceed 500 mg/m3 and this until 1 January 2008, — with a nominal capacity of >6 tonnes per hour but equal or less than 16 tonnes per hour, provided the permit foresees the daily average values do not exceed 400 mg/m3 and this until 1 January 2010, — with a nominal capacity of >16 tonnes per hour but <25 tonnes per hour and which do not produce water discharges, provided that the permit foresees the daily average values do not exceed 400 mg/m3 and this until 1 January 2008. Until 1 January 2008, exemptions for dust may be authorized by the competent authority for existing incinerating plants, provided that the permit foresees the daily average values do not exceed 20 mg/m3. (b) Half-hourly average values Kåre Helge Karstensen [email protected] Page 380 of 420 (100%) A (97%) B Total dust 30 mg/m3 10 mg/m3 Gaseous and vaporous organic substances, expressed as total organic carbon 20 mg/m3 10 mg/m3 Hydrogen chloride (HCl) 60 mg/m3 10 mg/m3 Hydrogen fluoride (HF) 4 mg/m3 2 mg/m3 200 mg/m3 50 mg/m3 400 mg/m3 (*) 200 mg/m3 (*) Sulphur dioxide (SO2) Nitrogen monoxide (NO) and nitrogen dioxide (NO2), expressed as nitrogen dixoide for existing incineration plants with a nominal capacity exceeding 6 tonnes per hour or new incineration plants (*) Until 1 January 2007 and without prejudice to relevant Community legislation the emission limit value for NOx does not apply to plants only incinerating hazardous waste. Until 1 January 2010, exemptions for NOx may be authorized by the competent authority for existing incineration plants with a nominal capacity between 6 and 16 tonnes per hour, provided the half-hourly average value does not exceed 600 mg/m3 for column A or 400 mg/m3 for column B. (c) All average values over the sample period of a minimum of 30 minutes and a maximum of 8 hours Cadmium and its compounds, expressed as cadmium (Cd) Total 0 05 mg/m3 Kåre Helge Karstensen [email protected] Total 0 1 mg/m3 (*) Page 381 of 420 Thallium and its compounds, expressed as thallium (Tl) Mercury and its compounds, expressed as mercury (Hg) 0,05 mg/m3 0,1 mg/m3 (*) Total 0,5 mg/m3 Total 1 mg/m3 (*) Antimony and its compounds, expressed as antimony (Sb) Arsenic and its compounds, expressed as arsenic (As) Lead and its compounds, expressed as lead (Pb) Chromium and its compounds, expressed as chromium (Cr) Cobalt and its compounds, expressed as cobalt (Co) Copper and its compounds, expressed as copper (Cu) Manganese and its compounds, expressed as manganese (Mn) Nickel and its compounds, expressed as nickel (Ni) Vanadium and its compounds, expressed as vanadium (V) (*) Until 1 January 2007 average values for existing plants for which the permit to operate has been granted before 31 December 1996, and which incinerate hazardous waste only. These average values cover also gaseous and the vapor forms of the relevant heavy metal emissions as well as their compounds. (d) Average values shall be measured over a sample period of a minimum of 6 hours and a maximum of 8 hours. The emission limit value refers to the total concentration of dioxins and furans calculated using the concept of toxic equivalence in accordance with Annex I. Dioxins and furans 0,1 ng/m3 Kåre Helge Karstensen [email protected] Page 382 of 420 (e) The following emission limit values of carbon monoxide (CO) concentrations shall not be exceeded in the combustion gases (excluding the start-up and shut-down phase): — 50 milligrams/m3 of combustion gas determined as daily average value; — 150 milligrams/m3 of combustion gas of at least 95% of all measurements determined as 10-minute average values or 100 mg/m3 of combustion gas of all measurements determined as half-hourly average values taken in any 24-hour period. Exemptions may be authorized by the competent authority for incineration plants using fluidized bed technology, provided that the permit foresees an emission limit value for carbon monoxide (CO) of not more than 100 mg/m3 as an hourly average value. (e) Member States may lay down rules governing the exemptions provided for in this Annex. ANNEX VI Formula to calculate the emission concentration at the standard percentage oxygen concentration ES = 21 − OS × EM 21 − O M ES = calculated emission concentration at the standard percentage oxygen concentration EM = measured emission concentration Kåre Helge Karstensen [email protected] Page 383 of 420 OS = standard oxygen concentration OM = measured oxygen concentration Kåre Helge Karstensen [email protected] Page 384 of 420 Annex 8 The example of Brevik, Norway, HeidelbergCement Group Brevik is co-processing waste fuels in its kiln (clinker capacity 1,2 mio ton/year) since 1986. In 2005 130.000 tons of waste materials were recovered to substitute 55% of fossil fuels. A number of waste materials can be burned directly into the kiln. Other materials have to be pre-treated before burning. In order to be able to use a wider range of waste materials, HeidelbergCement – Norway decided to found the company Renor S.A. This company is owned by HeidelbergCement and is responsible for pre-treatment of wast materials. Waste materials are received by Renor and after testing the characteristics, they are shredded and blended in a way to ensure a waste derived fuel with homogenous properties. The facility is constructed by Renor S.A. directly near the Norcem plant in Brevik-Norway. Renor S.A. also assists Norcem when applying for permits, licenses and approvals for increased use of alternative fuels. Optimization works have been executed at the kiln’s calciner in order to be able to burn upto 60% of waste fuels. Realising significant levels of waste fuels into the kiln process requires a thorough analysis of the emission levels of the kiln exhaust gas. Brevik is equipped with the most modern emission measurement devices and besides this, independent institutes make their measurements yearly to check consistency. As can be seen in next table, the emission levels are far below the permit levels and generally spoken there is no increase although the waste fuel percentage has increased from 30% in 2000 to 40% in 2004. Careful examination of the waste materials at recieval is essential to be sure that no peaks in emission will occur. Reliable relation ship with the suppliers is, together with the above described control mechanisms, a guarantee that the material is within the specification limits. Kåre Helge Karstensen [email protected] Page 385 of 420 Well educated and experienced operators at the cement-plant is the next pre-requisite for a safe and reliable operation of the next pre-requisite for a safe and reliable operation of the kiln including the waste fuels. Norcem will continue to burn waste fuels and try to reduce the fossil fuels to less than 40%. The pre-treatment company Renor S.A. will be an essential partner in achieving these goals. If you want to be successful in waste material recovery you have to pay a lot of attention to the reliability of material specifications. If a waste material cannot be burned as it is available, careful shredding and/or blending can create new possibilities. Founding an independent company for the pre-treatment process can offer benefits for both the suppliers as for the end users. Presentation material of Renor AS (2007): Kåre Helge Karstensen [email protected] Page 386 of 420 Kåre Helge Karstensen [email protected] Page 387 of 420 Kåre Helge Karstensen [email protected] Page 388 of 420 Kåre Helge Karstensen [email protected] Page 389 of 420 Kåre Helge Karstensen [email protected] Page 390 of 420 Kåre Helge Karstensen [email protected] Page 391 of 420 Annex 9 Permit for NORCEM cement plant, Brevik, Norway (1998) SFT Discharge Permit for NORCEM