ANALYSIS OF ALTERNATIVES PUBLIC
Legal name of applicant(s):
SPOLANA, a.s.
Submitted by:
SPOLANA, a.s.
Substance:
Trichloroethylene
Use title:
Use as an extraction solvent in caprolactam production
Use number:
Use 1
ANALYSIS OF ALTERNATIVES
CONTENTS
DECLARATION .......................................................................................................................................................... 4
1. SUMMARY ............................................................................................................................................................ 5
2. ANALYSIS OF SUBSTANCE FUNCTION.......................................................................................................... 8
2.1 General information about trichloroethylene .................................................................................................. 8
2.1.1 Physical–chemical properties of trichloroethylene .............................................................................. 8
2.1.2 Production of trichloroethylene ........................................................................................................... 8
2.1.3 Uses of trichloroethylene ..................................................................................................................... 9
2.2 General information about caprolactam ......................................................................................................... 9
2.2.1 History of ε-caprolactam synthesis ...................................................................................................... 9
2.2.2 Physical – chemical properties of ε-caprolactam ................................................................................ 10
2.2.2.1 Physical properties of ε-caprolactam ..................................................................................... 10
2.2.2.2 Chemical properties of ε-caprolactam ................................................................................... 11
2.2.3 Synthesis of ε-caprolactam .................................................................................................................. 11
2.2.3.1 Synthesis of ε-caprolactam from cyclohexanone .................................................................. 11
2.2.4 Use of ε-caprolactam ........................................................................................................................... 12
2.2.4.1 Properties of polyamides ....................................................................................................... 13
2.2.4.2 Polyamide 6 – NYLON ......................................................................................................... 13
2.2.4.3 Continual polymerization of POLYAMIDE 6 ...................................................................... 13
2.2.5 Global production and consumption of ε-caprolactam ........................................................................ 14
2.2.5.1 Global production of an ε-caprolactam ................................................................................. 14
2.2.5.2 Consumption of ε-caprolactam .............................................................................................. 15
2.3 Caprolactam production process in SPOLANA a.s. ....................................................................................... 16
2.3.1 Basic information about SPOLANA a.s. ............................................................................................. 16
2.3.2 Caprolactam production process in SPOLANA a.s. ............................................................................ 17
2.3.3 Goal of TRI in SPOLANA a.s. caprolactam production ..................................................................... 18
3. ANNUAL CONSUMPTION OF TRI..................................................................................................................... 20
4. IDENTIFICATION OF POSSIBLE ALTERNATIVES......................................................................................... 21
4.1 Description of efforts made to identify possible alternatives .......................................................................... 21
4.1.1 Research and development .................................................................................................................. 21
4.1.2 Data searches ....................................................................................................................................... 21
4.1.2.1 Data searches – substances .................................................................................................... 22
4.1.2.2 Data searches – technologies ................................................................................................. 24
4.2 Results of AoA research ................................................................................................................................. 25
4.2.1 Alternative substances ......................................................................................................................... 25
4.2.2 Alternative technologies ...................................................................................................................... 27
4.3 Consultations .................................................................................................................................................. 30
5. SUITABILITY AND AVAILABILITY OF POSSIBLE ALTERNATIVES ......................................................... 31
5.1 ALTERNATIVE 1: Tetrachloromethane ....................................................................................................... 31
5.1.1 Name and other identifiers for the substance ...................................................................................... 31
5.1.2 Technical feasibility for the applicant ................................................................................................. 32
5.1.3 Reduction of overall risk due to transition to the alternative ............................................................... 34
5.1.4 Economic feasibility ............................................................................................................................ 34
5.1.5 Availability .......................................................................................................................................... 36
5.1.6 Conclusion of suitability and availability of tetrachloromethane ........................................................ 36
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ANALYSIS OF ALTERNATIVES
5.2 ALTERNATIVE 2: Chloroform ..................................................................................................................... 37
5.2.1 Name and other identifiers for the substance ...................................................................................... 37
5.2.2 Technical feasibility for the applicant ................................................................................................. 38
5.2.3 Reduction of overall risk due to the transition to the alternative ......................................................... 39
5.2.4 Economic feasibility ............................................................................................................................ 39
5.2.5 Availability .......................................................................................................................................... 41
5.2.6 Conclusion on suitability and availability for chloroform ................................................................... 41
5.3 ALTERNATIVE 3: Tetrachloroethylene ....................................................................................................... 42
5.3.1 Name and other identifiers for the substance ...................................................................................... 42
5.3.2 Technical feasibility for the applicant ................................................................................................. 43
5.3.3 Reduction of overall risk due to transition to the alternative ............................................................... 44
5.3.4 Economic feasibility ............................................................................................................................ 45
5.3.5 Availability .......................................................................................................................................... 46
5.3.6 Conclusion on suitability and availability for tetrachloroethylene ...................................................... 46
5.4 ALTERNATIVE 4: Ionic liquids ................................................................................................................... 47
5.4.1 Name and other identifiers for the substance ...................................................................................... 47
5.4.2 Technical feasibility for the applicant ................................................................................................. 47
5.4.3 Reduction of overall risk due to transition to the alternative ............................................................... 48
5.4.4 Economic feasibility ............................................................................................................................ 48
5.4.5 Conclusion on suitability and availability for ionic liquids ................................................................. 50
6. OVERALL CONCLUSIONS ON SUITABILITYAND AVAILABILITY OF POSSIBLE ALTERNATIVES FOR
USE 1............................................................................................................................................................................ 51
6.1 Conclusion of alternatives for USE 1 ............................................................................................................. 51
6.2 Future plan of research ................................................................................................................................... 52
6.2.1 Literature sources survey and data compilation .................................................................................. 52
6.2.2 Laboratory research and projection of extractions .............................................................................. 53
6.2.3 Pilot plant ............................................................................................................................................ 53
6.2.4 Conclusions of the research ................................................................................................................. 54
7. REFERENCE LIST ................................................................................................................................................ 56
8. LIST OF ABREVIATTIONS, FIGURES AND TABLES ..................................................................................... 61
8.1. List of abreviattions ........................................................................................................................................ 61
8.2. List of figures.................................................................................................................................................. 61
8.3. List of tables ................................................................................................................................................... 61
9. APPENDIXES AND ANNEXES ........................................................................................................................... 63
ANNEX – JUSTIFICATIONS FOR CONFIDENTIALITY CLAIMS ........................................................................ 63
APPENDIXES .............................................................................................................................................................. 66
Appendix 1: ID Cards of possible substances alternatives ...................................................................................... 67
Appendix 2: Alternative technologies of caprolactam production study ................................................................ 100
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ANALYSIS OF ALTERNATIVES
DECLARATION
We, SPOLANA, a.s., request that the information blanked out in the “public version” of the
Analysis of Alternatives is not disclosed. We hereby declare that, to the best of our knowledge as of
today (18th August 2014) the information is not publicly available, and in accordance with the due
measures of protection that we have implemented, a member of the public should not be able to
obtain access to this information without our consent or that of the third party whose commercial
interests are at stake.
18th August 2014, Neratovice
Signature:
Karel Pavlíček
CEO and Chairman of the Board of Directors
18th August 2014, Neratovice
Signature:
Artur Sławomir Jabłoński
CFO and Member of the Board of Directors
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ANALYSIS OF ALTERNATIVES
1. SUMMARY
Trichloroethylene (TRI) was identified as a Substance of Very High Concern (SVHC) pursuant to
Article 57(a) as it is classified according to Annex VI, part 3, Table 3.1 (the list of harmonized
classification and labelling of hazardous substances) of Regulation (EC) No 1272/2008 as
carcinogen 1B, H350 (may cause cancer), and was therefore included in the Candidate List for
authorisation on 18 June 2010, following ECHA’s decision ED/30/2010 (ECHA – European
Chemical Agency, 2011).
Since 17th April 2013 trichloroethylene (TRI) is included in the REACH authorization list,
following the Regulation 348/2013 amending Annex XIV of the REACH Regulation 1907/2006
(Commision Regulation (EU) No 348/2013, 2013). The effort of this paper is to obtain as much
information as possible to determine if there is any suitable alternative to replace TRI in the
SPOLANA, a.s. production process of caprolactam. To fulfil all of the demands of the analyses of
alternatives it is essential to know the substance function in the process, the process itself and the
caprolactam domination in the worldwide trade.
During the AoA 32 substances were assessed based on the KIs as alternatives to replace TRI
(Chapter 4).
Only 3 substances (tetrachloromethane, chloroform, tetrachloroethylene) and the group of ionic
liquids fulfilled the KIs and were assessed in detail (technical, economic, environmental,
toxicological parameters) in Chapter 5. Even though detailed study of the current known
technologies for caprolactam production was made, no suitable technology meeting the KIs for
technical and economical (by-product of a fertilizer) demands was found. Therefore no technology
was assessed in Chapter 5.
The conclusion of the analysis of alternatives (Chapter 6) summarizes all knowledge and
information on possible alternatives to TRI in the production process of caprolactam in SPOLANA,
a.s.
Conclusions summarised in the Table 1 proved that no suitable alternative to TRI was found.
From the technology point of view another fact had to be considered. Replacing the
trichloroethylene-based extraction process at SPOLANA, a.s. site with any kind of substances
mentioned above (if suitable) would require at least the following assumed modifications, possibly
other changes in consequences (in concentration increasing stage, waste water treatment
technology…):




Change (rebuild) in the extraction of the crude lactam unit,
Change (rebuild) in the extraction of distillation residues from rectification unit,
Change (rebuild) in the extraction of sulphate liquors unit,
Change (rebuild) in the regeneration solvent.
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ANALYSIS OF ALTERNATIVES
Table 1: Overall conclusion of possible alternatives assessed
Substance
physicalchemical
parameters
toxicological
risks
environmental
risks
trade
availability
economic
parameters
conclusion
not acceptable
not acceptable
well
available
20 % more
expensive
than TRI,
acceptable
Not suitable, dangerous to the ozone layer
well
available
Acceptable
Not suitable, environment pollution into waste
water, long-term toxicity represents
a considerable risk to health
Tetrachloromethane
Suitable
Chloroform
Suitable
not acceptable
not acceptable
Tetrachloroethylene
Suitable
not acceptable
acceptable
well
available
Acceptable
Not suitable, suspected carcinogen
ionic liquids
lack of
information
lack of
information
lack of
information
insufficient
availability
not
acceptable
Not suitable to replace, lack of information,
insufficient availability and high price
It was not possible to determine the extent of changes that would be necessary to make according to the chosen possible alternative. It may be
estimated that a minor reconstruction of a facility could cost millions of €, whereas more extensive modifications of technology could cost up to
tens of millions of €.
A loss of turnover had to be taken into account. Within production of caprolactam based on the technology with extraction solvent
trichloroethylene by-products are produced, which generate the main income for SPOLANA, a.s. Loss of incomes from these by-products would
cause serious economic problems for the producer.
It should be noted that the “fault time” can occur not only due to a fault, but also due to absence of valid permits for example. Moreover, imports
of an extraction solvent from countries outside the EU means at least the additional cost of registration under REACH.
Among the costs associated with the introduction of alternative solvent it is also necessary to count the costs of laboratory research and pilot
testing or transformation of manufacturing equipment (see Section 6.2.2.). It would take about at least 14 years of research to identify a suitable
alternative (if any) if started in 2015. It is evident that SPOLANA, a.s. cannot afford to test alternative production in working conditions, as this
could have destructive consequences in the current situation.
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ANALYSIS OF ALTERNATIVES
According to research and development plan (see Section 6.2.2) and following duty resulting from a change in technology (use of alternative
substance) the Applicant applies for 12 years of a review period.
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ANALYSIS OF ALTERNATIVES
2.
ANALYSIS OF SUBSTANCE FUNCTION
The aim of this chapter is to give detailed and precise information on functions of trichloroethylene
(TRI) used in process of caprolactam production in SPOLANA a.s.
The chapter 2 starts with general information about TRI itself. As the assessed use of TRI is
production of caprolactam it is essential to give an overview about caprolactam, its physical and
chemical properties, possible ways of its production, its role on market, and others, too.
The third part of the chapter is dedicated to production process of caprolactam in SPOLANA a.s.
This part is focused on the extraction process where TRI is used as an extraction reagent
(dissolvent).
2.1
General information about trichloroethylene
TRI is a widely used industrial solvent. It is volatile, colourless liquid with ethereal (chloroformlike) smell (WHO air quality guidelines for Europe, 2nd edition, 2000).
Chemical formula C2HCl3 and chemical structure are shown in Figure 1.
Figure 1: Chemical formula and structure of TRI (Kim, 2007).
2.1.1
Physical–chemical properties of trichloroethylene
This chapter is dedicated to physical–chemical properties of TRI. As all of those properties can be
considered well-known from the background documents published by ECHA these documents
dedicated to physical–chemical properties are listed in chapter 6 Reference list. For more detail
information see also Annex 1 with the ID card of TRI.
Background document for trichloroethylene. (20.12.2011) ECHA

European Union Risk Assessment Report - Trichloroethylene. (2004) European Commission Join Research
Centre

