OZONE AND ELECTROLYZED WATER SYSTEMS FOR THE FOOD & BEVERAGE INDUSTRY DE NORA NEXT IS INSPIRED BY THE CORE VALUES OF DE NORA: research, innovation, attention to people and environment 1960 1983 1989 1998 2002 2005 2010 De Nora do Brazil established De Nora India (previously Titanor components ‐ acquisition of JV with Swedish atches) De Nora Deutschland (100% acquisition of Heraeus Electrochemie) Severn Trent De Nora (JV with Severn Trent Service) De Nora Tech (Eltech System Corp. is acquired) Permelec Electrode (acquisition of 100%) 1990 2000 1970 1980 1985 2005 2008 2010 2011 2012 1923 1969 1988 1993 2001 2005 2008 2011 2012 Oronzio De Nora Founded the company Permelec Electrode (50/50 JV between De Nora and Mitsui) Industrie De Nora Singapore (Titanor Singapore) Jiangyin De Nora Tianli Electrochemical (first production site in china) Uhdenora (50/50 JV with ThyssenKrupp Uhde) De Nora Elettrodi (Suzhou) (closing Jiangyin De Nora Tianli Electrochemical) MedNora and Verdenora established Chlorine Engineers (acquisition of 51%) Chlorine Engineers (acquisition of 100%) 2 OUR VALUES ARE IN OUR MISSION Supply technological and sustainable systems for the production on site and on demand of innovative solutions aimed at improving the health and quality of life for individuals, families and the planet. 3 OUR TARGET MARKETS Agricolture & Livestock Veterinary & Animal care Food Processing & Beverage Professional Cleaning 4 NEW ECO‐FRIENDLY SOLUTIONS FOR HEALTHY FOOD, WASTE REDUCTION AND WATER SAVINGS De Nora Next supply its target markets with high‐tech systems based on Electrolyzed water and Ozone produced on site from natural raw materials. Technologies that guarantee the lack of persistence and destroy pollutants in the water for a healthy and secure environment. OZONE SYSTEM ELECTROLYZED WATER BACK TO WATER AND SALT SALT ELECTRICAL CURRENT BACK TO TO OXYGEN WATER AIR ON SITE PRODUCTION ELECTROLYZED WATER FINAL USER ELECTRICAL CURRENT 1.5 kWh ON SITE PRODUCTION OZONE FINAL USER (0.5g/h‐52kg/h) FEATURES • • • • • No persistence in the environment No surplus production Less resources exploitation Less fuel consumption and transport costs Less plastic and chemicals to be disposed 5 ELECTROLYZED WATER Electrolyzed water contains sodium hypochlorite produced on site starting from sodium chloride, water and electricity. Salt & water solution 1) Salt (NaCl)+ Water (H2O) Na+ + Cl‐ + H2O NaCl+H2O 2) Salt & water + electric power Anode: 2Cl‐ Cathode : 2H2O + 2e‐ Cl2 + OH‐ NaCl + H2O + 2e‐ SIMPLIFIED ELECTROLYSIS CELL Na+ and Cl‐ From salt (NaCI) H+ OH Sodium Hypochlorite solution (NaClO) Cl2 + 2e‐ 2OH‐ + H2 ClO‐ + Cl‐ + H + NaClO + H2 SALT SOLUTION ELECTRICAL CURRENT H+ and OH‐ From water (H2O) 2 H gas O2 gas NaCl + H2O + 2e = SolevaTM Sodium Hypoclorite 6 OZONE Ozone is generated on site by oxygen through electric discharge. HEAT ELECTRODE O2 DISCHARGE GAP Oxygen + Electric discharge O2 + e‐ Oxygen radicals DIELECTRIC O3 ELECTRODE Oxygen radicals + Oxygen Ozone 2O + 2O2 2O 2O3 HEAT The usage of ozone provides a long list of advantages: • • • • • • High efficacy against bacteria, viruses, fungi, spores and biofilm It doesn’t create resistant bacteria Deep efficacy against dirt and odors, wherever it is hard to get No residuals on surfaces Not persistent in the environment Reduce usage, transport and storage of chemicals 7 OZONE Ozone can be used as gas or it can be mixed with water (ozonated water). OZONE GAS SYSTEM OZONE WATER SYSTEMS • For air sanitization • For surface sanitization • For deodorization • • • • To clean and sanitize equipments, surfaces, tools To sanitize process and waste water To treat waste water To reduce sludges production 8 FOOD PROCESSING & BEVERAGE Ozone and electrolyzed water proven efficacy for multiple uses: OZONE: • for a successful life extension in storage, transport and on the shelf • to guarantee higher food safety reducing bacteria, moulds, yeast, pesticides and mycotoxins • for process water saving (+ 50%) and treatment • for waste water treatment • for the sanitization of different surfaces (tools, equipments, barrels…) ELECTROLYZED WATER: • for surface sanitization of tools and equipment • for water treatment 9 FOOD LIFE EXTENSION + Fruits IN STORAGE TRANSPORT ON THE SHELF Vegetables HIGHER FOOD SAFETY ‐ BACTERIA