A.S. BREVIK granted by virtue of the act on protection from pollution and on waste of March 13, 1981, no. 6, art 11. This permit is given on the basis of information furnished in the application of 4/16/96 and on information obtained during the handling of the case. The terms of the permit are stated on pages 1 to 14. Any modifications the company may wish to make with regard to the information furnished in their application or during the examination of the case, for example regarding additives, products, production equipment or cleaning equipment, must be cleared with SFT [Norwegian Pollution Control Authority] in advance. This permit is valid from 01/01/98 The permit of 03/28/96 regarding the dumping of sludge and materials containing sediment from Elkern Mangan PEA in inactive mine galleries near the company remains valid. Effective 01/01/98, all prior permits granted for the production of cement and for the incineration of special waste and other waste at the plant in Brevik shall no longer be valid. Company data: Company: Branch: Postal address: Postal code/City: Location: Municipality: County: NORCEM AS BREVIK Cement production Post Box 38 3950 Brevik Brevik Porsgrunn Telemark SFT's reference: Filing code: 408/96-029 Date: AUG. 29, 1997 /signature/ Tor Færden Case Worker Amendment no.: Date of amendment: /signature/ Dag B. Granbakken Section Manager Kåre Helge Karstensen [email protected] Page 392 of 420 1. Production conditions / discharge conditions: 1.1. Production Authorization is given for the operation of the cement factory, with receipt of raw materials, fuel and waste, equipment for storage, crushing, grinding and processing of raw materials, fuel and finished products, clinker kilns 5 and 6, equipment for monitoring and control of the incineration process, equipment for postprocessing of products, and equipment for treating waste gasses from the process. Authorization is based on an annual production of approx. 1.4 million tons of clinker from kiln 6. Kiln 5 has a capacity of some 0.4 million tons of clinker per year. Before 12/31/2000 the kiln must be upgraded so that it can meet the same discharge thresholds as those established for coal-based clinker production in kiln 6 (see paragraph 3.1). In the meantime production in kiln 5 must be restricted to 200,000 tons clinker per year. In cases where discharge is proportional to the production volume, any reduction in the production level stated in the application must result in a corresponding reduction in discharge. 1.2. Use of fuel Coal, petroleum coke, heating oil, and waste oil may be used as fuel in both kilns. Heating oil may also be used to heat the Aerofall mill and in the boilers. For use of heating oil, provisions on sulfur content in various oil products apply. Waste oil received from external suppliers and from NORCEM may be used in kiln 6. The same applies to waste oil that does not satisfy the analysis thresholds specified in the previous section. Waste that is not listed below and which is not defined as special waste may be used in both kilns. The above-mentioned types of fuel may be added within the framework given below: Kåre Helge Karstensen [email protected] Page 393 of 420 Type of fuel Maximum allowance (mass flow) Waste oil (kiln 5 and 6) 1) Organic special waste (only kiln 6) 2) -Total (sum of liquid and solid) —Of which sum of special waste added in precalciner and kiln inlet 3) Car tires and rubber car fragment waste (kiln 5 and 6) Other (kiln 5 and 6) 5); -Pure biofuel -Plastic -Residual waste from waste treatment plant, excluding wet organic waste Total tons per year 30,000 31,000 Kiln 5 tons per hour 3 0 Kiln 6 tons per hour 8.5 8.5 0 3.5 12,000 0 4) 1.5 5) 5) 5) 1) This allowance includes both the company's own waste oil and that obtained externally, as defined in the regulation on the incineration of waste oil of May 20, 1995, that satisfies the quality requirements provided for in article 4 of the same regulation. Waste oil that does not meet these requirements falls under the group "organic special waste." 2) Covers organic special waste sorted under the following main categories in the regulation on special waste of May 19, 1994, with amendments of September 10, 1996, appendix 1, and similar types of waste defined as special waste according to the criteria specified in the said regulations, appendix 2: EAK code 02 03 04 05 06 07 08 09 10 12 13 14 16 17 19 20 Description Waste from primary production in farming, horticulture, hunting, fishing and aquaculture, preparation and processing of foodstuffs. Waste from tree industry, production of paper, cardboard, wood pulp, lumber and furniture. Waste from industrial production of leather goods and textiles Waste from oil refining, purification of natural gas and pyrolitical treatment of coal. Waste from inorganic chemical processes. Applies to waste types 0607, 0612 and 061302. Waste from organic chemical processes. Waste from production, treatment, distribution, and use of coating products (paints, varnishes and glass enamels), glue, sealants and printing colors. Waste from the photography industry Inorganic waste from heat processing. Applies to waste types 100104 and 100301. Waste from the molding and mechanical surface treatment of metals and plastics. Applies to waste types 1201 and 1203. Used oils Waste from organic substances used as solvents Waste not described elsewhere in the catalog. Applies to waste types under subcategories 1607, 1608 and 1609 Waste from construction and demolition work. Applies to waste type 170303. Waste from waste treatment plants, external purification treatment plants and water supply. Applies to waste types 1901 and 190803. Municipal waste and the like from trade, industry, and institutions, including separately collected waste types. Applies to waste types 200112, 200123, 200117, 200119 and 200123 The list deviates from that of the company, since the latter was based on a previous version of the regulations on special waste. Kåre Helge Karstensen [email protected] Page 394 of 420 3) Also includes incineration of substances (dirt, sludge, mud, etc.) that have been contaminated by the types of special waste listed in table 2). These allowances apply to the weight of the substance. 4) Authorization for incineration of tires in kiln 5 will be granted when tests have documented how much may be added without causing discharge problems. 5) This item only applies to pure biofuel and waste that is not defined as special waste. No threshold has been established for the amounts of such fuel. For this type of incineration, applicable discharge regulations are the same as those for coalbased cement production. The framework and conditions for such incineration may be modified, for example in connection with the adoption of EU directives for the incineration of waste. For the incineration of other types of waste (special waste and other waste) than those listed above, the company must obtain advance special authorization from SFT. Waste for incineration must not be radioactive, explosive, infectious, or be of a pathological nature. 