For others see the reference list (chapter 6)
2.1.2
Production of trichloroethylene
In 1990, estimated production of TRI was 131 kilotons in Western Europe, 79 kilotons in the USA,
and 57 kilotons in Japan, compared to 210, 121 and 82 kilotons, in 1980, respectively (WHO air
quality guidelines for Europe, 2nd edition, 2000). The estimated annual consumption in these areas
is 65-103 % of the production levels. European production of TRI is between 51,000 and
225,000 tonnes/annum (data from 1996) (European Commission – Joint Research Centre, 2004).
There are five companies producing or importing TRI into the EU (Registred substances-ECHA).
Production at a typical plant ranges from 1,000 to 50,000 tonnes/annum. Information on the balance
between production and import is not available. Afew companies also recycle a relatively small
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ANALYSIS OF ALTERNATIVES
amount of TRI. In the EU use of TRI has declined by over 50 % since the mid 1970s. This decline
is a result of improved operating conditions leading to better solvent recovery and the use of other
chlorinated solvents for metal cleaning (European Commission – Joint Research Centre, 2004).
According to the IUCLID data provided (data related to the period 1993-1996, no current data is
available), European production of TRI is between 51,000 and 225,000 tonnes/annum. However,
more recent information from the European Chlorinated Solvents Association (ECSA) indicates that
production of TRI in the EU was 138,000 tonnes per annum in 1996. Of this, 77,000 tonnes were
sold into the EU for uses other than as a chemical intermediate (see below). The remaining
61,000 tonnes were either exported or used as an intermediate but no breakdown between export
and intermediate use is available for 1996. More recent information (ECSA, 2001) indicates
a similar level of sales within the EU to that for 1996 with use as an intermediate of approx.
45,000 tonnes. (European Commission – Joint Research Centre, 2004).
2.1.3
Uses of trichloroethylene
The main use of TRI is vapour degreasing of metal parts. TRI is also used as an extraction solvent
for greases, oils, fats, waxes, and tars, as a chemical intermediate in production of other chemicals,
and as a refrigerant. Another use of TRI is in consumer products such as typewriter correction
fluids, paint removers/strippers, adhesives, spot removers, and carpet-cleaning solutions. TRI was
originally used as an anaesthetic for surgery prior to 1977 (EPA, rev. 2000)(Public Health
Statement Trichloroethylene, 1997).
According to industry sources, 82 % of TRI is sold and used for metal degreasing, 9 % in
adhesives, 6 % is for consumer uses, and 3 % is for other uses, e.g. extraction, leather preparation,
pharmaceuticals (see Table 1). 61,000 tonnes is exported or used as a feedstock chemical
intermediate. This tonnage is not included in the figures below (European Commission – Joint
Research Centre, 2004),(Institut pro perspektivní technologické studie, 2002), (Alessi, Penzo,
Slater, & Tessari, 1997).
Table 2: Uses of TRI sold into the EU market (European Commission – Joint Research Centre,
2004).
Use
Metal degreasing
vapour degreasers
Adhesives
Consumer uses
Others
Percentage of total sales
Quantitym used
(tonnes/year)
82
63,140
9
6
3
6,930
4,620
2,310
in
2.2
General information about caprolactam
2.2.1
History of ε-caprolactam synthesis
E-caprolactam (2-oxohexamethylenimine, hexyhydro-1H-azepin-2-one) is known since
19th century. In 1899, S. Gabriel and T. A. Maas synthesized ε-caprolactam by cyclization of
ε-aminocaproic acid. O. Wallach synthesized caprolactam by Beckmann rearrangement of
cyclohexanone oxime. The most important step in history of caprolactam was the discovery of a
German scientist P. Schlack (IG Farbenindustrie), who prepared the first spinnable polymer by
polycondensation of caprolactam – polycaprolactam or POLYAMIDE 6 or NYLON 6. After that,
commercial interest in caprolactam has increased and the caprolactam has gained importance.
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A Czech scientist, Otto Wichterle worked on polymerization of caprolactam in secret during World
War II and managed to draw a thin thread out of 5 grams of polycaprolactam. The name of the
original Czech polyamide WINOP (according to the research team Wichterle – Novotný –
Procházka) was later changed to SILON (RAAB), (RITZ, 2002).
2.2.2
Physical – chemical properties of ε-caprolactam
2.2.2.1 Physical properties of ε-caprolactam
E-caprolactam is white, hygroscopic, crystalline solid substance, which is sold as molten liquid,
solid tablets or as flakes. Caprolactam is used as precursor of polyamide NYLON 6 and it has some
use in making coatings, synthetic leather, plasticizers, and paints. Its structure is shown below
(Figure 2):
Figure 2: Structure of caprolactam.
Basic physical properties of ε-caprolactam are summarized in Table 3. Caprolactam is soluble in
polar and aromatic solvents and slightly soluble in high molecular mass aliphatic hydrocarbons, and
water.
Table 3: Basic physical properties of ε-caprolactam
Use number: 1
Physical quantity
Value
Unit
Relative molecular mass Mr
113.16
1
Melting point
69.2
[°C]
Boiling point at 101,3 kPa
268.5
[°C]
Density at 80 °C
1.0135
[kg/l]
Viscosity at 80 °C
8.82
[mPa.s]
Specific heat
2.135
[kJ.kg-1.K-1]
Heat of fusion
123.5
[kJ/kg]
Heat of polycondensation
138
[kJ/kg]
Heat of vapourization at 268 °C
481
[kJ/kg]
Vapour pressure 268 °C
101.3
[kPa]
Flash point
139.5
[°C]
Ignition temperature
375
[°C]
Lower explosion limit (at 135 °C)
1.4
vol. %
Upper explosion limit (at 180,5 °C)
8.0
vol. %
Thermal conductivity coefficient (76 -183 °C)
0.5
kJ.m-1.h-1.K-1
Coefficient of expansion volume (80–90 °C)
0.00104
K-1
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2.2.2.2 Chemical properties of ε-caprolactam
The most important chemical property of caprolactam is its ability of polymerization. A ring is
hydrolyzed at 260-270 °C. Linear polymer chains are formed by polycondensation. E-caprolactam
also reacts directly by polyaddition with polymer chains. These reactions lead to equilibrium
between the polymer and caprolactam, when 90 % of caprolactam is converted to polymer.
Caprolactam can also be polymerized by anionic polymerization at low mature contents, preferably
less than 100 ppm. A catalyst and co-catalyst systems are necessary. The reaction temperature is
lower than during hydrolytic polymerization.
2.2.3
Synthesis of ε-caprolactam
Over 95 % of global commercial caprolactam production is either from cyclohexane (from benzene)
or phenol via cyclohexanone and the cyclohexanone oxime. The remaining less than 5 % of
installed caprolactam capacity is via the cyclohexane photonitrosation process, which goes directly
from cyclohexanone to the oxime, or the cyclohexanecarboxylic acid nitrosation in presence of
sulphuric acid (RITZ, 2002; PERP Program – Caprolactam, 2011).
2.2.3.1 Synthesis of ε-caprolactam from cyclohexanone
Cyclohexanone is an essential reaction component in synthesis of caprolactam. The following
describes some frequently used methods of its conversion to caprolactam. Cyclohexanone is
produced by a catalytic reaction of phenol and hydrogen. Cyclohexanol and residues (tar) are
by-products of this reaction. Cyclohexanol is converted to cyclohexanone together with
a simultaneous formation of hydrogen. Tar is combusted to generate heat. The waste gas containing
the hydrogen and methane is burned as local fuel or intended for disposal.
Cyclohexanone reacts with hydroxylamine sulphate, produced by the Rashig process, to form the
cyclohexanone oxime and the resulting acid, which is neutralized using NH3 (Figure 3). The
product stream is decanted and the aqueous sulphate solution sent to the crystallization section for
salty recovery. The oxime is then sent to isomerisation reactor where it is transformed into
caprolactam via Beckmann rearrangement with oleum and the acid is neutralized using aqueous
ammonia. From the rearrangement section two liquids phases result: an aqueous solution rich in
ammonium sulphate (35-40 %) containing 1-1,5 % caprolactam, and crude caprolactam containing
about 25-30 % water and a small amount (≤ 1,5 %) of ammonium sulphate. Both streams also
contain organic and inorganic impurities. The two main products are required to be very pure
caprolactam and pure ammonium sulphate. Caprolactam is recovered from both of these phases and
partly purified by solvent extraction (PERP Program – Caprolactam, 2011), (Institut pro
perspektivní technologické studie, 2002), (Alessi, Penzo, Slater, & Tessari, 1997).
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Figure 3: Caprolactam via cyclohexanonoxim (PERP Program – Caprolactam, 2011).
2.2.4
Use of ε-caprolactam
As mentioned in Section 2.2.2.2 the most important property of caprolactam is its ability of
polymerization. This property is used in production of polyamides type AB, where the letter ”A“
means amino group and the letter ”B“ means carboxylic group. Both of these groups are part of the
same monomer molecules.
The reaction is catalysed by water, which starts to open a caprolactam ring. The formed linear
molecule reacts with more caprolactam, producing a dimer. The reaction continues between the
growing polymer and more caprolactam. The scheme of polymerization of polyamide is shown in
Figure 4 (Production of polyamide 6) (NEISER, 1988).
Figure 4: Polymerization of caprolactam (BAT in production of polymers, 2006).
Polymerization may be carried out in two stages, with an increased rate of ring opening in the first
stage. This makes the polymerization quicker, and increases the output, and therefore fewer reactors
are required. Typically, a single stage reactor has up to 130 tonnes output per day, whereas a two-
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ANALYSIS OF ALTERNATIVES
stage process can reach to 300 tonnes per day (CIEC, Greener Indrustry – Production of NYLON,
CIEC, 2013)
2.2.4.1 Properties of polyamides
According to physical-chemical properties, polyamides can be classified into a group of
thermoplastic polymer materials. These materials are more or less solid at room temperature and
can be melted by heat.
Polyamides may be readily formed. They are hard, brittle, and resistant to abrasion, shrinkage, and
heat. Polyamides are insoluble in common solvents (alkaline, organic solvents) and are resistant to
petroleum products. Conversely, hot phenol, formaldehyde, ultraviolet light, and mineral acids
destroy polyamides. Stretching improves the strength of the fibres – during processing to a fourfold
increase (NEISER, 1988; BAT in production of polymers, 2006).
2.2.4.2 Polyamide 6 – NYLON
The most widespread types of polyamides are NYLONs, which have various properties depending
on the feed stocks. NYLON was the first synthetic semi-crystalline plastic, the first man-made fibre,
and the first engineering plastic.
Polyamide 6 is processed into fibres or moulding, casting or others plastics processing methods.
They can be readily mechanically machined, e.g. turning, cutting, milling, etc. (NEISER, 1988;
BAT in production of polymers, 2006).
2.2.4.3 Continual polymerization of POLYAMIDE 6
Caprolactam is typically converted to POLYAMIDE 6 in a batch process, heating with water and
acetic acid (to regulate the length of the polymer chain produced) for 12 hours at about 350 °C.
However, continuous production is always preferable. The reaction vessels used are designed to
allow more precise temperature control, with heat being removed and recycled. This means that the
operating temperature does not exceed 280 °C but a higher percentage of caprolactam is
polymerised during the 16 to 20 hours spent in this stage of the process. Temperature is maintained
at a constant value by using a diathermic oil (the heat transfer fluid) to heat the reactor.
Since not all the caprolactam polymerizes to polyamide, the formed granules are scrubbed in the
counter current extractor with demineralised water. After the wash the demineralised water contains
a high concentration of caprolactam.
This demineralised water is lead to the thickening line for regeneration of caprolactam and the
remaining demineralised water is reused in the process.
Washed pellets enter the last reactor where they dry in stream of hot nitrogen. Finally, the dry
granules are conveyed to storage tanks.
The Figure 5 shows a simplified block diagram of the process. (BAT in production of polymers,
2006; CIEC, Greener Indrustry – Production of NYLON).
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ANALYSIS OF ALTERNATIVES
Figure 5: Block diagram of the continual process of POLYAMIDE 6 distribution (BAT in
production of polymers, 2006).
2.2.5
Global production and consumption of ε-caprolactam
2.2.5.1 Global production of an ε-caprolactam
The United States, Japan, Russia, Belgium, Netherlands, Italy and Germany are the main producers
of caprolactam. With the exception of France and the United Kingdom virtually all industrialized
nations possess caprolactam facilities of their own.
Over 3 million tons of caprolactam were produced every year since 1986. In 2004, the World
production of caprolactam was more than 4 million tons each year. The first place in the production
of caprolactam was divided between Europe and Asia. This pie chart (Figure 6) shows the
percentage of each country’s production of caprolactam in 2012.
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Figure 6: Global production of caprolactam in 2012 (Caprolactam (CPL): 2014 World Market
Outlook and Forecast up to 2018, 2014)
2.2.5.2 Consumption of ε-caprolactam
Global caprolactam operating rates reached 90 % in 2010, improving sharply from depressed
markets in 2008 and 2009. Steady economic recovery and strong Asian demand in end-use markets,
particularly automotive (tire cords, air bags, engine components, exterior and interior trims),
contributed to a 10 % leap from 2009 to 2010 and continuing into the first half of 2011. Production
levels slowed, however, in the second half of 2011 due to diminishing economic activity and
softening demand. The following pie chart shows world consumption of caprolactam (Figure 7):
Figure 7: World Consumption of Caprolactam in 2010 (Caprolactam, 2011).
About 90 % of all caprolactam produced is processed to NYLON 6 filaments, fibres, and resins.
NYLON 6 fibres are used in textile, carpet and industrial yarn industries. NYLON resins are used as
engineering plastics, with application in the automotive industry, specialty film packaging for food,
and wires, and cables. Nearly 10 % is used for production of plastics. Only small quantities are used
for chemical syntheses. Examples of well-known commercial products are brush bristles, textile
stiffeners, film coatings, synthetic leather, plastics, paint vehicles, and cross-linking for
polyurethanes. The distribution of global caprolactam demand by end use is illustrated in Figure 8
(Mettu, 2009; Caprolactam, 2011)
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ANALYSIS OF ALTERNATIVES
Figure 8: Global caprolactam demand by end use, 2005 (Mettu, 2009)
E-caprolactam is widely traded. Western Europe, Central and Eastern Europe, Japan, and the United
States send significant quantities to China, Taiwan and the Republic of Korea. China will remain
a major importer of caprolactam even with proper new capacity to begin operation over the next
several years. Antidumping duties placed on import of caprolactam and NYLON chips from United
States, EU countries, Taiwan, and Russia over the next five years will have little effect on levels of
imports.
Other Asia countries (excluding China and Japan) are among the most caprolactam-consuming
region in the world at approximately 30 % of global demand in 2010.
"The increase of import of NYLON 6 textile fibers to Asia, developments of automotive industry,
plastics, and electronics manufactures located in industrialized regions of North America, Western
Europe, and Japan contributed to growth of caprolactam production"
Regional demand growth will only be approximately 1 % per year during the forecast period (PERP
Program – Caprolactam, 2011).
2.3
Caprolactam production process in SPOLANA a.s.
2.3.1
Basic information about SPOLANA a.s.
SPOLANA a.s., based in Neratovice, Czech Republic, is one of significant chemical companies of
the Czech industry.
Its main activity is chemical production of:

Ethylene based products (PVC)

Base material for polyamide fibers and other plastics (caprolactam)
 Inorganic substances (NaOH, chlorine, HCl, H2SO4, (NH4)2SO4, brine)
Production of caprolactam takes the biggest part of SPOLANA a.s. business and 99 % of the
caprolactam production is exported. 10.1 % of the production is exported to the EU, 15.7 % to
America and 73.4 % to Asia. As mentioned in chapter 2.2.4 caprolactam is a basic material for
polyamide 6 production, and plays a big role in textile and plastics production.
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2.3.2
Caprolactam production process in SPOLANA a.s.
The production process in SPOLANA a.s. is based on synthesis of caprolactam from cyclohexanone
(see 2.2.3.1). The process steps of the caprolactam production are as follows (SPOLANA, 2004):
1. Oximation – cyclohexanone oxime is produced as an intermediate product with
concentration of 96 %. It is a direct reaction of cyclohexanone with hydroxylamine sulphate
in the oximation cascade of mixed reactors. The sulphuric acid that arises is neutralised by
liquid and gaseous ammonia. In this reaction must be pH, temperature and pressure
controlled.
2. Beckmann rearrangement – the preparation of raw caprolactam proceeds by the
Beckmann rearrangement in an acid non-aqueous environment in the rearrangement reactor.
The reaction heat is led away by cooling water in the system into the heat exchanger. In this
reaction must be temperature and pressure controlled.
3. Neutralization – caprolactam is isolated from a solution of sulphate acid during a so-called
desaltification (neutralization of acid by ammonia water). This operation leads to creation of
a ternary system water-caprolactam-ammonium sulphate. Out of those two phases: 72 % soil
of caprolactam in the water () and 40 % soil of ammonium sulphate in water with 0.8 %
caprolactam are separated. A lactam layer is continuously produced. After the extraction, the
sulphate layer is connected with ammonium sulphate from oximation step and this mixture
is led off to the production line ammonium sulphate.
4. Extraction – this process is done in two steps. The caprolactam is extracted from raw
lactam water solution into the TRI in the first step. The second step is based on extraction of
caprolactam from a TRI extract back into the demi-water. TRI is recycled and partially
regenerated by distillation.
5. Concentration – caprolactam soil of 35 to 38 % is concentrated in a two-step process
(atmospheric pressure) or in a 4-step process (1st pressure, 2nd – 3rd vacuum, and 4th
atmospheric). The output is caprolactam of 92 % concentration.
6. Rectification – Concentrated caprolactam is stripped into a 6-step rectification process,
where caprolactam is dried by separation of low or high boiling impurities. The final
product is taken from the 4th and 5th step of rectification.
7. Final product – So-called melted caprolactam is stored in expedition tanks. From those it is
drawn to the tankers or it goes to a granulation process. After crystallization the final
product is packaged into 25 kg sacks in the packaging and palletization line. The transport of
such product is done by rail, containers or trucks directly to the customers.
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ANALYSIS OF ALTERNATIVES
The production of caprolactam in SPOLANA a.s. is connected with the formation of byproducts such as a sulphuric acid and ammonium sulphate. Associated production of
sulphuric acid is the production of oleum. These by-products have a crucial role in the
economics of SPOLANA a.s. The production of 1 ton of caprolactam means production of
4 tons of ammonium sulphate as a by-product. For more information see SEA chapter 2.2.3.3.
Table 2 and Table 3.
Figure 9: The production process SPOLANA a.s. (SPOLANA, 2004).
2.3.3
Goal of TRI in SPOLANA a.s. caprolactam production
Based on the section 2.3.2 TRI is used for the extraction of caprolactam in the extraction step of
production. Caprolactam is extracted into TRI in the first step of extraction. In this production step
caprolactam is stripped to the bottom part of the extractor. At the same time TRI is stripped in too.
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ANALYSIS OF ALTERNATIVES
Raffinate of caprolactam falls into the separator. Raffinate with dissolved TRI is loaded from the
separator into the stripping column. After the stripping process flows the raffinate to the waste
water sewerage. Extract of caprolactam in TRI with the concentration 19 – 21 % is then cleaned by
demineralized water – cleaning step for dirt and water phase, the water phase is separated and then
the extract is led into the second step of the extraction. Caprolactam is re-extracted into the
demineralized water. Solution of 36 to 38 % caprolactam falls into the other separator where TRI
separates. The extract of caprolactam goes into concentration step of production, during which TRI
containing 0.02-0.1 % of caprolactam is partly cleaned and it is lead into the tank part for impure
TRI. 40-60 % of TRI is then stripped to the re-generation; the rest of TRI (mixed with the
regenerated TRI) is stripped into the first extraction step again. The use of TRI is a closed loop that
has to be refilled by approx. 150 tons/year. The total amount of TRI present in this closed loop is
315 tons (SPOLANA, 2004).
To satisfy customer demand for the quality of caprolactam (see Table 4, it is important to have
a stable production process. The stable process is guaranteed by technology and its setting and by
chemicals used in the process and their properties. To gain stable production process of
caprolactam, certain physical-chemical properties of the dissolvent (TRI) are essential in the
extraction part of the process:

density

non-miscibility with water

non-flammability – for the security reason
Table 4: Caprolactam quality specifications (SPOLANA, 2012)
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ANALYSIS OF ALTERNATIVES
3. ANNUAL CONSUMPTION OF TRI
The system of SPOLANA, a.s. production is closed. The maximal amount of TRI used in the
system is 315 tons. The long term target of SPOLANA, a.s. is to decrease and optimize the
consumption of TRI.
The decrease of the TRI use to produce 1 ton of caprolactam was 10 times lower in 2013 than in
1974 (see Figure 10).
Figure 10: The consumption of TRI in the long term period
Based on the data shown above it is more that significant that in the long term point of view
SPOLANA, a.s. devoted a big effort to minimize its impact to all risks: to human health,
environmental risks, and sustainability by optimizing the technology, and the process of
caprolactam production. The process is stable and the amount of TRI used per 1 ton of caprolactam
is stable since 2005.
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ANALYSIS OF ALTERNATIVES
4. IDENTIFICATION OF POSSIBLE ALTERNATIVES
4.1
Description of efforts made to identify possible alternatives
4.1.1
Research and development
SPOLANA, a.s. did its internal research to replace TRI in the past. The main solvents assessed in
this research were benzene and toluene and other solvents such as 1,2-dichloroethylene,
tetrachlormethane, 1,1,1-trichloroethane, tetrachloroethylene, and chlorobenzene were assessed too.
This research proved that there is no suitable solvent that might replace TRI in the current
technology used (change of high of colones, etc.). In case the new solvent was used, the demand for
the technology rebuilt would be needed – the new extractor has to be projected based on the
physical-chemical properties of the solvent. Physical-chemical properties of 1,2 di-chloroethylene
and chlorobenzene were the closest to the properties of TRI. The conclusion of the study was that
following research should focus on the design of extraction models based on the various properties
of 1,2-dichloroethylene and chlorobenzene, tetrachloroethylene, etc. The affinity to caprolactam and
impurities should be taken into the consideration in the future research.
As the research of the possible alternative is not up to today’s knowledge, new data research and
analyses had to be done for AOA for authorization process, based on the new knowledge of
caprolactam production in recent decades.
4.1.2
Data searches
The methodology for data search was divided into the two parts. Database was identified for the
data study to obtain alternative substances and technologies to TRI replacement (see
Table 5).
The first part of the study focused on the possible alternatives of substances that might be used for
caprolactam production instead of TRI in the current production line in SPOLANA, a.s. (extraction
step). See the outcome in section 4.1.2.1.
The second part of the study focused on the alternative technologies to the current one in
SPOLANA, a.s. that are used to produce caprolactam. See the outcome in the section 4.1.2.2.
Table 5: Databases for the alternative substances and technologies to TRI
Source
Google
Science direct
Google Books
EspaceNet
Google Patent
Search
Patent lens
Details
https://www.google.com
http://www.sciencedirect.com
http://www.google.com/advanced_book_search
http://www.epo.org/searching/free/espacenet.html
http://www.google.com/advanced_patent_search
Description
Search engine
Scientific articles
Books
Patents
Patents
http://www.patentlens.net/daisy/patentlens/patentlens.html
Patents
SureChem
https://www.surechem.com/
Patents
IPEXL
http://www.ipexl.com/shop/19-ipexl-patent-search-standard-edition.html
Patents
US Patent and
Trademark
Office
http://www.uspto.gov/
Patents
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ANALYSIS OF ALTERNATIVES
Source
China Patent
Trademark
Office
Scirus
Details
http://www.chinatrademarkoffice.com/index.php/ptsearch
Description
Patents
http://www.scirus.com
Science direct
ESIS
http://www.sciencedirect.com
http://esis.jrc.ec.europa.eu
ChemIDPlus
http://chem.sis.nlm.nih.gov/chemidplus
US EPA
Substance
Registry Services
TOXNET
http://semanticommunity.info/EPA/EPA_Substance_Registry_System
Scientific search
engine
Scientific articles
Chemical substance
inventory
Chemical substance
inventory
Chemical substance
inventory
ChemSpider
http://www.chemspider.com
ChemNet
http://www.chemnet.com
Chemical Book
http://www.chemicalbook.com
TRC
http://www.trc-canada.com/index.php
NIOSH
http://www.cdc.gov/NIOSH
ECHA
Pubchem
http://echa.europa.eu/web/guest/information-on-chemicals/registeredsubstances
http://pubchem.ncbi.nlm.nih.gov
Sigma-aldrich
http://www.sigmaaldrich.com
Chemical
Abstracts
Google Scholar
http://pubs.acs.org/
http://google.scholar.com/
Human health and
environmental data
Properties of
chemical substances
Properties of
chemical substances
Properties of
chemical substances
Properties of
chemical substances
Properties of
chemical substances
Properties of
chemical substances
Properties of
chemical substances
Properties of
chemical substances
Abstracts from
chemical literature
Scientific articles
Google Patents
http://google.patents.com/
Patents
http://toxnet.nlm.nih.gov
4.1.2.1 Data searches – substances1
A detailed study dedicated to all possible alternatives to TRI that might be used for caprolactam
production was carried out.
Key words used for alternative substances search:
“alternative production of caprolactam”, “caprolactam alternative for TRI”, “caprolactam
production”, “preparing caprolactam”, “synthesis of caprolactam”, “solvent for isolation of
caprolactam”, “preparing caprolactam with trichloroethylene”, “extraction of caprolactam”,
“extraction from trichloroethylene”, “extraction”, “extraction with caprolactam”, “extraction with
green solvent”, “extractant for caprolactam”, “extraction from trichloroethylene”.
Key words used for alternative solvents found to conduct a detailed study of properties:
1List
assessed as possible alternatives – substances see chapter Table 6
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ANALYSIS OF ALTERNATIVES
“tetrachloroethylene”,
“tetrachloromethane”,
“chloroform”,
“ionic
liquids”,
“1,2dichloroethane”,“1,1,2-trichloroethane”, “benzene”, “ligroine”, “2-heptanone”, “nitrobenzene”,
“1,1-dichloroethane“,“1,1-dichloroethylene”,“1,2-dichloroethylene”,“1,1,1-trichloroethane”,
“diethylether”, “cyclohexanol”, “2-methylcyclohexanol”, “methylcyclohexane”, “octanol (mixed
isomers)”, “cyclohexene”, “toluene”, “xylene (mixed isomer)”, “alkyl phenols”, “n-hexane”, “nheptane”,
“2-ethylhexanol”,
“1-heptanol”,
“bis-(2-ethylhexyl)
hydrogen
phosphate”,
“dichloromethane”, “CO2 supercritical”, “cyclohexane”.
Additional information sources for alternative substances search2:
2For

Ritz, J., Fuchs, H., Kieczka, H., & Moran, W. C. (1986). Caprolactam. V W. Gerhatz,
Ullmann’s Encyclopedia of Industrial Chemistry (pp. 31-51). Weinheim: VCH.