MOULDS YEASTS PESTICIDES REUSE OF PROCESS WATER +50% Cheese Fish Meat Bottled Water Wineries WATER SAVING 10 FOOD PROCESSING & BEVERAGE FRUITS & VEGETABLES Fruits Vegetables To ensure high quality, safe products and extended shelf life, the Fruit and Vegetable industry has to adopt optimal sanitation techniques throughout the entire production chain. Ozone and Electrolyzed water systems can be used to sanitize air, water and any kind of surface performing • significant microbial loads reduction • up to 100% increase in the storage time • dramatic mycotoxins removal (as patuline) • up to 70% residual pesticide reduction • no changes for fruits and vegetables quality and no residues are left • reuse of process water up to 50% water saving • efficient waste water and sludge treatment 11 FOOD PROCESSING & BEVERAGE FRUITS & VEGETABLES • AIR SANITIZATION Surfaces and rooms sanitization are essential to grant every product safety but it is not enough. Once surfaces are sanitized they still can come in contact with all the microorganism in the air. Ozone can be used to significantly reduce the microbial loads in the air. Furthermore, when vaporized in a room, gets to all those spots that can hardly be reached during the cleaning phases, thus ensuring the rooms’ complete sanitization: all without causing a humidity level increase, inhibiting bacteria, yeast and mould growth. O3 50%÷100% DECREASE OF BACTERIA, MOULD, YEASTS MITES AND INSECTS 12 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Ozone sanitization of storage cell demonstrated a significant reduction of microbial load on different kind of fruits and vegetables and by consequence reduction of mycotoxins and longer shelf‐life. FOOD LIFE EXTENSION + IN STORAGE TRANSPORT ON THE SHELF HIGHER FOOD SAFETY ‐ BACTERIA MOULDS YEASTS PESTICIDES 13 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Ozone usage demonstrated a significant reduction of microbial load on apples. CFUs/gr 100000 CFUs/gr without O3 10000 ROYAL GALA CFUs/gr with O3 1000 100 10 days 1 1 15 30 45 60 80 CFUs/gr 1000000 O3 during day and night at 1°C 100000 UP TO 10000 GOLDEN ‐99% 1000 100 OF FUNGI AFTER 60 DAYS 10 1 days 1 15 30 45 60 80 1 15 30 45 60 80 CFUs/gr 1000000 100000 10000 FUJI 1000 100 10 1 days CIHEAM/IAMB, CNR‐IBPM, DE NORA NEXT [1]. 14 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Ozone usage demonstrated a significant reduction of microbial load on citrus and cherries. CFUs/gr 60 CFUs/gr without O3 CFUs/gr with O3 40 CITRUS 20 0 days 1 O3 during day and night at 1°C‐3°C 2 3 4 5 6 7 8 9 10 11 ‐50% OF FUNGI IN THE FIRST 3 DAYS CFUs/gr 60 40 CHERRIES 20 0 days 1 2 3 4 5 6 7 8 9 10 11 CIHEAM/IAMB, CNR‐IBPM, DE NORA NEXT [8]. 15 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Ozone usage demonstrated a significant reduction of microbial load on berries like blueberries, strawberries and raspberries. CFUs/g fruit No Ozone 2000 Ozone pulse 1500 STRAWBERRIES Ozone 1000 500 days 0 O3 “pulse and continuous” at 4°C 0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7 CFUs/g fruit 250 200 BLUEBERRIES 150 100 50 days 0 CFUs/g fruit 100 80 RASPBERRIES 60 40 20 days 0 CIHEAM/IAMB, CNR‐IBPM, DE NORA NEXT [9]. 16 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Ozone usage demonstrated a significant reduction of microbial load on grapes as well as a decrease in disease severity and diffusion, making unnecessary the use of plastic bags and/or sulfur dioxide. FUNGI [CFUs/g grape] YEASTS [CFUs/g grape] 14 30 12 ‐31% 10 8 20 ‐63% 15 6 10 4 5 2 0 0 Plastic bag+ SO2 O3 for 20 days at 1°C + 4 days at 23°C 25 No treatment Only Ozone Plastic bag+ SO2 No treatment Only Ozone Disease severity & diffusion [McKinney index] 3,0 NO TREATMENT= no platic bag‐no SO2‐no Ozone 2,5 2,0 1,5 1,0 0,5 0,0 Plastic bag+ SO2 No treatment Only Ozone CIHEAM/IAMB, CNR‐IBPM, DE NORA NEXT [6]. 