1.3 Requirements for receipt of special waste Receipt and pretreatment of waste at NOAH's pretreatment plant are regulated by NOAH's license from SFT. There must be a written agreement between NOAH and the company on quality assurance of the deliveries. The company may only burn waste whose main components and contaminants are known. To the extent possible, the company must avoid burning waste which, because of environmental consequences, is not suitable for burning, such as waste containing mercury. Before special waste is received for incineration at the company's plant, the company must receive a description of the waste, which must include: - information on the physical and, if possible, the chemical composition of the waste and all information needed to assess its suitability for the incineration process. The waste must be declared on a valid form. - information on the hazardous properties of the waste, on the substances that it may not be mixed with, and on the regulations that must be met in handling the waste. Special waste received must be registered in a receipt journal. The journal must have a consecutive number with an entry for each declaration form. The journal must include information on the date of receipt, the declaration form's consecutive number, the waste supplier, the waste group, and the amount of waste. When receiving special waste directly from a supplier other than NOAH's pretreatment facility, the company must ensure that the shipping company and vehicle are authorized by the proper authorities to make such a delivery. The terms of item 1.3 do not release the company of its responsibility for environmental damage and negative consequences resulting from the incineration. Kåre Helge Karstensen [email protected] Page 395 of 420 When waste is added, the unloading site must be arranged so that spills and leaks are collected. The collection system for liquid waste must at least be able to contain the content of a tank truck or hanger. The tank unit for liquid special waste must be equipped with a collection system able to handle spills and leaks. The collection capacity must be at least 10% larger than the volume of the largest tank. Polluted water from the unloading site and collection unit, as well as impure water drained from the tanks for liquid special waste must be collected and fed into the clinker kilns in the same manner as the waste. Delivered waste must be stored where it cannot be accessed by unauthorized persons. 1.4. Conditions for burning special waste For the burning of special waste, the following allowances apply: Substance/component PCB Halogens (sum of chlorine (Cl), bromine (Br), iodine (J) and fluoride (F)) - Sum of which added in kiln inlet and precalciner Lead (Pb) Content in waste 50 kg/hr 110 kg/hr 35 kg/hr 5 kg/hr Special waste must be added to the clinker kiln in such a way that incineration of the waste is as complete as possible. The maximum allowance of organic special waste must be limited such that the heat generated from incineration never exceeds 40% of the total heat generated in the unit. The clinker kilns must be equipped with the following automatic recording measurement instruments: - Flue gas temperature measured at the lowest cyclone - Excess O2 in the flue gas - CO content - Concentration of dust in stack - Time for pumping liquid special waste into the kiln Special waste can only be incinerated when the kilns are stable and operating normally. Pumping of special waste must be stopped in case - the electrofilter stops - the feed of primary fuel is interrupted - the CO content in the flue gas is over 1.0% - the machines are stopped and started Incineration of special waste must also be halted as quickly as possible when there are any signs of or there is any suspicion of abnormal operating conditions. When incinerating special waste, the company must keep an accurate operating journal, in which the Kåre Helge Karstensen [email protected] Page 396 of 420 amount of special waste and significant operating and leakage parameters are recorded. The operating journals must be kept for at least 3 years and presented to environmental authorities at their request. Amounts and types of incinerated special waste must be reported annually to SFT in accordance with SFT's guidelines for reporting from companies. 1.5 Requirements for the receipt and storage of coal This permit allows for the receipt of up to 1,000,000 tons of lump coal / petroleum coke annually and storage of up to 300,000 tons in the area. The coal must be sufficiently humid so as to avoid dust when storing and handling. The company must install humidifying equipment if necessary. Petroleum coke must be covered with sufficient masses during storage. Procedures aimed at avoiding environmental problems in connection with the storage and handling of coal must be included in the company's internal monitoring plan. 1.6 Requirements for receipt of waste oil For the receipt of individual deliveries or batches of waste oil of over 2 tons, there must be test documents establishing that quality requirements have been met. This must be established before the oil is emptied into the main tank. 1.7 Conditions for incinerating waste other than special waste For incineration of waste other than special waste, the same discharge terms as those for coalbased cement production apply. Waste must be loaded into the clinker kiln in such a manner that waste is incinerated as completely as possible. The framework and conditions for such incineration may be modified, for example in connection with the adoption of EU directives on the incineration of waste. Storage and handling of waste must occur in a manner that avoids environmental drawbacks in the form of, for example, contaminated leaks or odors. Tires must be adequately cut up so as to obtain a controlled incineration that produces stable operating and discharge conditions. At any given time up to 3,000 tons of material from used car tires may be stored in "Bruddet " in the stone storage area at the company. 2. Discharge to water 2.1. Process water The company has no discharge of process water. Kåre Helge Karstensen [email protected] Page 397 of 420 2.2 Sanitary drainage water The company undertakes to meet the requirements defined by the provincial commissioner for the discharge of sanitary drainage water. This permit does not affect the municipality's right to make demands in case of association with a municipal network. 2.3 Use of chemicals Fungicides that the company wishes to use in the cooling systems, etc., must be tested for toxicity and the bioaccumulation and decomposing capacities. The results of these tests must be submitted to SFT. Only GLP-approved (Good Laboratory Practice) laboratories or EN45000 accredited laboratories may be used to test the fungicides. For chemicals already in use at the company and which may be present in water discharge, test results must be submitted to SFT before 03/30/1998. After such time, only chemicals with test results that were submitted to SFT for prior approval may be used. SFT may, in individual cases, grant dispensation from the requirements specified in point 2.3. 2.4 Oily drainage water from workshops and the like Oily drainage water must be purified in sand sifters and oil separators which are shaped and operated according to the regulations on discharge of oily drainage water and on the use and labeling of detergents. 2.5 Ground water seepage Seepage from the mining activity may be conducted to recipients without prior purification. 