Hansch C., Leo A., Hoekman D., Exploring QSAR, Hydrophobic, Electronic, and Steric
Constants, ACS Professional Reference Book, Washington DC (1995)

Horvath A., Getzen F.W., Maczynska, IUPAC-NIST Solubility Data, Series 67,
Halogenated Ethanes and Ethenes, Journal of Physical and Chemical Reference Data, 28,
pp. 395-507 (1999)

Večeřa M., Gasparič J., Churáček J., Borecký J., Chemické tabulky organických sloučenin,
Státní nakladatelství technické literatury (SNTL), Praha (1975)

Funasaki N., Hada S., Neya S., Prediction of retention times in reversed-phase highperformance liquid chromatography from the chemical structure, Journal of
chromatography, 361, pp. 33-45 (1986)

Proposal of identification of a substance as a CMR, PBT, vPvB or a substance of an
equivalent level of concern, ECB – Summary fact sheet, PBT working group, List No. 55
(available
1.
May
2014
at:
http://esis.jrc.ec.europa.eu/doc/PBTevaluation/PBT_sum055_CAS_27193-86-8.pdf)

Brooke D., Mitchell R., Watts C., Dungey S., Environmental risk evaluation report: paraC12-alkylphenols (dodecylphenol and tetrapropenylphenol), Environment Agency, Bristol,
United
Kingdom
(2007)
(available
1.
May
2014
at:
https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/290856/scho0
607bmvn-e-e.pdf)

Vohlídal J., Julák A., Štulík K., Chemické a analytické tabulky, Grada Publishing, Praha
(1999)

Boublík T., Fried V., Hála E., The Vapour Pressures of Pure Substances, Elsevier,
Amsterdam (1984)

Yalkowsky S.H., Dannenfelser R.M., AQUASOL database of aqueous solubility, version 5
(PC version), College of Pharmacy, University of Arizona, Tucson (1992)

The Merck Index - An Encyclopedia of Chemicals, Drugs, and Biologicals. O'Neil M.J.
(editor), Royal Society of Chemistry, Cambridge, UK, p. 17 (2013)
detail informationaboutreferencesseechapter 7 Reference list
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4.1.2.2 Data searches – technologies
The detailed study dedicated to all possible technologies that might be used for caprolactam
production was carried out. It contains three parts of outputs. Two of them are current technologies
used by industry. The third part is concerned with laboratory scale of caprolactam production. The
study claims that practically all commercial caprolactam production globally is based on aromatics
feedstocks:
Most of the world’s caprolactam production is based on the reactions of cyclohexane (from
benzene) or cyclohexane / cyclohexanone oxime (from phenol). The remaining part of the
production capacity, about 5 %, use different technology. For example, Toray uses for the
production of caprolactam cyclohexanone photonitrosation process that is based on the formation
cyclohexanone oxime from cyclohexanone. The SNIA Viscosa utilizes toluene as feedstock and
proceeds via oxidation-hydrogenation-nitrosation (Heese, 2011)
This aromatics-based technology, which is currently the only actual method employed for
commercial production, is mature and consequently there have been a few developments noted in
the last five years.
The study of possible alternative technologies of caprolactam production is divided into three parts:

Synthesis of caprolactam from cyclohexanone oxime (see description of technologies below
in this chapter),

Synthesis of caprolactam without cyclohexanone oxime as an intermediate product (see
description of technologies below in this chapter),

Study focused on capraloctam production in laboratory scale (see description of
technologies below in this chapter).
The third part of this study focused on experiments in laboratory scale may serve as an inducement
for processing study in the future research in SPOLANA, a.s. (see This approach expects changes of
the current technology. Detailed study of all possible technologies to produce caprolactam has been
carried out. The base of the study (Annex 2)
Key words used for alternative technologies search3:
“alternative production of caprolactam”, “caprolactam production process”, “caprolactam from6aminocapronile”, “honeywell phenol process lactam”, “Teijin 2-cyklohexanone”, “preparation of
lactam”, “method making lactam”.
Additional information sources for alternative technologies search 4:

Ritz, J., Fuchs, H., Kieczka, H., & Moran, W. C. (1986). Caprolactam. V W. Gerhatz,
Ullmann's Encyclopedia of Industrial Chemistry (pp. 31 - 51). Weinheim: VCH.
3For
information about technologies see the text below in this chapter
4For
detailed information about references see Chapter 6: Reference list
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4.2
Results of AoA research
More than over 200 references were assessed for the study about possible alternatives to
caprolactam production in SPOLANA, a.s. Thirty one potential alternatives of substances and
thirteen alternative technologies were found to assess. For selection of possible alternatives or
technologies that were found the key indicators (KIs) for SPOLANA’s process were determined.
4.2.1
Alternative substances
This approach presupposes the use of current technology of caprolactam production without
significant changes. Only TRI would be replaced. KIs to the alternative have to have determined
properties for this approach:

No SVHC substance – No risks would be mitigated by use of the SVHC substance.

Water solubility – Solubility in water is a key feature of alternative solvent as these liquids
should be used for extraction from/to water. Therefore, low solubility in water is crucial
property for course of the extraction process. In addition it is important parameter for
material losses via environment.

Density – The density of substance should be approximately 1.5 g/cm3. During extraction of
caprolactam density of the extract is reduced due to addition of the dissolved substance.
When density decreases to value close to 1 g/cm3, the two liquid phases will be separated
with difficulty or not at all.

Flammability – Use of flammable solvent brings change of technological scheme that
includes working with combustibles. Such technology brings an increased risk of fire and
therefore results in expenses for fire protection measure
For the results see Table 6 List of possible alternatives – Substances.
.
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Table 6: List of possible alternatives – Substances5
Green lines – substances meeting KIs (key indicators), possible alternatives are assessed in Chapter 4 of AoA, pink lines –SVHC or CMR substances, Yellow lines –
substances not meeting KIs criteria for physical or chemical properties.
5
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Based on the KIs 4 possible substances were identified (green lines). Those substances meeting
these KIs and are assessed in chapter 5 in more detailed way.
Four possible alternatives assessed in chapter 5:

Tetrachloroethylene – Tetrachloroethylene has lower solubility in water and the same
partition coefficient octanol/water as TRI. It is not classified as flammable. Its negative is its
classification as a possible carcinogen (Carc. 2 according to CLP) and a lack of data in
literature.

Tetrachloromethane – Carbon tetrachloride has lower solubility in water and higher
partition coefficient octanol/water then TRI. It is not classified as flammable. From
toxicological point of view it is classified as a possible carcinogen (Carc. 2) and is toxic by
prolonged exposure (STOT RE 1). Two patents and one paper were found on the topic of
extraction of caprolactam.

Chloroform – Chloroform is more than 7 times more soluble in water then TRI. It is also
classified as a possible carcinogen (Carc. 2) and can be dangerous in case of prolonged use
(STOT RE 2). Several patents and articles were found in literature.

Ionic liquids – There are many types of ionic liquids are still part of the laboratory
preparation rather than part of high-tonnage industrial production. Several ionic liquids
mentioned in the article on the extraction of caprolactam have better solvent ability to
caprolactam then benzene and toluene (Chen D.X., Ou Yang X.K., Wang Y.G., Yang L.Y.,
He Ch. H., Liquid – liquid extraction of caprolactam from water using room temperature
ionic liquids, Separation and Purification Technology, 104, pp. 263-267 (2013)). The
toxicological properties of ionic liquids have not been explored yet.
4.2.2
Alternative technologies
This approach expects changes of the current technology. Detailed study of all possible
technologies to produce caprolactam has been carried out. The base of the study (Annex 2) and as
proved in SEA chapter 2.3. “non-use scenario 1” it would not be possible to build up a totally new
technology (“green-field plant”) in the close future. Based on that fact KIs had to be set with respect
to use of the current technology and change (or replace) only the extraction step of the process
where TRI is used6. Therefore the feedstock has to be the same. Inseparable part of SPOLANA’s
caprolactam production is production of a by-product. This by-product (fertiliser) generates a large
part of SPOLANA’s incomes from business. It is more than advisable to keep this a part of their
business.
To set up a proper alternative technology to replace the extraction step of the process it was
essential to respect the fact that this technology does not use the substance that is placed in SVHC
list or it would be placed there due to its risk in the near future.
The conclusions from these facts KIs for alternative technology are:

6For
By-product – During this process a by-product for the same use as today´s arises (a
fertiliser), the amount of this by-product should be nearly the same to keep the business.
detailed information about the principles of technologies assessed see Appendix 2:
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
Traditional Beckmann rearrangements are used – Only extraction process needs to be
rebuilt.