17 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Ozone usage demonstrated a significant reduction of microbial load on durum wheat grain. BACTERIA [CFUs/g] YEASTS [CFUs/g grape] 3.000 15.000 2.500 2.000 10.000 ‐98% ‐100% 1.500 1.000 5.000 500 0 0 UNTREATED O3 TREATMENT OZONE UNTREATED OZONE FUNGI [CFUs/g] 700 600 500 400 ‐90% 300 200 100 0 UNTREATED OZONE CNR, Divella s.p.a, De Nora Next. 18 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Ozone usage demonstrated a significant reduction of microbial load on asparagus ensuring excellent quality in terms of physical consistency. FUNGI [CFUs/g grape] 15 10 CELL STORAGE WITH OZONE ‐93% 5 0 NO OZONE T=2°c OZONE AFTER 23 DAYS FORCE [g/cm2] 140 CELL STORAGE 120 +75% 100 80 60 40 20 0 NO OZONE OZONE CIHEAM/IAMB, De Nora Next. 19 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Ozone usage demonstrated a significant reduction of microbial load on red chicory ensuring better quality. PASSIVE REFRIGERATION + OZONE WEIGHT LOSS [g] MICROBIAL LOAD [CFUs] 30 1.000 T=1°C 30 DAYS ‐39% ‐40% 20 500 10 0 0 CONVENTIONAL P.R. + OZONE CONVENTIONAL P.R. + OZONE CONVENTIONAL STORAGE CIHEAM/IAMB, CNR‐IBPM, GEOFUR [2]. 20 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Stocking and storage in ozone‐treated chambers strongly reduce the presence of microorganisms such as Penicillium expansum and, consequently, the contamination of patulin*, a mycotoxin extremely dangerous to human health, especially to that of children. APPLE FUJI inoculated by Penicillium Expansum APPLE FUJI inoculated by Penicillium Expansum 4 months at 2°C 4 months at 2°C STANDARD CELL OZONE CELL *Patulin level in EU must less than 0.05 mg/Kg for baby fruit juice CIHEAM/IAMB, CNR‐IBPM, DE NORA NEXT [12]. 21 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Tests demonstrated that patulin, on different kinds of apple,was below the quantification limit in case of ozone sanitization. Patulin presence on Gala Apples [ng/g] 10000 No Ozone Ozone ROYAL GALA 100 1 days 0 15 30 45 60 Patulin presence on Golden Apples [ng/g] O3 during day and night at 1°C 10000 GOLDEN 100 1 days 0 15 30 45 60 Patulin presence on Fujj Apples [ng/g] 10000 FUJI Limit of patulin quantification: 5ng/g of fresh fruit 100 1 days 0 15 30 45 60 CIHEAM/IAMB, CNR‐IBPM, DE NORA NEXT [1]. 22 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Tests demonstrated the reduction of mycotoxins like Deoxynivalenol (DON) on durum wheat grain after ozone usage, without affecting grain quality. DON [μg/kg] 300 250 ‐37% 200 150 100 50 0 UNTREATED O3 TREATMENT OZONE EFFECT ON GLUTEN CONTENT AND QUALITY EFFECT ON MEALY GRAIN, MOISTURE, PROTEIN CONTENT 20 10 80 8 15 60 6 10 40 4 5 20 2 0 0 MEALY GRAIN MOISTURE No Ozone PROTEINS 0 GLUTEN CONTENT GLUTEN INDEX Ozone CNR, Divella s.p.a, De Nora Next. 23 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Apples stocked in a cell sanitized by ozone demonstrated a shelf‐life double than apples preserved in standard cells. Damages appear after 1 week on apples in standard cells, after 2 weeks on apples in ozone treated cells. Mycobacterial load data are aligned with these measurements. APPLE GRANNY SMITH TANKEN ON 14‐3‐2014 OZONE CELL 36 UFC/G 1 WEEK IN AIR outside of storage cell 1 WEEK IN AIR outside of storage cell T=18° T=18° 870 UFC/G APPLE GRANNY SMITH TANKEN ON 14‐3‐2014 STANDARD CELL Cristian Carboni, De Nora Next. 24 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Kiwi preserved in ozone sanitized cell show a 4% decrease of losses compared to kiwi in standard cells. After 13 days, the pulp is more solid and colour is more uniform: ozone blocks the development of mycelia and spores. AFTER 3.5 MONTHS PRODUCT BEFORE TREATMENT AND STORAGE (1 stock with low fungi, 1 stock with high fungi‐Botrytis) Sample in OZONE CELL OZONE CELL Spores only in contact zones 5 points (red) mycelia 29 points (blue) mold 13 DAYS IN AIR T=18° CELL WITH ETHYLENE ABSORBER (PERMANGANATE) Sample in standard cell Widely distributed spores 21 points (red) mycelia 41 points (blue) mold 25 FRUITS & VEGETABLES • OZONE AIR SANITIZATION On strawberries treated with ozone, preservation time can increase and even double: treated fruits do show higher quality and no decay after 10 days, while untreated fruits show decomposition traces already after 5 days. Microbial load is also lower after ozone treatment. TREATMENT WITH OZONE FOR 24H PRODUCT BEFORE TREATMENT AND STORAGE CFU/g CELL STORAGE WITH OZONE T=2° AFTER 5 DAYS NO TREATMENT AFTER 10 DAYS CFU/g CELL STORAGE CFU: Colony‐Forming Units CIHEAM/IAMB, CNR‐IPP,ISPP [10]. 26 FRUITS & VEGETABLES • OZONE AIR SANITIZATION When treated with ozone, strawberry preservation time can increase significantly also in absence of cold room storage. AFTER 5 DAYS PRESERVATION WITH CONTINUOUS OZONE T=20° PRESERVATION WITH AIR CIHEAM/IAMB, CNR‐IPP,ISPP [10]. 