2.6 Surface water Surface water from the coal storage and from other bulk storage must be collected and purified in an adequate manner before being released into the recipient. Kåre Helge Karstensen [email protected] Page 398 of 420 3. Discharge into air 3.1 Discharge thresholds for clinker kilns The discharge thresholds listed below for kiln 6 apply to the weighted average of the discharges from strings 1 and 2. The following discharge thresholds apply: Discharge components (mg/Nm3) Kiln 5 Kiln 6 Kiln 6 Discharge Discharge Discharge thresholds for thresholds for thresholds for incineration of coal incineration of coal incineration of and coal mixed and coal mixed special waste with waste that is with waste that is together with coal not special waste not special waste *) and any waste other than special waste **) Dust in flue gas from kilns 1) Dust from clinker coolers Tot. org. carbon TOC 1) Chlorine compounds counted as HCl 1) Fluoride compounds counted as HF 2) SOx as SO2 1) and 9) SOx as SO2 1) and 10) Sum of Cd and Tl 3) Hg 3) Sum of other metals 3) and 4) Dioxins 3) *) **) Discharge thresholds apply if special waste is not added to clinker kiln over the course of 24 hours. Discharge thresholds apply if up to 30% of the total volume of waste gas from the process comes from special waste. (This satisfies the requirement under point 1.4 that the maximum allowance of organic special waste be limited such that the generation of heat from incineration does not at any time exceed 40% of the total heat generated in the unit.) The discharge thresholds apply even if less than 30% of the total volume of waste gas from the process comes from special waste. ***) No requirements have been defined for these components, since special waste is not used as fuel. 1) This discharge threshold applies to 24-hour and 30-minute average values. The conditions are met when all 24-hour average values and 97% of all 30-minute average values do not exceed the discharge threshold. 2) This discharge threshold applies to 24-hour and 30-minute average values. The conditions are met when all 24-hour average values do not exceed the discharge threshold and up to 97% of all 30-minute average values do not exceed 2 mg/Nm3. 3) This discharge value applies to the average of measurements taken in a test period of at least 30 minutes and no more than 8 hours. 4) Other metals include Sb, As, Pb, Cr, Co, Cu, Mn, Ni, V, and Sn. 5) Dioxins are expressed as I-TE ng/Nm3. Apply as discharge thresholds from 07/01/2000 and as recommended values before that date. 6) This discharge threshold applies from 01/01/99. Before that date, the discharge threshold is 50 mg/Nm3. 7) Until 12/31/2000, the discharge threshold is 75 mg/Nm3. For as long as this discharge threshold is valid, production in kiln 5 must be limited to 200,000 tons clinker per year. 8) Until 12/31/2000 the discharge threshold is 50 mg/Nm3. For as long as this discharge threshold is valid, production in kiln 5 must be limited to 200,000 tons clinker per year. 9) This discharge value applies when the Aerofall mill is operating. 10) This discharge value applies during shutdown of the Aerofall mill for maintenance. The company must notify SFT in advance if the shutdown is to last so long that the old raw mill must be used. Kåre Helge Karstensen [email protected] Page 399 of 420 All discharge thresholds are 24-hour average values. Discharge concentrations refer to 11% O2 excess and dry flue gas. By-passing of filters to open air is not permitted. 3.2 Discharge thresholds when burning waste oil If over the course of a day no special waste other than waste oil that satisfies the quality requirements in article 4 of the regulation on the burning of waste oil, then the following discharge thresholds apply: Discharge components Discharge thresholds (mg/Nm3 ) Dust Chlorine compounds counted as HCl Fluoride compounds counted as HF Lead (Pb) Sum of chrome (Cr) + copper (Cu) + vanadium (V) Nickel (Ni) Cadmium (Cd) All discharge thresholds are 24-hour average values. Discharge concentrations refer to 3% O2 excess and dry flue gas. The discharge thresholds only apply to the portion of waste gasses that arise from the burning of the waste oil. If waste oil is used in combination with other special waste, the discharge requirements in the right column under point 3.1 apply. 3.3 Discharge thresholds from other process equipment The concentration of dust in discharge from process equipment other than the equipment regulated in point 3.1 must not exceed 25 mg/Nm3, measured as a 24-hour average value. This applies to discharge from - coal mills and other coal processing - crushing, grinding and handling of limestone - grinding and other processing, transport, and storage of cement 3.4 Diffuse dust discharge Diffuse dust discharge must be kept to a minimum. If necessary, SFT may make demands for special measures to reduce such discharge. 3.5 Discharge-reducing measures, purification installations, etc. The handling of raw materials, products, and waste should generally take place in such a manner that the risk of pollution, for example in the form of dust and seepage into the sea, is kept to a minimum. Kåre Helge Karstensen [email protected] Page 400 of 420 Specific demands regarding measures can be made by the SFT, if necessary. In order to limit odors from the activity, ventilation from day silos for solid waste must be conducted to coolers for kiln 6. When kiln 6 is shut down, aspiration from the day silos must be directed to the stack for kiln 6. If necessary, SFT may make further demands for measures to reduce odors. The company is required to record the time that the kilns warm up and shut down without the regular cleaning devices hooked up. Similarly, emergency discharge from kilns, clinker coolers and Aerofall mills must be recorded. A summary of such records must be reported to SFT as part of the annual report described in point 9.2. 3.6 Discharge height requirements It is the responsibility of the company to make sure that discharge is released at a height and in a manner that does not represent an unacceptable nuisance for the surroundings. SFT may require a change in discharge heights or a change in measures if the negative effects on the surrounding environment are greater than presumed in the discharge requirements established in the permit. 3.7 Measurement and monitoring Discharge from the kiln filters must be monitored via continuous measurement of the concentrations of dust and SO2. For incineration of special waste, measurements of discharge and operating parameters should be taken in accordance with the requirements established in article 11 of the incineration directive. If no special waste other than waste oil is burned (see point 3.2), measurements must, at least, be taken in accordance with the requirements in articles 6 and 7 of the regulation on the burning of waste oil. For other discharge sites than those mentioned above and where the amount of waste gas is roughly over 10,000 Nm3 per hour, representative measurements of dust discharge must be taken. For other discharge sites, regular visual monitoring is required (see point 9.2). Sampling, measurements, and analyses must be quality assured. For components where NS, EN, or ISO standards exist for sampling, measuring- and analysis methods, such standards must be used. SFT may require that sampling and analysis be carried out by an accredited institution. SFT can accept that another method is used where NS, EN, or ISO standards exist, providing it can be documented that the other method is at least as accurate as NS. 4. Noise 4.1 Maximum noise allowance The company must minimize the noise level to the extent possible. The initial goal is to reduce the company's contribution to the noise level to under 50 dB(A), measured as the freefield value at the neighboring building experiencing the most noise pollution (see point 7.2). Kåre Helge Karstensen [email protected] Page 401 of 420 5. Own waste 5.1 General terms To the extent possible, the company must minimize the generation of waste resulting from its activities. This also applies to the final use of its products. In particular, the content of hazardous substances in the waste should be reduced as much as possible. Alternatively, the waste should be returned to the company's production, and production possibly changed. Combustible waste must be used whenever possible for energy production internally or externally. The company is not authorized to incinerate waste outside of the clinker kilns without express authorization from SFT. The company must establish a plan for minimizing waste (see point 7.3), in which the company should assess process reorganization and recirculation and use of waste as raw material in other production, as well as use of the waste for energy production. Consumption waste and production waste, with the exception of waste that is allowed to be used in accordance with point 5.2, must be returned for recycling when recipient and recycling facilities for sorted waste are available. Furthermore, such waste must be delivered to municipal waste treatment or other waste treatment facilities licensed by SFT or the provincial commissioner. Such a license shall not affect the municipality's right to make special demands with regard to the composition of the waste. 