Feedstock – Cyclohexanone.
Based on the KIs no possible alternative to the current one was identified (see Table 7).
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Table 7: List of possible alternatives – Technologies7
7Pink
lines – Technologies not meeting KIs for production.
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4.3
Consultations
During preparation and drafting of the AoA several consultations were held basically between the
company SPOLANA, a.s. as an applicant and the compiling consultant centre under the head of the
university VŠB-TU Ostrava.
As the initiative brainstorming meeting was held on 27th March 2014 to describe the process of
caprolactam production, the need to use TRI in the process, stakeholders of SPOLANA, a.s., etc.
This meeting set the boundaries for the following compilation of AoA. The cooperation between
SPOLANA, a.s. and the compiling company continued via e-mail and phone consultations, and 3
check days.
During those check days current status of AoA was discussed, key indicators to set up the possible
alternatives were discussed and given. Notes raised by the applicant were implemented. The next
meeting’s focus was to discuss and agree on a list of possible alternatives and technologies carried
out by the compiling company. The time for open discussion about the process and possible
alternatives had some space at this meeting– the production technician and the production engineer
were present during this meeting too. The outputs of these days were agreed on by both sites. The
third check day was dedicated to closing discussion about all outputs, outputs were agreed and the
public and confidential data were discussed and agreed. This gave the basic for public and
confidential AoA.
The responsible person of the applicant for chemical substances was present at meetings (e.g. court
of “Committee for chemical substances management”). The responsible person attended
education trainings to have the possibility to judge the outputs from the compiling company of
AoA. And to give proper data that the compilation of AoA needs. A meeting with another applicant
from Czech Republic that went through the application (authorization) process was organized.
The applicant had an opportunity to discuss the prepared AoA during the PSIS Webex meeting with
ECHA. This meeting took place online 24th June 2014.
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5. SUITABILITY AND AVAILABILITY OF POSSIBLE ALTERNATIVES
5.1
ALTERNATIVE 1: Tetrachloromethane
Tetrachloromethane is used as a solvent in laboratories and industry. It is also used as a reagent in
chemical synthesis, for example in preparation of alcylchlorides (Apell reaction). It was used as a
cooling medium for dry cleaning of fabrics and garments, for industrial degreasing, as a solvent in
paints, aerosol propellant gas or as an extinguishing agent in the past.
5.1.1
Name and other identifiers for the substance
The identity of tetrachloromethane is shown in the following Table 8:
Table 8: Identity of tetrachloromethane
Parameter
Value
EC number
200-262-8
CAS number
56-23-5
IUPAC name
Tetrachloromethane
Other names
carbon tetrachloride
Molecular formula
CCl4
SMILES notation
ClC(Cl)(Cl)Cl
Molecular weight
153.82
Molecular
structure
Source
Cl
Cl
Cl
Cl
Source:
The following
Table 9 summarises the available information on the physical-chemical properties of
tetrachloromethane. The information has been collected from the website of ECHA, Registered
substances.
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Table 9: Physical - chemical properties of tetrachloromethane
Property
Value
Source
Physical state at 20oC and 101.3 kPa
Liquid
1
Water solubility
0.85 g/ l
1
Boiling point
76.8 °C
1
Density
1.59 g/cm3
1
Vapour pressure
15.2 kPa (25 °C)
1
Partition coefficient (log)
Source:
2.83
1
1.
(ECHA, 2014)
Tetrachloromethane is already registered substance according to REACH regulation. The
classification is mentioned in the following table.
Table 10: Classification of tetrachloromethane
Registration
(self-classification) (ECHA, 2014)
Regulation (EC) No. 1272/2008
Hazard class and category
codes
Hazard
codes
statement
Acute Tox. 3
H301+H311+H331
Hazard class and category
codes
Hazard
codes
Acute Tox. 3
H301+H311+H331
Skin Sens. 1B
H317
Carc. 2
H351
Carc. 2
H351
STOT RE 1
H372
STOT RE 1
H372
Aquatic Chronic 3
H412
Aquatic Chronic 3
H412
Ozone 1
H420
Ozone 1
H420
5.1.2
dossier
statement
Technical feasibility for the applicant
The fundamental selected properties for assessment of alternative solvents were solubility in water,
toxicity, density, and flammability. The first property – solubility in water – is essential since that
solvent is used to extraction of caprolactam from/to water. Therefore, as low as possible miscibility
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with water is requested of the solvent. It affects not only extraction but also the solvent recovery
and quality of waste water.
It is necessary to know the toxicity to human health in order to evaluate the effects on human health
of the solvent. Of course, since toxicity is the reason for search of alternative solvent for
trichloroethylene. Summary of existing knowledge about toxicity of tetrachloromethane is
presented in registration dossier available on the ECHA website (ECHA, 2014). Partition
coefficient n-octanol/water, resp. its logarithm closely related with toxicity. Although it is
a physical-chemical property, it is used as a very important parameter in assessing especially the
long-term toxicity.
Density namely specific gravity is an important property in regard to technology. The existing
technology and the extraction device are based on the fact that the organic layer after separation is
located on the bottom.
Non-flammable solvent would result in significant simplification of the whole technology.
Apparatus, construction elements, electrical equipment, etc. would need not to be designed for
potentially explosive atmospheres, which would imply lowering the risk of a fire. Administrative
requirements are reduced too (for example fire protection measures pursuant to Directive
1999/92/EC on minimum requirements for improving the safety and health protection of workers
potentially at risk from explosive atmospheres). In this paper flammability is rated in accordance
with the CLP criteria.
Boiling point is not an essential property, but it is a useful subsidiary parameter. A low boiling point
means that the substance is light-volatile. High boiling point might cause problems for example in
the regeneration of the solvent (possibility of polymerization of caprolactam residues, working at
high temperatures, risk of an accident and casualty, selection of appropriate construction materials
etc.).
Comparison of the properties of tetrachloromethane and trichloroethylene are shown in Table 11.
Tetrachloromethane is less soluble in water than trichloroethylene and it has a higher density.
Table 11: Properties of tetrachloromethane and trichloroethylene
Property
Tetrachloromethane
trichloroethylene
water solubility (g/ l)
0.85
1.1
density (g/cm3)
1.59
1.46
log Kow
2.83
2.53
flammability
No
no
boiling point ( °C)
76.8
86.7
The properties mentioned above are well available and they were collected in order to compare
relevant properties of large group of solvents. Moreover, there are lots of other unknown properties
which affect technology. For example solubility of caprolactam in tetrachloromethane, composition
and properties of ternary mixture caprolactam-tetrachloromethane-water and their dependence on
temperature, any phase separation problems, effects of inorganic salts especially of ammonium
sulphate etc. Different solvent and modification of the extraction method can cause changing the
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composition and the quantity of impurities that strongly affect the quality of the final product.
Extraction process can be affected by the quality of available solvent (solvent can contain some
impurities, which can negatively affect the course of extraction or the quality of the extract).
The conditions of production cannot be reliably predicted with a sufficient precision, and thus the
expenses and the time frame for the alternative technology cannot be accurately evaluated.
5.1.3
Reduction of overall risk due to transition to the alternative
The main reason for finding a substitute for trichloroethylene is carcinogenicity. Trichloroethylene
is classified (among others) according to the table 3.1 of Annex VI of Regulation (EC) No.
1272/2008 as Carc. 1B (H350). This means that, for this substance, carcinogenicity to animals was
proved and carcinogenicity to humans is expected. Among serious health risks mutagenic properties
(Muta. 2 (H341)) should be suspected. As a proved carcinogen is this substance included in
Authorisation List (REACH, Annex XIV).
In comparison with trichloroethylene, tetrachloromethane is classified (among others) according to
the table 3.1 of Annex VI of Regulation (EC) No. 1272/2008 as a suspected carcinogen (Carc. 2
(H351)). According to the same Regulation tetrachloromethane is classified as STOT RE 1 (H372).
That means this substance causes serious damage to health by long-term exposure. This health
damage is usually reported for liver. The usual route of exposure is inhalation. As to the acute
toxicity, tetrachloromethane is more toxic than trichloroethylene via oral, dermal, and inhalation
exposure (classification Acute Tox. 3 (H301+H311+H331)).
Furthermore, tetrachloromethane is included in the Community Rolling Action Plan (CoRAP) for
substance evaluation as there are grounds of concern relating to human health/CMR, exposure/high
exposure for workers with regards to high aggregated tonnage. A decision has been taken according
to which the registrant is required to replenish its dossier with An Extended One Generation
Reproduction Toxicity Study (OECD 443). Reproductive toxicity assessment of tetrachloromethane
is not completed yet.
In terms of environment, tetrachloromethane is in the same hazard class and category as
trichloroethylene (Aquatic Chronic 3 (H412)). Tetrachloromethane is classified as ozone-depleting
substance (Ozone 1 (H420) in addition. Tetrachloromethane is more harmful to environment than
trichloroethylene.
In conclusion, it is evident that substitution of tetrachloromethane for trichloroethylene would not
cause reduction of risk, but rather the risk would be minimally the same or higher due to potential
of negative effect on the environment.
5.1.4
Economic feasibility
The assessment of economic feasibility of tetrachloromethane for SPOLANA, a.s. should take into
account the following cost elements:



Cost arising from the changed price of the solvent;
Cost arising from the modifications to the plant in order to start using tetrachloromethane
instead of trichloroethylene;
Loss of turnover from the production of by-products which could be produced at lower
quantity and/or quality if tetrachloromethane was used.
Cost element 1: Price of tetrachloromethane
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Publicly available sources have been searched for price of tetrachloromethane. Unfortunately the
only available data about the price were found on the website alibaba.com. Tetrachloromethane is
offered for prices 810-950 € per ton. Price of trichloroethylene is from 550 to 1,030 € per ton (TRI),
the mean value is approx. 734 € per ton. Cost of the solvent tetrachloromethane is about 20 %
higher. According to current economic status of SPOLANA, a.s. the increase of price of alternative
substance could have strong impact on the factory and its economy.
It is necessary to consider the costs of disposal of trichloroethylene. Disposal of one ton of
chlorinated solvents in hazardous waste incinerators costs at least € 250 per ton, total cost for
disposal 316 ton of trichloroethylene is 79.000 €. According to the current economic status of
SPOLANA, a.s. the increase in the price of alternative substance could have strong impact on the
factory and its economy (SEA chapter 2.2.3.3. Table 3).
Cost element 2: Cost of plant conversion
Replacing the trichloroethylene-based extraction process at SPOLANA, a.s. site with an alternative
solvent would require the following assumed modifications:
 Change (rebuild) in the extraction of the crude lactam unit,
 Change (rebuild) in the extraction of distillation residues from rectification unit,
 Change (rebuild) in the extraction of sulphate liquors unit,
 Change (rebuild) in the regeneration solvent.
Currently it is not possible to determine the extent of changes that would be necessary to make. It
may be estimated that a minor reconstruction of the device would cost millions of €, whereas more
extensive modifications of the technology would cost up to tens of millions of €.
Cost element 3: Loss of turnover
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5.1.5
Availability
Tetrachloromethane is registered as a substance manufactured in quantity 1,000-10,000 t/year.
There are seven producers at this tonnage volume who submit the registration dossier. It is possible
to find a number of other producers/distributors of tetrachloromethane using public available
sources (websites). Most of them are from countries outside the EU.
Table 12: Market availability of tetrachloromethane
Supply ability
(t/y)
Company
Location
Purity ( %)
Akzo Nobel Industrial Chemicals GmbH
Germany
-
> 1,000
CHS Epi, a.s.
Czech Republic
-
> 1,000
Germany
-
> 1,000
INEOS Chlorvinyls Limited
United Kingdom
-
> 1,000
Kem One IMMEUBLE SOLARIS
France
-
> 1,000
Solvay Chimica Italia S.p.A.
Italy
-
> 1,000
Solvay-Electrolyse-France S.A.S.
France
-
> 1,000
Tianjin Chengyuan Chemical Co., Ltd.
China
99.9
60,000
DOW DEUTSCHLAND
ANLAGENGESELLSCHAFT GmbH
Company Tianjin Chengyuan Chemical Co., Ltd. (alibaba1) offers tetrachloromethane for price
810-950 € per ton (availability 5,000 t/month).
When the total volume of solvent for extraction is less than 500 tons tetrachloromethane can be
considered as easily available.
5.1.6
Conclusion of suitability and availability of tetrachloromethane
Based on the information listed above it can be concluded that physical-chemical parameters of
tetrachloromethane are appropriate for the replacement of trichloroethylene. Tetrachloromethane is
non-flammable it has a higher specific gravity and low water solubility.
From a toxicological point of view, tetrachloromethane is not a positive carcinogen but it is
a suspected carcinogen. Unlike trichloroethylene tetrachloromethane it is classified as a substance
that causes damage to organs through prolonged or repeated exposure and it is more acute toxic (in
oral, dermal and inhalation route) than trichloroethylene. Reproductive toxicity is still in course of
evaluation.
Tetrachloromethane needs to be regarded as dangerous for environment due to its danger to
ozone layer.
Tetrachloromethane is well available. There are seven suppliers in European Union whose capacity
is about one to two orders of magnitude higher than the capacity of the production facility. From the
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economic point of view, tetrachloromethane is about 20 % more expensive than TRI, which is not a
reason for rejection.
Based on current knowledge with regard to environmental hazards and uncertainties associated with
reproductive toxicity tetrachloromethane cannot be considered a suitable alternative solvent.
5.2
ALTERNATIVE 2: Chloroform
Chloroform is used as a solvent in industry and chemical laboratory and manufacturing of pesticides
and paints. Previously, chloroform was used in medicine such as inhalation anaesthetic. It is used in
manufacturing of some refrigerants today.
5.2.1
Name and other identifiers for the substance
The identity of chloroform is shown in the following table.
Table 13: Identity of chloroform
Parameter
Value
Source
EC number
200-663-8
CAS number
67-66-3
IUPAC name
Trichloromethane
Other names
chloroform, methyl trichloride, Freon 20, R 20, methane
trichloride
Molecular formula
CHCl3
SMILES notation
ClC(Cl)Cl
Molecular weight
119.38
Molecular
structure
Cl
Cl
Cl
Source:
The following table summarizes the available information on the physical-chemical properties of
chloroform. The information has been collected from the website of ECHA, Registered substances.
Table 14: Physicochemical properties of chloroform
Property
Value
Source
Physical state at 20 C and 101.3 kPa
Liquid
2
Water solubility
8 g/ l
2
Boiling point
62 °C
2
Density
1.48 g/cm3
2
o
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Vapour pressure
211 Pa (20 °C)
2
Partition coefficient (log)
Source:
1.97
2
2.
(ECHA, 2014)
Chloroform is already a registered substance according to REACH regulation. The classification is
mentioned in the following
Table 15.
Table 15: Classification of chloroform
Registration dossier (self-classification) (ECHA,
2014)
Regulation (EC) No. 1272/2008
Hazard class and category
codes
Hazard
codes
Acute Tox. 4
H302
Acute Tox. 3
H331
Skin Irrit. 2
Eye Irrit. 2
statement
Hazard class and category
codes
Hazard
codes
Acute Tox. 4
H302+H332
H315
Skin Irrit. 2
H315
H319
Eye Irrit. 2
H319
STOT SE 3
H336
Carc. 2
H351
Carc. 2
H351
Repr. 2
H361d
Repr. 2
H361
STOT RE 1
H372
STOT RE 2
H373
5.2.2
statement
Technical feasibility for the applicant
Comparison of properties of chloroform and trichloroethylene are shown in Table 16. The density
of both substances, chloroform and trichloroethylene, is practically the same. Chloroform is more
soluble in water than trichloroethylene. This can result in considerable losses of chloroform via
waste water. These losses may be even higher due to the low boiling point and thus greater
evapouration capacity of chloroform.
Table 16: Physical-chemical properties of chloroform and trichloroethylene
Property
Chloroform
Trichloroethylene
water solubility (g/l)
8
1.1
density (g/cm3)
1.48
1.46
log Kow
1.97
2.53
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Flammability
No
No
boiling point ( °C)
62
86.7
Advantage of chloroform is non-flammability as well as in the case of trichloroethylene.
The properties of chloroform mentioned above are well available and they were collected in order
to compare relevant properties of large group of solvents. There are lots of other unknown
properties which affect technology. For example solubility of caprolactam in chloroform,
composition and properties of ternary mixture caprolactam-chloroform-water and their dependence
on temperature, any phase separation problems, effects of inorganic salts especially of ammonium
sulphate etc. These properties have to be found prior to launch of an alternative technology.
Extraction process can be affected by the quality of the available solvent. A different solvent and
modification of the extraction method can cause changing composition and quantity of impurities
that strongly affect the quality of the final product.
The conditions of production cannot be reliably predicted with a sufficient precision, and thus the
expenses and the time frame for the alternative technology cannot be accurately evaluated.
5.2.3
Reduction of overall risk due to the transition to the alternative
The last amendment of CLP – Regulation (EC) No. 994/2013 – comprises a change of harmonised
classification of chloroform. Compared to the previous version, chloroform is a more acute toxic
(new feature is Acute Tox. 3 (H331)). Newly, a suspected reproductive toxicity (Repr. 2 (H361d))
is added and a long-term toxicity is transferred to more severe category (STOT RE 1 (H372)).
In comparison with trichloroethylene, chloroform is “only” suspected carcinogen (Carc. 2 (H351)).
Moreover, as noted above, chloroform is classified as suspected reproductive toxicant (Repr. 2
(H361d)). This assessment appears to be based on a study (Murray FJ, 1979) in which various
developmental defects among litters of pregnant mice after inhalation exposure of chloroform was
found.
Repeated dose toxicity (STOT RE 1 (H372)) is based on the effect on liver and kidney (ECHA,
2014). These adverse symptoms exhibit at concentration of chloroform vapours lower than
threshold limit given in paragraph 3.9.2.9.6 of Annex I of CLP (Assessment, 2011).
Chloroform is more acute toxic than trichloroethylene through oral (Acute Tox. 4 (H302)) but
especially through inhalation route (Acute Tox. 3 (H331)).
Although the narcotic effects of chloroform are well known, any specific data related to this effect
were not presented in the registration dossier, so that classification STOT SE 3 (H336) was not
accepted.
5.2.4
Economic feasibility
The assessment of economic feasibility of chloroform for SPOLANA, a.s. should consider the
following cost elements:


Cost arising from the increased price of the solvent;
Cost arising from the modifications to the plant in order to start using chloroform instead
of trichloroethylene;
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
Loss of turnover from the production of by-products which could be produced at lower
quantity and/or quality if chloroform was used.
Cost element 1: Price of chloroform
Publicly available sources have been searched for price of chloroform. Several producers or
distributors offer chloroform for 440-450 € per ton, resp. 455-485 € per ton (Chl14). This price is
approximately about 40 % lower than trichloroethylene, as price of trichloroethylene is from 550 to
1030 € per ton (TRI) (the mean value is approx. 734 € per ton). From these figures it is evident that
the costs would decrease.
It is necessary to consider the costs of disposal of trichloroethylene. Disposal of one ton of
chlorinated solvents in hazardous waste incinerators costs at least 250 € per ton, total cost for
disposal 316 tons of trichloroethylene is 79.000 €. According to the current economic status of
SPOLANA, a.s. the increase in the price of alternative substance could have strong impact on the
factory and its economy (SEA chapter 2.2.3.3. Table 3).
Cost element 2: Cost of plant conversion
Replacing the trichloroethylene-based extraction process at SPOLANA, a.s. site with an alternative
solvent would require the following assumed modifications:
 Change (rebuild) in the extraction of the crude lactam unit,
 Change (rebuild) in the extraction of distillation residues from rectification unit,
 Change (rebuild) in the extraction of sulphate liquors unit,
 Change (rebuild) in the regeneration solvent.
Currently it is not possible to determine the extent of changes that would be necessary to make. It
may be estimated that a minor reconstruction of the device would cost millions of €, whereas more
extensive modifications of the technology would cost up to tens of millions of €.
Cost element 3: Loss of turnover
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5.2.5
Availability
Chloroform is registered as substance manufactured in quantity higher than 1,000 t/year. There are
seven producers at this tonnage volume who submitted the registration dossier.
Table 17: Market availability of chloroform
Company
Location
Purity ( %)
Supply ability (t/y)
Akzo Nobel Industrial Chemicals GmbH
Germany
-
> 1,000
DOW DEUTSCHLAND
ANLAGENGESELLSCHAFT GmbH
Germany
-
> 1,000
Du Pont de Nemours
Netherlands
-
> 1,000
INEOS Chlorvinyls Limited
United Kingdom
-
> 1,000
Kem One IMMEUBLE SOLARIS
France
-
> 1,000
Ningbo Juhua Chemical & Science Co., Ltd.
China
99.9
70,000
Solvay Chimica Italia S.p.A.
Italy
99.9
> 1,000
Solvay-Electrolyse-France S.A.S.
France
-
> 1,000
Zibo Aiheng New Material Co., Ltd.
China
99.5
36,000
Number of other producers can be found around the world with production capacity of
1,000 t/month or higher (alibaba.com).
When the total volume of solvent for extraction is less than 500 tons, chloroform can be considered
easily available.
5.2.6
Conclusion on suitability and availability for chloroform
With regard to physical-chemical properties, chloroform seems to be a suitable replacement for
trichloroethylene. Density of both of the substances is almost the same and boiling points are
similar. A disadvantage is a relatively high water solubility (chloroform is approximately seven
times more soluble in water than trichloroethylene). That could mean significant loss of chloroform
through waste water. Chloroform is also more volatile, so losses can be increased by the vapourized
part.
Chloroform is not a proven carcinogen as trichloroethylene but it is a suspected carcinogen. Other
hazards of chloroform result from reproduction toxicity and long-term toxicity. Reproduction
toxicity is based on maternal toxicity with the developmental effects reported in toxicological
studies (ECHA, 2014). Toxicity after repeated exposure (long-term toxicity) is based on effects
observed in rats and mice at concentrations lower than threshold concentration specified in CLP
(Assessment, 2011). Negative effects are particularly on liver and kidney. In comparison with
trichloroethylene, chloroform has higher acute toxicity, in particular for inhalation.
Environmental hazards have not been classified in chloroform.
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Chloroform is a very well available substance and economically it is convenient too.
With respect to the above findings significant leakage of chloroform into the environment due its
higher solubility in water can be expected. This fact, in combination with meaningful long-term
toxicity represents a considerable risk to health (in combination with suspicion of reproductive
toxicity and carcinogenicity).
Therefore chloroform cannot be considered as suitable alternative solvent.
5.3
ALTERNATIVE 3: Tetrachloroethylene
Tetrachloroethylene is industrial and laboratory solvent of organic substances. It is used for dry
cleaning. It is used for degreasing metal components in the automotive and metalworking industry.
Tetrachloroethylene is also contained in some consumer products, such as paint strippers.
5.3.1
Name and other identifiers for the substance
The identity of tetrachloroethylene is shown in the following table.
Table 18: Identity of tetrachloroethylene
Parameter
Value
Source
EC number
204-825-9
CAS number
127-18-4
IUPAC name
Tetrachloroethene
Other names
tetrachloroethylene, perchloroethylene
Molecular formula
C2Cl4
SMILES notation
ClC(Cl)=C(Cl)Cl
Molecular weight
165.83
Molecular
structure
Cl
Cl
Cl
Cl
Source:
1:
2:
3:
The following table summarises the available information on the physical-chemical properties of
tetrachloroethylene. The information has been collected from the website of ECHA, Registered
substances.
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Table 19: Physicochemical properties of tetrachloroethylene
Property
Value
Source
Physical state at 20oC and 101,3 kPa
Liquid
3
Water solubility
0.15 g/ l
3
Boiling point
121.4 °C
3
3
Density
1.62 g/cm
3
Vapour pressure
2.5 kPa (25 °C)
3
Partition coefficient (log)
Source:
2.53
3
3.
(ECHA, 2014)
Tetrachloroethylene is already registered substance according to REACH regulation. The
classification is mentioned in the following table.
Table 20: Classification of tetrachloroethylene
Registration dossier (self-classification) (ECHA,
2014)
Regulation (EC) No. 1272/2008
Hazard class and category
codes
Hazard
codes
statement
Hazard class and category
codes
Hazard
codes
Skin Irrit. 2
H315
Skin Sens. 1B
H317
Eye Irrit. 2
H319
STOT SE 3
H336
Carc. 2
H351
Carc. 2
H351
Aquatic Chronic 2
H411
Aquatic Chronic 2
H411
5.3.2
statement
Technical feasibility for the applicant
Comparison of the physical-chemical properties of tetrachloroethylene and trichloroethylene is
shown in Table 21. Tetrachloroethylene is less soluble in water than trichloroethylene.
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Table 21: Physical-chemical properties of tetrachloroethylene and trichloroethylene
Property
Tetrachloroethylene
Trichloroethylene
water solubility (g/l)
0.15
1.1
density (g/cm3)
1.62
1.46
log Kow
2.53
2.53
Flammability
No
No
boiling point ( °C)
121.4
86.7
Tetrachloroethylene seems to be adequate alternative to trichloroethylene. Density of
tetrachloroethylene is slightly larger than trichloroethylene and both solvents are non-flammable. In
addition, tetrachloroethylene is very slightly soluble in water and it has a higher boiling point.
Therefore, it can be assumed that it causes emissions to the environment through waste water and
through exhalation.
There are lots of other unknown properties which affect technology. For example solubility of
caprolactam in tetrachloroethylene, composition and properties of ternary mixture caprolactamtetrachloroethylene-water and their dependence on temperature, any phase separation problems,
effects of inorganic salts especially of ammonium sulphate etc. Different solvent and modification
of the extraction method can cause changing composition and quantity of impurities that strongly
affect the quality of the final product. Extraction process can be affected by the quality of available
solvent (solvent can contain some impurities which can negatively affect the course of extraction or
the quality of the extract).
The conditions of production cannot be reliably predicted with a sufficient precision, and thus the
expenses and the time frame for an alternative technology cannot be accurately evaluated.
5.3.3
Reduction of overall risk due to transition to the alternative
In terms of CLP, tetrachloroethylene is obligatorily classified as suspected carcinogen (Carc. 2
(H351)). Most of the studies presented in the registration dossier are mentioning (in case this effect
is monitored) the occurrence of neoplasms, which is not evaluated as statistically significant or is
not proved to be associated with exposure.
According to the IARC classification (International Agency for Research on Cancer)
tetrachloroethylene is classified as probably carcinogenic to humans (Group 2A). This category is
used when there is a limited evidence of carcinogenicity in humans and sufficient evidence of
carcinogenicity in experimental animals (IARC). Practically, this classification matches
CLP-hazard class and category Carc 1B.
Tetrachloroethylene is not classified as acute toxic not even in self-classification stated in the
registration dossier. However, the results of studies of acute inhalation toxicity suggest that
tetrachloroethylene should be classified in this class of toxicity (Acute Tox. 4 (H332)).
Toxicity to the environment is similar for tetrachloroethylene and for trichloroethylene. Both of
these substances are classified as harmful to the environment with chronic effects (Aquatic Chronic
2 (H411)). Trichloroethylene is a little less dangerous for environment (Aquatic Chronic 3 (H412)).
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5.3.4
Economic feasibility
The assessment of economic feasibility of tetrachloroethylene for SPOLANA, a.s. should consider
the following cost elements:



Cost arising from the increased price of the solvent;
Cost arising from the modifications to the plant in order to start using tetrachloroethylene
instead of trichloroethylene;
Loss of turnover from the production of by-products which could be produced at lower quantity
and/or quality if tetrachloroethylene was used.
Cost element 1: Price of tetrachloroethylene
Publicly available sources have been searched for price of tetrachloroethylene. Data found on the
website alibaba.com (aliPCE) suggested that tetrachloroethylene is offered for prices from
660-675 € per ton to 1,150-1,175 € per ton. Price of trichloroethylene is from 550 to 1,030 € per ton
(TRI), the mean value is ca. 734 € per ton. This means that the price of tetrachloroethylene is about
€ 150 per ton higher than price of trichloroethylene. Total volume of trichloroethylene in
SPOLANA, a.s. site is 316 tons, thus full exchange of solvent would cost at least 209.000 €.
It is necessary to consider the costs of disposal of trichloroethylene. Disposal of one ton of
chlorinated solvents in hazardous waste incinerators costs at least € 250 per ton, total cost for
disposal 316 tons of trichloroethylene is 79.000 €. According to the current economic status of
SPOLANA, a.s. the increase in the price of alternative substance could have strong impact on the
factory and its economy (SEA chapter 2.2.3.3. Table 3).
Cost element 2: Cost of plant conversion
Replacing the trichloroethylene-based extraction process at SPOLANA, a.s. site with an alternative
solvent would require the following assumed modifications:
 Change (rebuild) in the extraction of the crude lactam unit,
 Change (rebuild) in the extraction of distillation residues from rectification unit,
 Change (rebuild) in the extraction of sulphate liquors unit,
 Change (rebuild) in the regeneration solvent.
Currently it is not possible to determine the extent of changes that would be necessary to make. It
may be estimated that a minor reconstruction of the device would cost millions of €, whereas more
extensive modifications of the technology would cost up to tens of millions of €.
Cost element 3: Loss of turnover
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5.3.5
Availability
Tetrachloroethylene is registered as a substance manufactured in quantity higher than 1,000 t/year.
There are four producers at this tonnage volume, who submit the registration dossier. Many others
suppliers can be found via internet (aliPCE).
Table 22: Market availability of tetrachloroethylene
Company
Location
Purity ( %)
Supply ability (t/y)
Banner Chemicals Ltd
United Kingdom
-
> 1,000
CHS Epi, a.s.
Czech Republic
-
> 1,000
Dongying City Longxing Chemical Co., Ltd.
China
99.9
50,000
DOW DEUTSCHLAND
ANLAGENGESELLSCHAFT GmbH k
Germany
-
> 1,000
Hainan Huarong Chemical Co., Ltd.
China
99.9
7,000
Ningbo Juhua Chemical & Science Co., Ltd.
China
99.9
50,000
Shijiazhuang City Horizon Chemical Industry Co., Ltd
China
99.9
40,000
Solvay-Electrolyse-France S.A.S.
France
-
> 1,000
Tianjin Ruifengtiantai International Trade Co., Ltd.
China
99.9
60,000
Zhejiang Junhao Chemical Co., Ltd.
China
99.95
60,000
When the total volume of solvent for extraction in SPOLANA, a.s. is less than 500 tons and there is
a number of suppliers who can supply the quantity of tetrachloroethylene by one to two orders of
magnitude higher, tetrachloroethylene can be considered as easily available.
5.3.6
Conclusion on suitability and availability for tetrachloroethylene
Based on the information mentioned above it can be concluded that physical-chemical parameters
of tetrachloroethylene are appropriate to replacement for trichloroethylene. Both of the substances
are non-flammable. Tetrachloroethylene is significantly less soluble in water and it has a higher
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boiling point, so release to the environment via waste water or exhalation would be reduced.
Specific gravity of tetrachloroethylene is slightly higher than in case of trichloroethylene.
Tetrachloroethylene is not a proven carcinogen like trichloroethylene but it is a suspected
carcinogen.
Environmental hazards are similar both for tetrachloroethylene and for trichloroethylene. Both
substances are classified as harmful/toxic to environment with long lasting effects;
tetrachloroethylene is little more toxic (Aquatic Chronic 2 (H411)).
Tetrachloroethylene is very well available substance; its price is about 20-25 % higher than
trichloroethylene.
According to physical-chemical properties availability tetrachloroethylene seems to be acceptable
alternative to trichloroethylene. With regards to a possible carcinogenic potential
tetrachloroethylene cannot be considered a suitable alternative solvent.
5.4
ALTERNATIVE 4: Ionic liquids
Ionic liquids are ionic substances existing in liquid state. Usually they have an organic cation and
inorganic or organic anion. There are some unique properties due to their structure. Use of ionic
liquids is still predominantly in laboratories, although some industrial uses are already known
(BASF).
5.4.1
Name and other identifiers for the substance
Ionic liquids are a group of substances, which have some common characteristics (ionic structure,
liquid state below 100 °C). Despite this many other properties vary across a wide range. The
parameters of ionic liquids vary according to the structure of particularly cations but also of anions.
A cation is mostly formed by ammonium salt derived from an aromatic or aliphatic amine.
Derivatives of 1-butyl-3-methyl imidazole are frequently mentioned. Anions are usually
tetrafluoroborate, hexafluorophosphate, bis((trifluoromethyl)sulfonyl)imide etc., but it can also be
a simple nitrate, chloride, bromide and others.
5.4.2
Technical feasibility for the applicant
As suggested above, ionic liquids have a wide variety of properties depending on their chemical
structure. They can be soluble or insoluble in water. Usually they are chemically and thermally very
stable. Ionic liquids have negligible vapour pressure (thus, a high boiling point) therefore it might
be problematic for their regeneration by distillation or rectification. Density of ionic liquids is
generally 1.12 – 2.4 g/cm3 and is not very dependent on temperature.
Ionic liquids generally have a relatively high viscosity. It may be both an advantage (improved
phase separation) and a disadvantage (difficult transfer material between phases) during extraction.
Ionic liquids are generally considered non-flammable materials due to their low vapour pressure.
But some ionic liquids can generate flammable gases on thermal decomposition.
It is necessary to find optimal structure of ionic liquids for extraction of caprolactam first of all.
Subsequently essential parameters may be determined for this solvent (solubility of caprolactam in
the solvent, composition and properties of ternary mixture caprolactam-solvent-water and their
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dependence on temperature, any phase separation problems, effects of inorganic salts especially of
ammonium sulphate etc.) and their effect on the extraction process evaluated.
5.4.3
Reduction of overall risk due to transition to the alternative
Ionic liquids are generally considered as non-toxicologic. This is often cited in literature. However,
their wide range of their structures and properties suggested that toxicity of ionic liquids might
differ too. Several articles have been published where the toxicity of some ionic liquids is
determined (Xu H., 2013), (Dumitrescu G., 2013). Carcinogenicity of ionic liquids has not been
systematically studied yet as well as reproduction toxicity and long-term toxicity.
Ionic liquids are usually referred to as “green solvents”. This term should suggest that ionic liquids
are not hazardous for environment. In previous years a numerous studies of environmental toxicity
have been reported in the world literature. Most of them confirmed their low toxicity to aquatic
organisms but (in accordance with the above mentioned structural diversity) some types of these
solvents would have to be classified as harmful to environment (Kalcikova G., 2012), (Ma J.M. Cai
L.L. Zhang B.J., 2010).
In addition, most studies of biodegradability have shown poor degradability (Romero A., 2008)
which results in an increased risk to the environment especially regarding long-term environmental
toxicity.
In comparison with common organic solvents (particularly with chlorinated organic solvents) ionic
liquids seem to be less hazardous for both human health and for environment. However, this
statement is not valid in general and individual solvents need to be evaluated case by case.
5.4.4
Economic feasibility
The assessment of economic feasibility of ionic liquids for SPOLANA, a.s. should consider the
following cost elements:



Cost arising from the increased price of the solvent;
Cost arising from the modifications to the plant in order to convert from using trichloroethylene
to alternative solvent;
Loss of turnover from the production of by-products which could be produced at lower quantity
and/or quality with using alternative solvent.
Cost element 1: Price of ionic liquids
As previously mentioned, there are many types of ionic liquids. With the current knowledge the
optimal type of ionic liquids that could replace trichloroethylene cannot be determined. This
document contains only general information about prices and availability of ionic liquids in order to
assess the economic aspects of replacing the solvent.
The lowest observed price for ionic liquid is 0.734-734 € per kilogram (Wuxi Sigma Chemical
Products Co., Ltd.), resp. 7.34-147 € per kilogram (Shaanxi King Stone Enterprise Co., Ltd.), which
are offers of industrial products. The offers of laboratory solvents are numerous but they are not
relevant to analysis of alternatives. It must be noted that the above offers are valid for the cheapest
ionic liquids available on the market. A suitable ionic liquid for extraction of caprolactam would be
most likely more expensive and therefore the above mentioned prices should be regarded as the
lowest cost estimate.
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ANALYSIS OF ALTERNATIVES
The cheapest ionic liquids cost 734-73.400 per ton. The total volume of trichloroethylene in
SPOLANA, a.s. site is 316 tons, thus a full exchange of the solvent would cost 232.000 € to
23.194.000 €. However, it is likely that the actual cost could be even higher as the real ionic liquid
would probably be more expensive.
It is necessary to consider the costs of disposal of trichloroethylene. Disposal of one ton of
chlorinated solvents in hazardous waste incinerators costs at least 250 € per ton, the total cost for
disposal of 316 tons of trichloroethylene is 79.000 €. According to the current economic status of
SPOLANA, a.s. the increase in the price of alternative substance could have strong impact on the
factory and its economy (SEA chapter 2.2.3.3. Table 3).
Cost element 2: Cost of plant conversion
Replacing the trichloroethylene-based extraction process at SPOLANA, a.s. site with an alternative
solvent would require the following assumed modifications:
 Change (rebuild) in the extraction of the crude lactam unit,
 Change (rebuild) in the extraction of distillation residues from rectification unit,
 Change (rebuild) in the extraction of sulphate liquors unit,
 Change (rebuild) in the regeneration solvent.
Currently it is not possible to determine the extent of changes that would be necessary to make. It
may be estimated that a minor reconstruction of the device would cost millions of €, whereas more
extensive modifications of the technology would cost up to tens of millions of €.
Cost element 3: Loss of turnover
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5.4.5
Availability
Availability of ionic liquids is currently quite limited. In some rare cases these solvents are
available in quantity of tens to hundreds of tons per year. However ionic liquids are generally
produced and supplied in small volumes for laboratory use.
5.4.6
Conclusion on suitability and availability for ionic liquids
Ionic liquids are a group of substances that have various properties. It is very likely that among
those it may be found the optimal structure for extraction of caprolactam. The advantage of ionic
liquids is the possibility to modify the properties of the solvent through its structure. An ionic liquid
suitable for the extraction of caprolactam is currently not known; therefore it is not possible to
assess its properties (physical-chemical parameters, toxicity, and environmental hazards).
An important disadvantage of ionic liquids is their high price but also insufficient availability. In
combination with the lack of information on toxicity and environmental hazards it is not possible to
consider ionic liquids as an alternative solvent to trichloroethylene at present.
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6. OVERALL CONCLUSIONS ON SUITABILITYAND AVAILABILITY OF POSSIBLE ALTERNATIVES FOR USE 1
6.1
Conclusion of alternatives for USE 1
During the AoA 32 substances were assessed based on the KIs as alternatives to replace TRI. Only 3 substances (tetrachloromethane, chloroform,
tetrachloroethylene) and the group of ionic liquids fulfilled the KIs and were assessed in the Chapter 5. Even though a detailed study of the
currently known technologies for the caprolactam production was made, no suitable technology meeting the KIs for technical and economical (a
by-product of a fertilizer) demands was found. To make a clear overview of alternatives assessed from the point of view of their suitability and
availability, risk reducing, etc. Table 23 was created. The conclusions summarised in the table proved no suitable alternative to replace TRI was
found.
Table 23: Overall conclusion of possible alternatives assessed
Substance
physicalchemical
parameters
toxicological
risks
environmental
risks
trade
availability
economic
parameters
conclusion
not acceptable
not acceptable
well
available
20 % more
expensive
than TRI,
acceptable
Not suitable, dangerous to the ozone layer
well
available
acceptable
Not suitable, environment pollution into waste
water, long-term toxicity represents
a considerable risk to health
tetrachloromethane
suitable
chloroform
suitable
not acceptable
not acceptable
tetrachloroethylene
suitable
not acceptable
acceptable
well
available
acceptable
Not suitable, suspected carcinogen
ionic liquids
lack of
information
lack of
information
lack of
information
insufficient
availability
not
acceptable
Not suitable to replace, lack of information,
insufficient availability and high price
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From the technology point of view another fact had to be considered. Replacing the
trichloroethylene-based extraction process at SPOLANA, a.s. site with any kind of the substances
mentioned above (if suitable) would require the following assumed modifications:
 Change (rebuild) in the extraction of the crude lactam unit,
 Change (rebuild) in the extraction of distillation residues from rectification unit,
 Change (rebuild) in the extraction of sulphate liquors unit,
 Change (rebuild) in the regeneration solvent.
It was not possible to determine the extent of changes that would be necessary to make in order to
start using the selected alternative. It may be estimated that a minor reconstruction of the device
would cost millions of EUR, whereas more extensive modifications of the technology would cost
up to tens of millions of EUR.
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6.2
Future plan of research
Based on the results of the previous research 4.1.1 and the results from Sections 4.2 and 6 the future
research should focus on detection of the appropriate substance to replace TRI and detection of
suitable extraction process changes. The research plan consists of 4 parts:
6.2.1
Literature sources survey and data compilation
Expected period for this part of research is 2015-2017.
All relevant literature sources focused on the alternatives from the Chapter 5 or those that might
replace TRI in future (ionic liquids) are to be undertaken to the detail study. The key indicators as:
affinity, density, water solubility, interfacial tension should be considered as the main important to
indicate if the solvent was suitable for extraction process. The detail survey of technologies should
be done to include flammable substances suitable to be used as alternative, which is not possible
nowadays due to the technology of SPOLANA, a.s.
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The research will be done using the sources of SPOLANA, a.s. itself so the financial costs are
considered low. Only man power and some cost of sources are expected.
6.2.2
Laboratory research and projection of extractions
Expected period for this part of research is 2018-2021
Based on outputs from the “Literature sources and data compilation” part of the research following
steps of laboratory research should be done to determine the solvent that could be used in the
laboratory experiments. Those experiments should show how efficient the extraction of caprolactam
would be by use of a proper solvent that meets the criteria of caprolactam production (caprolactam
quality, properties, etc.)
An important parameter monitored during the laboratory experiments is the efficiency of
caprolactam extraction by an alternative solvent. The extraction efficiency depends on the following
points:


the distribution coefficient;
the separating effect of rectification columns (number of theoretical stages, the ratio of
injected components);
 the impurities in crude caprolactam;
 the concentration of extract;
 and the temperature of extraction.
All the relevant outputs should point the key parameters for the extraction process projection –
modified extraction step itself and the solvent re-generation process.
The research will be done by the third party.
Financial costs of the laboratory research are hard to predict so we can only expect those based on
the Design of Experiments (DOE) methodology approach (Erikson, 2008).
6.2.3
Pilot plant
Expected period for this part of research is 2022-2027.
Based on the results of laboratory experiments a pilot plant for caprolactam production will be
projected, incl. preparation of crude caprolactam, extraction of caprolactam in the new constructed
extractor with a suitable number of stages, and regeneration of the selected solvent.
Caprolactam obtained by this new technology would be analysed in laboratory. In case those
conditions fulfil requirements below, it would be possible to project this pilot plant in fully-scale
production:

purity of caprolactam ˃ 92 %;