27 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Tests demonstrated that ozone can reduce the ethylene concentration, produced during ripening by fruits, and as consequence the ripening process becomes longer as well as the shelf life STANDARD CELL OZONE CELL OZONE CELL STANDARD CELL ETHYLENE IN STORAGE ROOM Ozone switch on Ozone switch off Ozone switch on Set‐up of constant ozone conc. 0,02 0,018 0,016 0,014 0,012 0,01 0,008 0,006 0,004 0,002 0 28‐feb 21‐feb 14‐feb 07‐feb 31‐Jan 24‐Jan 17‐Jan 10‐Jan 3‐Jan 27‐dec 20‐dec 13‐dec ETHYLENE Cristian Carboni, De Nora Next. 28 FRUITS & VEGETABLES • OZONE AIR SANITIZATION Proper set‐up of process parameters as well as their control are the key to make ozone properly working. De Nora Next long experience in testing is the Key for success. EFFECT OF UNCORRECT PROCESS PARAMETERS SET‐UP 29 FOOD PROCESSING & BEVERAGE FRUITS & VEGETABLES • PROCESS AND WASHING WATERS TREATMENT Ozonated water advantages: • reduction of the microbial loads on fruits surfaces • decrease in goods losses and shelf life extension • Patulin levels’ reduction • 70% less pesticides residual • 50% reduction in water consumption (process water can be re‐used) • reduction of bad tastes and odours O3 NaClO Electrolyzed water, based on sodium hypochlorite, can be an alternative and less expensive solution. Combined with Ozone treatments for an even greater effectiveness. 30 FRUITS & VEGETABLES • PROCESS AND WASHING WATERS Apples washed with ozonated water have lower microbial load and longer shelflife… BACTERIA [CFUs/cm2] 1,0 WASHING WITH PURIFIED WATER 5 MIN 0,8 3months at 2°C 0,6 RINSING WITH OZONATED WATER 1MIN 0,4 0,2 0,0 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 BACTERIA [CFUs/cm2] 3months at 2°C 1000,0 WASHING WITH WATER 800,0 5 MIN 200,0 600,0 400,0 0,0 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 De Nora Next. 31 FRUITS & VEGETABLES • PROCESS AND WASHING WATERS …and Patulin contamination can be reduced up to 100% in only 2 minutes. BACTERIA [CFUs/cm2] 80 WASHING WITH PURIFIED WATER 5 MIN RINSING WITH OZONATED WATER Patilina ug/l 70 60 50 100% 40 30 20 2 MIN 10 0 SAMPLE OZONE 2 MINUTES OZONE 5 MINUTES Cristian Carboni, De Nora Next. 32 FRUITS & VEGETABLES • PROCESS AND WASHING WATERS Bacteria load on fresh cut salad can be significantly reduced washing it with ozonated water respect to standard washing. MESOPHILIC BACTERIA [CFUs/g] 10.000.000 8.800.000 8.000.000 6.000.000 ‐86% 4.000.000 1.200.000 2.000.000 0 BEFORE WASHING O3 in washing cycles WASHING WITH OZONATED WATER ENTEROBACTERIACEAE [CFUs/g] 25.000 25.000 20.000 15.000 ‐52% 12.000 10.000 5.000 0 BEFORE WASHING WITH WASHING OZONATED WATER De Nora Next. 33 FRUITS & VEGETABLES • PROCESS AND WASHING WATERS When process water is not recycled electrolyzed water is a more effective and less expensive alternative method of water treatment, ensuring strong reduction of the microbial contamination of process water… BACTERIA [UFC/ml] 6.000 COLIFORM BACTERIA [UFC/100 ml] 5.600 2.000 300 1.600 5.000 ENTEROCOCCUS [UFC/100 ml] 290 250 1.500 4.000 200 ‐100% 3.000 ‐100% 1.000 2.000 ‐100% 150 100 500 1.000 0 0 + ELECTROLYZED WATER 0 0 PROCESS WATER PROCESS WATER + E.W. 50 0 0 PROCESS WATER PROCESS WATER + E.W. PROCESS WATER PROCESS WATER + E.W. De Nora Next. 34 FRUITS & VEGETABLES • PROCESS AND WASHING WATERS … as well as a decrease in the percentage of rotten fruits. % of rot apples Washing RINSING WITH ELECTROLYZED WATER Washing + Rinsing with E.W. 37 40 35 30 1 MIN WASHING IN PROCESS WATER STORAGE FOR 32 DAYS AT 20°C 25 20 15 10 14 9 11 3 5 3 MIN 9 0 SAMPLE 1 SAMPLE 2 SAMPLE 3 NO RINSING De Nora Next. 35 FRUITS & VEGETABLES • PROCESS AND WASHING WATERS Combination of pre‐sanitization with ozone followed by washing with electrolyzed water can guarantee strong reduction of fungi, as shown in tests on cherries, without affecting their quality in terms of hardness and sugar content. FORCE [g/cm2] FUNGI [CFUs/g] 25 22 18 20 STANDARD CELL E.W washing 54 60 13 15 No washing Ozone washing 78 71 80 40 10 20 5 0 0 NO WASHING WASHING WASHING WITH WITH OZONATED ELECTROL. WATER WATER NO WASHING WASHING WASHING WITH WITH OZONATED ELECTROL. WATER WATER 30 DAYS