5.2 Requirements for own depots for production waste In the "Raset" depot, the following types of waste may be stored if the waste cannot be returned to the process: - Filter dust and refuse - Sludge from filtration - and sand-sifter pits and sludge from seepage from the bulk storage. - Used fire-resistant casings. The sludge masses and cement dust must be covered with suitable filling and sowed each time the depot is filled up. The depot area must be fenced in, with a gate that is kept locked when the depot is unmanned. Operating instructions for the depot must exist. The company was authorized on 03/28/96 to store certain types of production waste from Elkem Mangan PEA in the mining chamber at the company's mining district. The terms for such storage are specified in the permit. Together with the waste from Elkem Mangan PEA, the company may store the following types of waste from its own activities in these mining chambers: - Used fire-resistant materials - Calcium-based production waste that cannot be reused in the process. Kåre Helge Karstensen [email protected] Page 402 of 420 6. Preparedness for acute pollution 6.1 Preventing acute discharge The company is obliged to take steps to avoid, and if necessary limit, the risk of acute discharge. These measures must be based on a systematic review of the company's activities, including storage tanks and piping systems for oil and chemicals. 6.2 Preparedness obligation To the extent that the activity presents a risk of acute pollution, the company must see to it that it is properly prepared to prevent, detect, or stop such pollution. The preparedness obligation also applies to equipment to clean up and limit the effects of pollution. The company's preparedness must be reasonably matched with the likelihood of acute pollution and the extent of damage and negative effects that can be produced. 6.3 Notification obligation Acute pollution or danger of acute pollution must be announced in accordance with the regulation on notification of acute pollution or danger of acute pollution. In addition, the company must report excess discharge/accidental leaks to SFT's inspection department in Lower Telemark, as described in a letter dated 03/02/93 from SFT. 7. Further studies and reports 7.1 Discharge into the air Based on the current work in the EU to determine the causes of NOx build-up in cement kilns, the company must submit to SFT by 06/30/98 a report of possible measures to reduce discharge of NOx. Based on the report, SFT may require the implementation of measures to reduce such discharge. 7.2 Noise Once new filters have been installed in kiln 6, the company must produce the results of representative noise measurements taken in the company's surroundings. At the same time, it must produce a plan forecasting the costs of measures needed for the company to achieve the goals for noise provided for in point 4.1. Measurement results and the plan must be sent to SFT before 05/31/99. Based on the plan, SFT may require noise-reduction measures and establish limits for noise. Noise measurements must be carried out according to the Veiledning for måling av støy fra industri [Guideline for Measurement of Noise from Industry] (SFT TA 590) and must be taken by an independent consultant. 7.3 Waste The company must present a report on the waste situation. The report must contain an overview of the current situation (waste types, volumes, and form), describe the possibilities for waste reduction and recycling, and present a plan for the implementation of specific measures. The report must be submitted to SFT before 08/30/98. Based on the report, SFT may require the implementation of specific measures, if necessary. Kåre Helge Karstensen [email protected] Page 403 of 420 8. General terms 8.1 Internal monitoring In accordance with regulations on systematic health, environmental, and safety work in companies (the Internal Monitoring Regulation), the company is required to keep an updated internal monitoring system in place in its company. The internal monitoring system is to ensure that the company observes the requirements provided for in this discharge permit, the pollution control act, the product control act, and relevant regulations concerning these acts. This requires that the internal monitoring system contain the described routines and procedures for operation and systematic maintenance of the installations in the objective of preventing and limiting discharge, such that negative effects and damage is limited as much as possible at all times. 8.2 Observance of threshold values Thresholds set for discharge to air and water and for noise must be observed during the specified reporting periods. The company must endeavor, to the extent possible, to prevent abnormal operating conditions that cause increased discharge and to reduce or adjust operation under such conditions if normal discharge levels will be significantly exceeded. The company must notify SFT of conditions which are or may be of significance in terms of pollution. 8.3 Operating regularity and cleaning effectiveness of cleaning installations One year after the cleaning facility is installed, the company must submit to SFT a report on the facility's operating regularity and cleaning effectiveness. If the cleaning facility has not worked in a satisfactory manner, the company must put forth suggestions for improvements. The company is required to notify SFT when new cleaning facilities become operational. 9. Discharge measurements and reporting 9.1 Monitoring class The company is classified in monitoring class 1. 9.2 Measurement of discharge and reporting to SFT The company must design and implement a program for monitoring measurements of discharge to water and air, as well as ambient noise. The objective of the program is to document that the prescribed requirements are being observed. The company's monitoring of its own discharge must be quality assured. The measurement program must be sent to SFT for comments before 10/31/97. The company must report on its total discharge to air and water, as well as ambient noise. Waste volumes and energy consumption must also be presented. The company must also report any departures from applicable requirements and how they are dealt with. Reporting must take place before 03/01 of the subsequent year on standardized forms issued by SFT. Kåre Helge Karstensen [email protected] Page 404 of 420 SFT may require that the company take noise measurements in the surrounding area in addition to the monitoring program carried out by SFT in collaboration with the companies in the region. 