AT 0°C FORCE [g/cm2] FUNGI [CFUs/g] 15 OZONE CELL No washing Ozone washing 13 150 100 10 5 E.W washing 0 2 SUGAR CONTENT [brix] 130 79 15 14 15 14 102 50 10 5 1 NO WASHING WASHING WASHING WITH WITH OZONATED ELECTROL. WATER WATER 0 NO WASHING WASHING WASHING WITH WITH OZONATED ELECTROL. WATER WATER 0 NO WASHING WASHING WASHING WITH WITH OZONATED ELECTROL. WATER WATER 36 FRUITS & VEGETABLES • PROCESS AND WASHING WATERS Process water saving can achieve 50% using ozone in water recycling. PROCESS WITH RECYCLING AND OZONE FROM TANK 2, A WATER QUANTITY OF 40 L/MIN IS COLLECTED, TREATED WITH OZONE AND TRANSFERED TO TANK 1. WATER SAVING: TRADITIONAL PROCESS +50% TANK 1 AND TANK 2 RECEIVE A WATER QUANTITY OF 40 L/MIN 37 FOOD PROCESSING & BEVERAGE FRUITS & VEGETABLES • SURFACES & EQUIPMENT SANITIZATION Electrolyzed water and Ozone solutions, both characterized by antimicrobial properties, can be used on every surface, for an immediate sanitation and a significant microbial load reduction. Effectiveness test* 99.99% gram positive and gram negative bacteria reduction when 0.1% electrolyzed water was used on non‐porous surfaces O3 NaClO *in compliance to the EPA GUIDELINES 38 FRUITS & VEGETABLES • SURFACES & EQUIPMENT SANITIZATION Ozonated water, well know for its antimicrobial efficacy, can be used on every surface, for an immediate sanitation and a significant microbial load reduction in one step. MICROBIAL LOAD [UFC/cm2] 10 9 ‐33% ‐67% 8 6 6 4 2 2 0 0 CLEANING + RINSING WITH WATER CLEANING + STD SANITIZER OZONATE D WATER CLEANING + RINSING WITH OZONATED WATER 39 FRUITS & VEGETABLES • SURFACES & EQUIPMENT SANITIZATION For an even higher surface sanitization electrolyzed water is the right solution. Effectiveness tests, in compliance with EPA guidelines, proven a 99.99% gram positive and gram negative bacteria reduction. Electrolyzed water 0.1% One‐step sanitizer for hard, non‐porous surfaces, environmental and food contact surfaces. • 0.1% active ingredient • contact time: 2min • shelflife: 48h • active in presence of organic soil (5%) Kill Gram positive and negative Bacteria Staphyloccocus aureus ATCC 6538 Klebsiella pneumoniae ATCC 4352 EPA GUIDELINE OCSPP 810.2300 40 FOOD PROCESSING & BEVERAGE FRUITS & VEGETABLES • WASTE WATER Water is at the core of food processing. High volumes of wastewater contaminated by organic products and extremely rich in COD and BOD need to be treated before release in the sewage system, such as disposal of sludges, generated in the bioreactor, is required. DeNora Next developed Ozone systems that can be used to: • decrease COD and BOD levels • remove a wide range of microorganism • reduce the amount of sludge produced, with a positive impact on the disposal costs • reduce the amount of chemicals required for the sanitization from 30‐40% reduction in the amount of produced sludge 41 OZONE FOR WASTE WATER TREATMENT Ozone can be used in waste water treatment before or after biological treatment. BEFORE BIOLOGIC TREATMENT TO INCREASE BIOLOGICAL EFFICIENCY OZONE Biological aeration tank Equalization tank COD is reduced by ozone before waste water goes into the biological reactor, in this way the ratio BOD/COD increases. AFTER BIOLOGIC TREATMENT OZONE Pre‐treatment Biological aeration tank TO RESPECT DISCHARGE LIMIT BEFORE DISPOSAL INTO WATER BODY residual COD and germs are reduced by ozone. 42 OZONE FOR WASTE WATER TREATMENT Ozone can be used also to reduce biological sludge production: • Decrease of 30‐40% of dry matter biological sludge production • Improve water treatment plant efficiency: better sludge settling ‐ lower sludge volume index • Improve sludge characteristics (better sludge dewatering with less chemicals needed) PRE‐TREATMENT BIOLOGICAL AERATION TANK CLARIFIER OZONE Recirculation sludge 43 REFERENCES 1. Ozone for post‐harvest treatment of apple fruits. Yaseen, T., et all 2015. Phytopathologia Mediterranea, 54 (1), 94‐103. doi:10.14601/Phytopathol_Mediterr‐14478 2. PASSIVE refrigeration and ozone‐enriched atmosphere to extend the shelf‐life of baby leaf lettuce, arugula and red chicory Thaer Yaseen, Eade Damara, Marilita Gallo, Franco Santoro, Cristian Carboni and Anna Maria D’Onghia IOA‐EA3G Conference, Barcelona, Spain – 28 June 3 July, 2015 3. Influence of continuous exposure to gaseous ozone on the quality of red bell peppers, cucumbers and zucchini Glowacz M.,Colgan R., Rees D. Postharvest Biology and Technology 99 (2015) 1–8 4. L’ozono nella tutela della qualità della frutta: uno strumento efficace e sostenibile. Yassen T., Albanese P., Turan B., Carboni C.,Ferri V., D’Onghia A.M, Ricelli A. Post‐raccolta 2014 5. L’impiego dell’acqua elettrolizzata nelle fasi di post‐raccolta degli agrumi Yaseen T., Damara E., Albanese P., Ferri V, Carboni C, D’Onghia A.M e Ricelli A. Post‐raccolta 2014 6. Influence of postharvest ozone treatment on decay, catalase, lipoxygenase activities, and anthocyanin content of ‘Redglobe’ table grapes Thaer Yaseen1, Alessandra Ricelli2, Pietro Albanese1, Isabella Nicoletti3, Salwa Essakhi1, Cristian Carboni4 and Anna Maria D’Onghia1 IOA‐EA3G Conference, Dublin, Ireland – June 3‐5, 2014 7. Thermopallet a refrigerazione passive e rilascio controllato di ozono per la frigoconservazione dell’uva da tavola Cefola Maria, Pace Bernardo, Cardinali Angela Post‐raccolta 2014 8. Use of electrolyzed water, ozone and passive refrigeration in post‐harvest to preserve the quality of cherry, table grape and citrus. Yaseen T., Damara E., Albanese P., Ferri V., Carboni C., D’Onghia A. M. and A. Ricelli (2014). UProceedings of Postharvest Unlimited ISHS international conference 10‐13 June 2014. Cyprus. P142. 9. Effect of storage in ozone‐enriched atmosphere on fungal contamination, catalase, superoxide dismutase and glutathione peroxidase activity in berries. Thaer Yaseen, Alessandra Ricelli, Pietro Albanese, Cristian Carboni and Anna Maria D’Onghia IOA‐EA3G Conference, Dublin, Ireland – June 3‐5, 2014 44 REFERENCES 10. The use of ozone in strawberry post‐harvest conservation. Biological Control of Fungal and Bacterial Plant Pathogens. Yaseen T., D’Onghia A.M., Ricelli A. . IOBC‐WPRS Bulletin Vol. 86. pp. 143‐ 148, 2013. 14. Quality and shelf‐life of washed fresh‐cut asparagus in modified atmosphere packaging Rungsinee Sothornvit, Peeriya Kiatchanapaibul LWT ‐Food Science and Technology, Volume 42, Issue 9, November 2009 11. Un nuovo strumento efficace e sostenibile per la tutela della qualità della frutta: l’ozono. Thaer Yaseen., Burak Turan., Cristian Carboni., Anna Maria D’Onghia., Alessandra Ricelli Torinoscienza 20‐11‐2012 15. Deployment of low‐level ozone‐enrichment for the preservation of chilled fresh produce Nikos Tzortzakis, Ian Singleton, Jeremy Barnes Postharvest Biology and Technology 43 (2007) 261–270 12. FRESCHE E BELLE PIÙ A LUNGO. L'utilizzo dell'ozono consente di mantenere inalterata nel tempo la qualità di frutta e verdura. Yaseen T., Turan B., Carboni C, D’Onghia A. M., Ricelli A.‐ Torinoscienza 2012 13. Ozone application for postharvest treatment on orange and cherry fruits. Yaseen T., Rahim Y., D’Onghia A. M., Ligorio A., Ricelli A., (2012). In: Proceeding of MPU Workshop: Plant Protection for the Quality and Safety of the Mediterranean Diet., pp. 59‐59. 16. EVALUATION OF THE EFFECT OF OZONE EXPOSURE ON DECAY DEVELOPMENT AND FRUIT PHYSIOLOGICAL BEHAVIOR L. Palou., C.H. Crisosto., J.L. Smilanick., J.E. Adaskaveg., J.P. Zoffoli Proc. 4th Int. Conf. on Postharvest,2001 17. Ozone for control of post‐harvest decay of table grapes caused by Rhizopus stolonifer P.Sarig.,T.Zahavi.,Y.Zutkhi.,S.Yannai.,N.Lisker., R.Ben‐Arie Physiological and Molecular Plant Pathology (1996) 48, 403‐415 45 OZONE SYSTEMS 46 OZONE SYSTEMS Ozone is generated on site by oxygen through electric discharge. HEAT ELECTRODE O2 DISCHARGE GAP DIELECTRIC O3 ELECTRODE Oxygen + Electric discharge O2 + e‐ Oxygen radicals Oxygen radicals + Oxygen Ozone 2O + 2O2 2O 2O3 HEAT A cooling system is required due the generation of heat. Cooling can be done by: air or water 47 OZONE SYSTEMS Oxygen can be generated from air or it can be provided as pure gas, depending on the quantity of ozone to be generated. Oxygen from air Pure oxygen ~ 2g/h of ozone ~ 70 kg/h of ozone from 53 to 735 g/h of ozone AIR • Air must be filtered in order to avoid contaminants damage the ozone generator • Air must be dried in order to avoid the formation of nitric acid (HNO3) • Oxygen in air can be concentrated in order to increase efficiency from 70 to 1000 g/h of ozone PURE OXYGEN OZONE SYSTEM MCP SERIE 48 OZONE SYSTEMS Ozone can be used as gas or it can be mixed with