10. Equipment replacement Should the company replace equipment, making it technically possible to prevent pollution in a substantially better way than when authorization was granted, the company must notify SFT thereof in advance, in accordance with article 19 of the pollution control act. 11. Closure Should a facility be closed or an activity be stopped for a longer period, the owner or user must do whatever is necessary to prevent pollution at all times. If the facility or activity may cause pollution after closure or shutdown, reasonable advance notice thereof must be given to SFT. In case of closure or shutdown, the company must further ensure that chemical residue and unused chemicals and the like be handled in a responsible manner. Unused chemicals must be sold or stored in a responsible way (see the regulation on special waste). The measures taken in that regard must be reported to SFT no later than 3 months following closure or shutdown. The report must contain documentation on the handling of chemical residue and the name of the buyers of unused chemicals, if any. Should the company wish to relaunch operations, SFT must be notified in due time before the planned launch date. 12. Inspection The company is required to allow representatives of pollution control authorities or their delegates access to inspect the facilities. Kåre Helge Karstensen [email protected] Page 405 of 420 Annex 10 Swiss Guidelines (1998) Appendix I Positive List The positive list specifies certain types of waste that may be disposed of in cement plants, despite the fact that, as experience shows, they exceed the standard values in Table 1. The disposal of the waste in question in cement plants is permitted either on ecological grounds, to ensure safe use, or owing to a lack of other suitable treatment plants. SAEFL will periodically scrutinise the positive list to establish whether certain types of waste should be removed or if new types should be added. To this end, SAEFL appoints an expert group comprising representatives of the cantons, the cement industry and the waste processing industry. The expert group convenes at regular intervals, at least once per year. The expert group suggests to SAEFL any changes in the Guidelines that may seem necessary. Kåre Helge Karstensen [email protected] Page 406 of 420 Kåre Helge Karstensen [email protected] 407 Appendix I 1/6 Status: March Positive list / A) Alternative fuels No. OMS Description of waste W Code Remarks / Requirements Supplement 1440 Hydraulic oils A1 1460 Non-chlorinated insulating oils These shall comply with the standard values in Table 1, column A, if not otherwise permitted in the supplement organic halogen compounds PCB/PCT These shall comply with the standard values in Table 1, column A, if not otherwise permitted in the supplement Lead Zinc organic halogen compounds PCB/PCT 1470 Motor and gearbox oils A2 1480 Mineral oil mixtures 1481 Other lubricating oils Standard value 1 1% p.wt. 50 mg/kg Pb 800 Zn mg/kg 1000 mg/kg 1% p.wt. 50 mg /kg A3 - Used wood A4 - Sewage sludge from municipal effluent treatment plants A5 1 - Used wood, for example from building sites, building demolition, conversions, renovation, furniture and packagings, from which metals and bulk contaminants have been removed. Independent of fulfilment of the standard values in Table 1, determination of the pollutant content of the clinker and flue gas emission shall be assured based on appropriate sampling and analysis. Disposal independent of compliance with standard values in Table 1. Throughput is dependent, among other things, on maintenance of quality in clinker and cement (Table 2 of the Guidelines). The prohibition on topping up (no significant increase) for the relevant pollutants must be observed. Tyres and industrial rubber waste such as used conveyor belts, buffers and escalator belts can be disposed of, but not chlorinated rubber or other chlorinated Car tyres and other rubber polymer compounds or sportsground coverings containing Hg. The throughput waste depends, among other things, on compliance with clinker quality (Table 2 of the Guidelines). Car tyres contain, among other things, zinc compounds. The Cf. intended Appendix III --- --- --- 408 Appendix I 1/6 Status: March Positive list / A) Alternative fuels No. OMS Description of waste W Code Remarks / Requirements Supplement Standard value 1 standard value for zinc in clinker limits the quantity that may be used. A6 - Paper, cardboard Only paper and cardboard fractions from separate collections and industrial paper waste that owing to its poor quality or market saturation cannot be recycled. Available data indicate that the pollutant content of used paper and cardboard complies with the standard values in Table 1. In justified cases, the cantonal agency responsible can require analyses to be carried out and, if necessary, restrict the quantity incinerated. --- 409 Appendix I 2/6 Status: March, Positive list / A) Alternative fuels A7 - Petroleum coke Paper sludge (incl. that from used paper) A8 - A9 A1 0 2 - - Vanadium Like coal, petroleum coke has been used for many years as a fuel in cement Nickel plants. It has been included in the positive list owing to its specific contamination with vanadium and nickel. For these elements, the standard values opposite apply: V 1000 Ni mg/kg 300 mg/kg May be used in cement plants if the standard values opposite and the values of the remaining pollutants in Table 1, column A, are fulfilled. The throughput depends, among other things, on compliance with clinker quality (Table 1 of the Guidelines). Suitable technical measures shall be taken to limit mercury emission to max. 0.1 mg Hg/Nm3 flue gas. The prohibition on topping up (no significant increase) for the relevant pollutants must be observed. Pb Cd Cr Co Cu M o Ni H g Zn Plastics (graded and mixtures) Clean plastics waste from separate collection, i.e. not mixed with household waste, or homogeneous plastics fractions from industry and agriculture, if these cannot be recycled. Plastics waste shall fulfil the standard value based on calorific value in Table 1, column A. Polyester, PET Homogeneous polyester waste from industry or from return systems/separate collection, that cannot be recycled. Polyester waste must fulfil the standard values in Table 1, column A, if not otherwise specified in the supplement 2 Lead Cadmium Chromium Cobalt Copper Molybdenum Nickel Mercury Zinc 500 mg/kg 5 mg/kg 500 mg/kg 60 mg/kg 600 mg/kg 20 mg/kg 80 mg/kg 5 mg/kg 2000 mg/kg --- Sb 800 Antimony Cd mg/kg Cadmium 10 mg/kg organically compounded chlorine Cl 2% p.wt. Antimony compounds are used as additives (scintillation agents) in PET production, and thus an increase in the standard value for this element is indicated. The value of 10 ppm for cadmium permits any plastics fractions containing cadmium to be excluded even when less sensitive analytical methods are adopted. As experience shows, this is sufficient to distinguish PET fractions containing cadmium from those without. 410 A1 1 - Polyurethane, PUR foam Compacted residue from disposal of cooling equipment (i.e. foamed CFC insulating materials). 