water (ozonated water). OZONE GAS SYSTEM OZONE WATER SYSTEMS Injection and diffuser systems are required in order to solubilize ozone in water • For air sanitization • To clean and sanitize equipments, surfaces, tools • For deodorization • To sanitize process and waste water • For surface sanitization • To treat waste water • To reduce sludges production 49 OZONE SYSTEMS Safety aspects need to be considered in order to avoid toxic effect on people. • Usage of destructors of excess of ozone in vent gas or of out‐gassing from water is required: ‐Thermal destructor ‐Catalytic destructor ‐UV destructor • Ambient air sensors of ozone coupled with automatic ozone generator shut‐off device is recommended. 50 OZONE SYSTEMS Low ozone concentration, used in food industry, should limit the possibility of exposure to toxic concentrations in case security protocols aren’t respected. 10,000 OZONE CONCENTRATION, ppm FATAL REGION Concentration typically used: 1,000 • 0.3 ppm for mould control • 20 ppm for environment sanitization PERMANENT TOXICITY REGION 100 1 hour of exposure is below the limit for toxicity TEMPORARY TOXICITY REGION 10 1 NON SYMPTOMATIC REGION NON TOXIC REGION 0,1 0,1 1 10 100 1,000 10,000 EXPOSURE TIME, min 51 OZONE SYSTEMS WATER TREATMENT SANITIZATION We provide a wide range of systems for all the applications: air, water, surfaces sanitization and water treatment. • Sanitizer • Deodorizer • Corona discharge (DBD*) from air and oxygen • Gas /water/ “gas +water” systems For environment, equipments, tools, process water • Waste water treatment • Drinking water treatment • Process water treatment • Ozone capacity: 0,5‐1000g/h • Process time: 30 min‐24h‐continuous • Ozone sensors and alarms (water and air) • Corona discharge (DBD) from air and oxygen • (Gas) /water/ “gas +water” systems • Ozone capacity: 53g/h‐52kg/h • Ozone sensors and alarms (water and air) *DBD=dielectric barrier discharge 52 OZONE SYSTEMS • AIR SANITIZATION FEATURES OZ‐MODULAR OZ80 /OZ1000/OZ2000 O3 POWER (S_M_L_H) GAS GAS GAS OZONE GENERATION OZONE PRODUCTION WITH AIR 0,5 g/h OZONE PRODUCTION WITH AIR (PSA) 4‐32 g/h (possible increase up to 80 g/h) 4 g/h; 8 g/h 16 g/h; 32 g/h; 64 g/h; 104 g/h OZONE PRODUCTION WITH LIQUID PURE OXYGEN N.A. N.A. N.A. COOLING SYSTEM Air Air Air AIR FILTERS X X OZ1000 / OZ 2000 X AIR DRYER X X OZ1000 / OZ 2000 X OZONE DESTRUCTION Optional Optional Optional OZONE MIXING AND CONTACT SYSTEM N.A. N.A. N.A. INSTRUMENTATION & CONTROL Ozone sensors (process & safety) PLC; Remote control; Data storage Ozone sensors (process & safety); PLC: optional Safety Ozone sensors; Process Ozone sensors: optional; PLC; Mobile 53 OZONE SYSTEMS • AIR SANITIZATION OZ‐MODULAR APPLICATIONS FRUIT & VEGETABLES PROCESSING X Cell storage volume: 500‐2000 m3 OZ80 /OZ1000/OZ2000 O3 POWER (S_M_L_H) X Cell storage volume: 500‐1000 m3 BOTTLED WATER & SOFT DRINKS WINERIES X CHEESE X Cell storage volume: 500‐2000 m3 X Cell storage volume: 500‐1000 m3 MEAT PROCESSING X Cell storage volume: 500‐2000 m3 X Cell storage volume: 500‐1000 m3 FISH PROCESSING X Cell storage volume: 500‐2000 m3 X Cell storage volume: 500‐1000 m3 54 OZONE SYSTEMS • PROCESS WATER & SURFACE SANITIZATION FEATURES O3 POWER MIX (S_M_H) STERILINE 1 ON SKID SYSTEMS GAS+WATER (1m3 batch) WATER (batch & continuous) WATER (batch & continuous) OZONE GENERATION OZONE PRODUCTION WITH AIR N.A 53g/h 53g/h‐735g/h (@O3 10% w/w) OZONE PRODUCTION WITH AIR (PSA) 24g/h;35g/h; 160g/h 70g/h(@O3 10% w/w) 70g/h‐1000g/h (@O3 10% w/w) OZONE PRODUCTION WITH PURE OXYGEN N.A. 70g/h(@O3 10% w/w) 70g/h‐1000g/h (@O3 10% w/w) COOLING SYSTEM Air Water Water AIR FILTERS X X X AIR DRYER X X X OZONE DESTRUCTION Optional X X OZONE MIXING AND CONTACT SYSTEM X X X INSTRUMENTATION & CONTROL Safety Ozone sensors in air; Process Ozone sensors in water; PLC; Mobile Safety sensors for Ozone ; Oxygen leak detector; Process controls(optional): Redox and Ozone sensors in water; PLC Siemens S7‐1200 Touch Screen 4”; Interface: MODBUS, PROFIBUS, ETERNET Remote control: optional Safety sensors for Ozone ; Oxygen leak detector; Process controls(optional): Redox and Ozone sensors in water; PLC Siemens S7‐1200 Touch Screen 4”; Interface: MODBUS, PROFIBUS, ETERNET Remote control: optional 55 OZONE SYSTEMS • PROCESS WATER & SURFACE SANITIZATION FEATURES O3 POWER MIX (S_M_H) STERILINE 1 ON SKID SYSTEMS FRUIT & VEGETABLES PROCESSING X up to 2,5m3/h X from 1 up to 10m3/h X from 10 up to 40m3/h BOTTLED WATER & SOFT DRINKS X up to 2,5m3/h X from 1 up to 10m3/h X from 10 up to 40m3/h WINERIES X up to 2,5m3/h X from 1 up to 10m3/h X from 10 up to 40m3/h CHEESE X up to 2,5m3/h X from 1 up to 10m3/h X from 10 up to 40m3/h MEAT PROCESSING X up to 2,5m3/h X from 1 up to 10m3/h X from 10 up to 40m3/h FISH PROCESSING X up to 2,5m3/h X from 1 up to 10m3/h X from 10 up to 40m3/h 56 OZONE SYSTEMS • WATER TREATMENT FEATURES OZONE GENERATION MCP1‐2‐4‐7‐14 TPF DTPF WATER (batch & continuous) WATER (batch & continuous) WATER (batch & continuous) OZONE PRODUCTION WITH AIR 53 g/h; 105 g/h; 210 g/h; 367 g/h; 735 g/h From 1 kg/h up to 20 kg/h From 9,6 kg/h up to 40 kg/h OZONE PRODUCTION WITH AIR (PSA) 70 g/h; 140 g/h; 280 g/h; 500 g/h; 1000 g/h From 1,3 kg/h up to 26 kg/h (@O3 10% w/w) From 12,8 kg/h up to 52 kg/h (@O3 10% w/w) OZONE PRODUCTION WITH PURE OXYGEN 70 g/h; 140 g/h; 280 g/h; 500 g/h; 1000 g/h From 1,3 kg/h up to 26 kg/h (@O3 10% w/w) From 12,8 kg/h up to 52 kg/h (@O3 10% w/w) COOLING SYSTEM Water Water Water AIR FILTERS X X X AIR DRYER X X X OZONE DESTRUCTION X (Not integrated) X (Not integrated) X (Not integrated) OZONE MIXING AND CONTACT SYSTEM X (Not integrated) X (Not integrated) X (Not integrated INSTRUMENTATION & CONTROL Safety sensors for Ozone ;Oxygen leak detector; Process controls (optional): Redox and Ozone sensors in water; PLC Siemens S7‐1200 Touch Screen 4”; Interface: MODBUS, PROFIBUS, ETERNET; Remote control: optional Safety sensors for Ozone ;Oxygen leak detector; Process controls (optional) : Redox and Ozone sensors in water; PLC Siemens S7‐300 Touch Screen 7”; Interface: MODBUS , PROFIBUS, ETERNET; Remote control: optional Safety sensors for Ozone; Oxygen leak detector; Process controls (optional): Redox and Ozone sensors in water; PLC Siemens S7‐ 300 Touch Screen 7”; Interface: MODBUS, PROFIBUS, ETERNET; Remote control: optional 57 OZONE SYSTEMS • WATER TREATMENT MCP1‐2‐4‐7‐14 APPLICATIONS TPF DTPF FRUIT & VEGETABLES PROCESSING X X X BOTTLED WATER & SOFT DRINKS X X X WINERIES X X X CHEESE X X X MEAT PROCESSING X X X FISH PROCESSING X X X 58 OZONE SYSTEMS • OZONE DESTRUCTORS FEATURES DOT‐serie (Thermal Ozone Destroyers) DOCAT‐serie (Thermal and catalytic Ozone Destroyers) DTR‐serie (Thermal Ozone Destroyers with recovery) OPERATING TEMPERATURE 360°C 60°C 360°C MAX GAS FLOW TREATED 110Nm3/h 500Nm3/h 500Nm3/h OTHER Electrical cabinet and ozone destroyer are provided separate Electrical cabinet and ozone destroyer are assembled on the same skid Electrical cabinet and ozone destroyer are assembled on the same skid POWER CONSUMPTION 0.1 kW/Nm3 0.03kW/Nm3 0.04kW/Nm3 INDICATIONS OF USE Applications requiring low capacity (process water) Applications requiring high capacity (waste water treatment, drinking water) Applications requiring high capacity (waste water treatment, drinking water). In presence of specific pollutants that could poison the catalyst (DOCAT). 59 OZONE SYSTEMS • ANCILLARY EQUIPMENT Air preparation systems Oxygen generation systems (PSA) Control systems Ozone analyzer in air Ozone analyzer in water Water cooling system Ozone mixing and contact systems Safety systems Ozone detector 60 ELECTROLYZED WATER SYSTEMS 61 ELECTROLYZED WATER SYSTEMS Electrolyzed water contains sodium hypochlorite produced on site starting from sodium chloride, water and electricity. Salt & water solution 1) Salt (NaCl) + Water (H2O) Na+ + Cl‐ + H2O NaCl + H2O 2) Salt & water + electric power Anode: 2Cl‐ Cathode : 2H2O + 2e‐ Cl2 + OH‐ NaCl + H2O + 2e‐ SIMPLIFIED ELECTROLYSIS CELL Na+ and Cl‐ From salt (NaCI) H+ OH Sodium Hypochlorite solution (NaClO) Cl2 + 2e‐ 2OH‐ + H2 ClO‐ + Cl‐ + H + NaClO + H2 SALT SOLUTION ELECTRICAL CURRENT H+ and OH‐ From water (H2O) 2 H gas O2 gas NaCl + H2O + 2e = SolevaTM Sodium Hypoclorite 62 ELECTROLYZED WATER SYSTEMS Electrolyzed water is produced in batches of 100 litres at 6 g/l starting from 2 kg of sodium chloride. NaCl 2 kg 3h 100 litres of Electrolyze water (NaClO) 6g/l dilution To 1 g/l depending on customer needs WATER 100L ELECTRICAL POWER 4.5kWh SALT ‐KCl 2 kg INSTEAD OF 1 Cubic meter of chemicals 63
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