2 Polyurethane waste must fulfil the standard values in Table 1 excepting those in the supplement Zinc Zn 1500 mg/kg 411 Appendix I 3/6 Status: March, 1.1Positive List / B) Alternative raw materials No. OMS Waste description W Code B1 B2 Ash from incineration of paper sludge Waste from smelting works, i.e. sands, dust, slag and furnace linings, provided the waste in question is not special waste under OMSW Remarks / Requirements value Ash from paper sludge incineration plant must comply with the standard values in Table 1, column B, if not otherwise specified in the supplement. Lead Cadmium Copper Zinc PCDD/PCDF Pb Cd Cu Zn 250 mg/kg 5 mg/kg 250 mg/kg 2000 mg/kg 10 ng TEQ/kg Pb Cr Co Cu Ni 200 mg/kg Must comply with the standard values in Table 1, column B, unless stipulated otherwise in the supplement. The prohibition on topping up (no significant increase) for the relevant pollutants must be observed. Lead Chromium Cobalt Copper Nickel Annealing loss TOC Pb Cd Cr Zn Sn 100 mg/kg 5 mg/kg 400 mg/kg 1’500 mg/kg 100 mg/kg B3 9100 Waste from road cleaning Sludges of refuse dumps and other waste from road maintenance following allocation by the canton and after consultation with the cement plant concerned is independent of the standard values. B4 2430 Contaminated calcium residues from tin recycling This residue may be disposed of provided the standard values for waste in Table 1, column B, are complied with and unless otherwise specified in the supplement. B5 3041 Residue from soil and cleaning equipment and 3042 soil, concrete and mixed demolition waste, mainly contaminated with organic substances For this waste (OMSW Code 3041 and 3042), separate regulations apply. The substances concerned are residues from rehabilitation of polluted sites. The authority concerned must decide in each individual case whether disposal in cement plants is permissible. In general, residues from soil washing and preparation plant that are contaminated with organic components may be disposed of in cement plants if the organic components are burned as completely as possible and the cement plant has flue gas filtration equipment 3 Standard Supplement Use of this waste must not lead to a significant increase in the chromate content in the clinker. 3 600 mg/kg 150 mg/kg 200 mg Kg 150 mg/kg max. 8% max. 1% --- Lead Cadmium Chromium Zinc Tin see page 4/6 412 Appendix I 4/6 Status: March 1.1Positive List / B) Alternative raw materials No. OMS Waste description W Code Remarks / Requirements Standard Supplement value suitable for organic substances (e.g. active carbon filters). The waste must comply with the requirements for alternative raw materials (pollutant concentrations in Table 1, column B), where the following supplement applies: 3041 Exceptions are specified to the standard values in Table 1, column B, and Residue from soil for a series of heavy metals (see supplement). A maximum of three of 3042 washing plant and soil, these exceptions may be invoked in any individual case. Should the concrete and mixed content of four or more heavy metals exceed the standard values in Table demolition waste, mainly 1, column B, then disposal in cement plants is not permissible. contaminated with organic compounds The same requirements also apply to contaminated materials that for technical reasons cannot be recycled or whose recycling is not beneficial for environmental reasons, and which (e.g. contaminated concrete) are therefore passed on to a cement plant with appropriate exhaust filtration. When contaminated soil is to be disposed of in cement plants without prior preparation, its pollutant content must be determined relative to the fine particle fraction (particles less than 63 micrometer). Thus, for example, sandy soil with 50% fine particle fraction and an effective chromium content of 90 ppm has a chromium content relative to the fine particle fraction of 180 ppm (100/50 x 90). The pollutant content based on the fine particle fraction calculated in this way must fulfil the above regulations on pollutant content. Lead Cadmium Chromium Cobalt Copper Nickel Mercury Zinc PCDD/PCDF PCB Pb Cd Cr Co Cu Ni Hg Zn 500 mg/kg 5 mg/kg 500 mg/kg 100 mg/kg 500 mg/kg 500 mg/kg 2 mg/kg 1.500 mg/kg 10 mg TEQ/kg 50 mg/kg 413 Positive list / C) Materials added at the grinding stage No. OMS Waste description W Code C1 Ash from incineration of paper sludge Remarks / Requirements Ash from paper sludge incineration plant used as grinding additive must comply with the standard value in Table 1, column C, unless otherwise permitted in the supplement. Appendix I 5/6 Status: March, Supplement Barium Lead Cadmium Copper Zinc C2 2440 Gypsum from sulphate precipitation in flue gas desulphurisation plant (REA gypsum) The gypsum waste used must fulfil the standard values in Table 1, column C, Selenium with the addition in the supplement. C3 Slag from high-temperature processes, such as for example DEGLOR, HSR, Thermoselect, Seiler, Plasmox: The standard values in Table 1, column C, must be complied with if not otherwise permitted in the supplement. Glassy molten fractions from high-temperature waste treatment Chromium Copper Cr-VI in the eluate, according to TOW Test 2 Standard value Ba Pb Cd Cu Zn not specified 250 mg/kg 5 mg/kg 250 mg/kg 2000 mg/kg Se 20 mg/kg Cr 2.000 mg/kg Cu 600 mg/kg 0.01 mg/l in the eluate 414 Appendix I 6/6 Status: March, 1998 Positive list / C) Materials added at the grinding stage No. OMS Waste description W Code D1 Waste containing ammonia Remarks / Requirements Supplement (Exceptions) Arsenic Lead Certain aqueous waste can be valorised by use as DeNOx agent or for flame Cadmium temperature regulation in the cement production process (injection in the Chromium-VI temperature range 900-950°C). No entry is made in Table 1 of the Guidelines Chromium III for process materials. These are treated as individual cases in the positive list. Cobalt The permissible level of heavy metal contamination is based on the standard Copper values in the current Ordinance on Effluent Release SR 814.225.21. Nickel Specifically, this applies to: effluent containing ammonia, e.g. from the Mercury ammonia stripping process in effluent treatment plant. Silver Zinc Tin TOC D2 1240 Aqueous waste not contaminated with halogenated solvents D3 1084 Developer baths 1087 (photographic and reproduction developers, bleach, fixative and This is permitted as DeNOx agent (flame cooling, with direct injection). With Chromium VI Copper two exceptions, the standard values in D1 apply to heavy metals. The exceptions and additions are given in the standard values opposite: Organic halon compounds e.g. The heavy metal fraction in clinker shall not exceed 10% of clinker content halog. solvents (excl. waste). TOC These are permitted as DeNOx agents (flame cooling, with direct injection). With three exceptions, the standard values in D1 apply to heavy metals. Heavy metal fractions in clinker must not exceed 10% of the remaining heavy metal fractions in clinker. The exceptions and additions mentioned are given TOC Copper Silver Chromium VI Standard value As Pb Cd CrV I CrII I Co Cu Ni Hg Ag Zn Sn CrV I Cu PCB Cu Ag CrV 0.1 mg/l 0.5 mg/l 0.1 mg/l 0.1 mg/l 2.0 mg/l 0.5 mg/l 0.5 mg/l 2.0 mg/l 0.01 mg/l 0.1 mg/l 2.0 mg/l 2.0 mg/l not specified 0.5 mg/l 1.0 mg/l 50 ppm relative to TOC 250 mg Cl/l not specified not specified 1.0 mg/l 5 mg/l 0.5 mg/l 415 Positive list / C) Materials added at the grinding stage No. OMS Waste description W Code sensitising baths and mixed photographic effluent) Remarks / Requirements Supplement (Exceptions) in the supplement opposite: Organic halon compounds e.g. halog. solvents Standard value I 1 mg Cl/l PCB Appendix II 2/4 Status: March, 1998 Appendix II Requirements for the disposal of special wastes in the form of alternative solid fuels (Combustibles solides de substitution, CSS) 1. Introductory remarks This Appendix contains special requirements for preparation and use of CSS mentioned in Chapter 6 of the Guidelines. Unless otherwise specified in this Appendix, the general provisions of the Guidelines apply. 2. Requirements for CSS a) Annual load As CSS is produced intentionally, its components may be manipulated. The requirements for CSS limit the permissible annual load of certain heavy metals and other pollutants. So that modification of the plant and its mode of operation can comply with the new standard values, the permissible annual load is reduced in two steps according to Table A II/1. For heavy metals not specified there, the standard values in Section 3.2, Table 1, column A, of the Guidelines apply. Tab. AII/1: Permissible pollutant loads in CSS (basis: 15.000 t CSS per year) Max. annual load in t/a to 2000 to 2004 after 2004 Pollutant Lead Cadmium Chromium Copper Nickel Zinc Pb Cd Cr Cu Ni Zn 12.0 0.15 7.5 15.0 4.5 75.0 9.0 0.075 4.5 7.5 3.0 60.0 Halogenated organic compounds in [% by weight] Poorly degradable toxic halogenated organic compounds (e.g. PCB) in [ppm] 6.0 0.075 4.5 6.0 3.0 30.0 Content in ppm to 2000 to 2004 after 2004 800 10 500 1000 300 5000 600 5 300 500 200 4000 < 0.5 % from now < 10 ppm from now 400 5 300 400 200 2000 Page 417 of 420 Assuming Cridec produces less than 15.000 t CSS a year, the annual loads in [t/a] diminish in proportion to the quantity of CSS produced. The quantity specifications are to be regarded as nominal values. They are intended for monitoring individual deliveries. b) Quality control Quality control is intended to ensure first, that the annual pollutant loads in the alternative fuels produced do not exceed the values given in Table A II/1 and, second, that the cement plant complies with the specified exhaust values and the standard values for clinker. The quality of the individual CSS deliveries to the cement plants must be documented in an appropriate form and samples retained to enable the annual loads subsequently to be checked on the basis of the documents and (if necessary) further analysis. The average monthly values of the individual pollutant loads must be checked periodically, and at least once every six months, by the canton responsible. 3. Requirements for waste allowed in CSS production a) Basic principles Waste for conversion to CSS must in general have the following properties: have low heavy-metal content, be largely free of halons, have only traces of poorly degradable halogenated organic compounds such as PCB, have low VOC content (volatile organic compounds such as solvents), be non self-igniting, have high ignition temperature, and be acceptable from the point of view of toxicity and workplace hygiene. In general, only waste that because of its physical properties cannot be fed directly to the burner without excessive effort, should be converted to CSS. b) Permitted waste Only special waste specified in Table A II/4 may be used for the production of CSS. Additionally, the general restrictions in Tables AII/2 and AII/3 apply. Tab. AII/2: General restrictions for problematic substances in special waste used for the production of CSS Halogenated organic compounds Poorly degradable halogenated organic compounds (e.g. PCB) Solvent content Ignition point max. 1% per weight max. 50 ppm below 15% above 55 °C The special waste shall not derive from production, preparation, distribution or use of highly active or biologically active substances, or otherwise be problematical from the point of view of workplace hygiene. Kåre Helge Karstensen [email protected] Page 418 of 420 Appendix II 3/4 Stand: March, 1998 Tab. AII/3: Standard values for maximum tolerable heavy metal content in waste permitted for production of CSS. Designation Standard value in [mg/kg] Lead Pb 600 Cadmium Cd 10 Chromium Cr 400 Copper Cu 500 Nickel Ni 300 Zinc Zn 4.000 all other heavy metals according to Table 1 of the Guidelines For the waste designated * in Table AII/4, the above standard values will apply from 1 January, 2004 onwards. Quality controls according to Chapter 2, section B, must be carried out to ensure that the permitted annual loads in Table A II/1 are not exceeded. 4. Requirements for production and use of CSS a) State of the art Processes must comply with the regulations concerning water protection, clean air (e.g. emission of organic substances) and safety (e.g. explosion protection), both in converting special waste to CSS and for temporary storage by the CSS producer and at the cement plants. Open shredding and mixing without exhaust treatment is, for example, not state of the art. b) Acceptance controls, inclusive of the necessary chemical analyses, must ensure that only permitted special waste is converted to CSS, and that problematical, heavily polluted waste or waste fractions that are unsuitable for other reasons are delivered to appropriate special waste incineration plants. c) Acceptance of premixed waste Waste premixed with sawdust is only permitted when the waste used, as well as the production and composition of the premixture, satisfy the present regulations. Waste containing solvents is, however, excepted. The waste codes 1260, 1620, 1640 and 1641 are not, therefore, permitted for the production of premixtures. Copies of the consignment document of the "original waste" shall be attached to the consignment on delivery of the premixtures. To protect the client, the address and the identification number of the "original consignor" may be concealed. Kåre Helge Karstensen [email protected] Page 419 of 420 d) Use CSS shall be introduced directly to the main burner of the cement kiln. Kåre Helge Karstensen [email protected] Page 420 of 420 Appendix II 4/4 Status: March, 1998 Tab. AII/4: Special waste permitted in the production of CSS OMSW Codes 1260 Designation Unhalogenated non-aqueous distillation residues, originating from solvent regeneration operations; see also category 8 1472 Residuals from oil or petrol gasoline separators; tank cleaning sludges and oily sludges 1473 Tank cleaning and oil sludge 1610* Paint, varnish and glue wastes having an aqueous phase (emulsions) Paint, varnish and glue wastes having an organic phase 1620* (solvents) 1630* Paint, varnish and glue wastes without a liquid phase 1631* Paints in powder form 1632* Hardened paints and pastes 1640* Waste of printing ink or coloring media having an organic phase (solvents) Restrictions Waste containing solvents (solvent content max. 15%) are permitted provided the peripheral plant at the cement works (e.g. temporary storage, charging systems including transport to the cement plants) complies with the regulations in OAPC and with the state of the art regarding safety. For existing plant not complying with these requirements the canton responsible specifies a reasonable rehabilitation period, not however extending beyond the end of 1999. See below for explanation of (*) 1641* Old paints and pigments The restrictions in Chapter 4 apply 1650* Waste of printing ink or coloring media without an to the production of organic phase (without solvents) Soaps, fats, lubricating oils or films of vegetable or premixtures 1740 animal origin 2231 Solid distillation residues 2240 Residues from coking, tar-containing wastes (except the wastes covered by codes 2870 and 2871) Settling, filtration and centrifuging residues (except the 2840* wastes covered by codes 1500, 2450, 2810-2821, 3020 and 3030) 3050 Contaminated packages and containers which have contained special waste unless they are used again for the transport of wastes of the same nature ∗ Heavy metal fractions (e.g. anti-corrosive paints or workshop sludge possibly classified under code 2840) must be eliminated by means of separation, and disposed of in a special waste incineration plant, or, if possible, recycled. The supplier must be kept informed. The Kåre Helge Karstensen [email protected] Page 421 of 420 specified annual pollutant loads should not be exceeded. Separation must be performed in compliance with the heavy metal loads (distributed over time) in Tab. AII/1. Kåre Helge Karstensen [email protected]
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