a sufficient amount of extraction by-product (ammonium sulphate).
Before the construction of a new pilot plant starts the following legal steps must be ensured:

building permission
Expected financial costs for research of the alternative substance and the pilot plant project are
estimated at approx. 1-1.2 million €. Based on the data from (Mount, 2008) and (Alpert, 1980) costs
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ANALYSIS OF ALTERNATIVES
of the pilot plant with the production of 1 000 tons of caprolactam per year would be approx. 11.5
million €.
6.2.4
Conclusions of the research
If the conclusion of all research steps were that alternative for TRI was found and the pilot plant
project was successful, than the building of new technology (or its part) should start. It is difficult to
predict the financial costs of the build-up of the new technology. Expected time for construction is
approx. 2-3 years. The construction is connected to the legal steps that might be undertaken before
the construction begins and some of those run simultaneously:

project of the technology (1 year),

allowance of the EIA (2-3 years),

building permission, IPPC licence (2-3 years),

testing period (1 year).
Expected period for the new technology build up is 2028-2034.
Expected financial costs for the new technology or a significant technology change are estimated
between 25 million € to 46 million €8 (DSM, Corporate Communications, 2007), (Mount, 2008).
Time schedule for the research plan is shown in the
Table 24.
Table 24: Time schedule of the research plan
Time schedule of the research plan
Year(s)
Literature research
2
Laboratory research and projection of extractions
3
Pilot plant
5
Project of the technology
1
The allowance of the EIA
2-3
Building permit, IPPC licence
2-3
Testing period
Total time
8
1
16 - 18
35 million USD (resp. 31 million EUR) year 1994; conversion USD 1 = EUR 0,8897;
Converted for year 2014 = 46 million EUR; Inflation over the period: 48.18 % (Inflation was calculated using an
inflation calculator http://fxtop.com).
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ANALYSIS OF ALTERNATIVES
The here presented research plan is only the schedule that should be followed. It is difficult to
predict how the research will progress and what the conclusion of the data survey and laboratory
experiments will be. Those outputs can influence the time schedule or financial cost mentioned here
significantly. It might happen, that data survey and laboratory experiments would not bring any new
piece of knowledge and thus it would have to be started over again with new substances or a new
methodological approach. Even if the laboratory experiments were successful, problems might
occur in the projection of the pilot plant or the outputs of this part of research would not bring any
new piece of knowledge either. The investments and the economical part of the research might be
those that might prolong the time scheduled here and there also are potential high risk indicators of
the research success. All the facts mentioned above generate uncertainties that potentially may
influence the research.
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ANALYSIS OF ALTERNATIVES
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Ishii, Y., Hashimoto, M., & Sakaquchi, S. (2006). One-pot synthesis of lactams from cycloalkanes
and tert-butylnitrite by using N-hydroxyphtalimide as key catalyst. Chem. Asian J., pp. 712 716.
Jubb, A. H. (1971). Education Chemistry, pp. 23-25.
Kalcikova G., Z.-K. J.-P. (2012). Assessment of environmental impact of pyridinium-based ionic
liquid. Fresenius Environmental Bulletin, 8b(2320-2325).
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Tomáše Bati ve Zlíně.
Kirby, G. S., & Ostermaier, J. J. (2004). Patent No. US6716977 B1.
KROISOVÁ, D. (2009). Biodegradovatelné polymery - úvod do problematiky. Liberec: Technická
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Safety, 6(1465-1469).
Mettu, A. (2009). New synthesis routes for production of e-caprolactam by Beckmann
rearrangement of cychlohexanone oxime and ammoximation of cyclohexanone over
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ew+Patented...-a050145019
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http://www.chemsystems.com/about/cs/news/items/PERP%200910_1_Caprolactam.cfm
PROKOPOVÁ, I. (2004). Makromolekulární chemie. Praha: VŠCHT.
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Puffr, R., & Kubanek, V. (1991). Lactam-based polyamides. CRC Press.
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(2008). The continuous synthesis of caprolactam from 6-aminocapronitrile in hightemperature water. Green Chemistry, pp. 98 - 103.
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monoacetyldiglycerine. Keye ngeneering materials, 277-279, pp. 137-141.
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ANALYSIS OF ALTERNATIVES
8. LIST OF ABREVIATTIONS, FIGURES AND TABLES
8.1.
List of abreviattions
AoA
CLP
CNB
EC
ECHA
EIA
EU
ID card
IPPC
KIs
REACH
SVHC
TRI
8.2.
Analysis of Alternatives
Regulation (EC) No. 994/2013
Czech National Bank
European Commision
European Chemical Agency
Environmental Impact Assessment
European Union
Identification card
Integrated Pollution Prevention and Control
Key Indicators
Regulation (EC) No. 1907/2006
Substance of Very High Concern
Trichloroethylene
List of figures
Figure 1: Chemical formula and structure of TRI........................................................................... 8
Figure 2: Structure of caprolactam.................................................................................................. 10
Figure 3: Caprolactam via cyclohexanonoxim ............................................................................... 12
Figure 4: Polymerization of caprolactam ........................................................................................ 12
Figure 5: Block diagram of the continual process of POLYAMIDE 6 distribution ....................... 14
Figure 6: Global production of caprolactam in 2012 ...................................................................... 15
Figure 7: World Consumption of Caprolactam in 2010 ................................................................. 15
Figure 8: Global caprolactam demand by end use, 2005 ................................................................ 16
Figure 9: The production process SPOLANA a.s. .......................................................................... 18
Figure 10: The consumption of TRI in the long term period .......................................................... 20
8.3.
List of tables
Table 1: Overall conclusion of possible alternatives assessed ........................................................ 6
Table 2: Uses of TRI sold into the EU market ................................................................................ 9
Table 3: Basic physical properties of ε-caprolactam ...................................................................... 10
Table 4: Caprolactam quality specifications ................................................................................... 19
Table 5: Databases for the alternative substances and technologies to TRI ................................... 21
Table 6: List of possible alternatives – Substances......................................................................... 26
Table 7: List of possible alternatives – Technologies ..................................................................... 29
Table 8: Identity of tetrachloromethane .......................................................................................... 31
Table 9: Physical - chemical properties of tetrachloromethane ...................................................... 32
Table 10: Classification of tetrachloromethane .............................................................................. 32
Table 11: Properties of tetrachloromethane and trichloroethylene ................................................. 33
Table 12: Market availability of tetrachloromethane ...................................................................... 36
Table 13: Identity of chloroform ..................................................................................................... 37
Table 14: Physicochemical properties of chloroform ..................................................................... 37
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Table 15: Classification of chloroform ........................................................................................... 38
Table 16: Physical-chemical properties of chloroform and trichloroethylene ................................ 38
Table 17: Market availability of chloroform................................................................................... 41
Table 18: Identity of tetrachloroethylene ........................................................................................ 42
Table 19: Physicochemical properties of tetrachloroethylene ........................................................ 43
Table 20: Classification of tetrachloroethylene .............................................................................. 43
Table 21: Physical-chemical properties of tetrachloroethylene and trichloroethylene ................... 44
Table 22: Market availability of tetrachloroethylene ...................................................................... 46
Table 23: Overall conclusion of possible alternatives assessed ...................................................... 51
Table 24: Time schedule of the research plan................................................................................. 54
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ANALYSIS OF ALTERNATIVES
9. APPENDIXES AND ANNEXES
ANNEX – JUSTIFICATIONS FOR CONFIDENTIALITY CLAIMS9
Blanked out
item reference
Page
number
Blanked no.1
19
Blanked no.2
35
9
Justification for blanking
(CBI) Blanked information has no relation to substance under this
AOA (trichloroethylene) regarding to its chemical or physical
characteristics, nevertheless, this information represents
confidential business information relating to the quality of
product that applicant produces using substance under this AOA.
Moreover, blanked information is not covered by REACH Article
118 or 119. This information is not generally known among or
readily accessible to persons within the circles that normally deal
with the kind of information in question, has commercial value
because is secret, and has been subject to applicant’s reasonable
steps to keep it secret. Its disclosure could directly harm
applicant’s business strategies and plans, commercial interests
and could lead his customers to decide to switch supplier of the
product if other competitors obtain this information. Moreover,
there is no overriding public interest in the disclosure such
information, because its non-disclosure does not exclude main
purpose of Regulation REACH which is to ensure a high level of
protection of human health and the environment. Referring to
Agreement TRIPS Article 39 we, hereby, apply to not disclose
those information to prevent their unfair commercial use.
(CBI) Blanked information has no relation to substance under this
AOA (trichloroethylene) regarding to its chemical or physical
characteristics, nevertheless, this information represents
confidential business information relating to applicant’s turnover
in case he would use alternative substance. Moreover, blanked
information is not covered by REACH Article 118 or 119. This
information is not generally known among or readily accessible to
persons within the circles that normally deal with the kind of
information in question, has commercial value because is secret,
and has been subject to applicant’s reasonable steps to keep it
secret. Its disclosure could directly harm applicant’s business
strategies, plans and commercial interests if other competitors
obtain this information. Moreover, there is no overriding public
interest in the disclosure such information, because its nondisclosure does not exclude main purpose of Regulation REACH
which is to ensure a high level of protection of human health and
the environment. Referring to Agreement TRIPS Article 39 we,
hereby, apply to not disclose those information to prevent their
Valid for the public version
Use number: 1
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ANALYSIS OF ALTERNATIVES
unfair commercial use.
Blanked no.3
40
Blanked no.4
45-46
(CBI) Blanked information has no relation to substance under this
AOA (trichloroethylene) regarding to its chemical or physical
characteristics, nevertheless, this information represents
confidential business information relating to applicant’s turnover
in case he would use alternative substance. Moreover, blanked
information is not covered by REACH Article 118 or 119. This
information is not generally known among or readily accessible to
persons within the circles that normally deal with the kind of
information in question, has commercial value because is secret,
and has been subject to applicant’s reasonable steps to keep it
secret. Its disclosure could directly harm applicant’s business
strategies, plans and commercial interests if other competitors
obtain this information. Moreover, there is no overriding public
interest in the disclosure such information, because its nondisclosure does not exclude main purpose of Regulation REACH
which is to ensure a high level of protection of human health and
the environment. Referring to Agreement TRIPS Article 39 we,
hereby, apply to not disclose those information to prevent their
unfair commercial use.
Blanked no.5
49
(CBI) Blanked information has no relation to substance under this
AOA (trichloroethylene) regarding to its chemical or physical
characteristics, nevertheless, this information represents
confidential business information relating to applicant’s turnover
in case he would use alternative substance. Moreover, blanked
information is not covered by REACH Article 118 or 119. This
information is not generally known among or readily accessible to
persons within the circles that normally deal with the kind of
information in question, has commercial value because is secret,
Use number: 1
(CBI) Blanked information has no relation to substance under this
AOA (trichloroethylene) regarding to its chemical or physical
characteristics, nevertheless, this information represents
confidential business information relating to applicant’s turnover
in case he would use alternative substance. Moreover, blanked
information is not covered by REACH Article 118 or 119. This
information is not generally known among or readily accessible to
persons within the circles that normally deal with the kind of
information in question, has commercial value because is secret,
and has been subject to applicant’s reasonable steps to keep it
secret. Its disclosure could directly harm applicant’s business
strategies, plans and commercial interests if other competitors
obtain this information. Moreover, there is no overriding public
interest in the disclosure such information, because its nondisclosure does not exclude main purpose of Regulation REACH
which is to ensure a high level of protection of human health and
the environment. Referring to Agreement TRIPS Article 39 we,
hereby, apply to not disclose those information to prevent their
unfair commercial use.
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ANALYSIS OF ALTERNATIVES
and has been subject to applicant’s reasonable steps to keep it
secret. Its disclosure could directly harm applicant’s business
strategies, plans and commercial interests if other competitors
obtain this information. Moreover, there is no overriding public
interest in the disclosure such information, because its nondisclosure does not exclude main purpose of Regulation REACH
which is to ensure a high level of protection of human health and
the environment. Referring to Agreement TRIPS Article 39 we,
hereby, apply to not disclose those information to prevent their
unfair commercial use.
Blanked no.6
Use number: 1
52
(CBI) Blanked information has no relation to substance under this
AOA (trichloroethylene) regarding to its chemical or physical
characteristics, nevertheless, this information represents
confidential business information relating to applicant’s turnover
in case he would use alternative substance. Moreover, blanked
information is not covered by REACH Article 118 or 119. This
information is not generally known among or readily accessible to
persons within the circles that normally deal with the kind of
information in question, has commercial value because is secret,
and has been subject to applicant’s reasonable steps to keep it
secret. Its disclosure could directly harm applicant’s business
strategies, plans and commercial interests if other competitors
obtain this information. Moreover, there is no overriding public
interest in the disclosure such information, because its nondisclosure does not exclude main purpose of Regulation REACH
which is to ensure a high level of protection of human health and
the environment. Referring to Agreement TRIPS Article 39 we,
hereby, apply to not disclose those information to prevent their
unfair commercial use.
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ANALYSIS OF ALTERNATIVES
APPENDIXES
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ANALYSIS OF ALTERNATIVES
Appendix 1: ID Cards of possible substances alternatives
List of substances:

1,1 – dichloroethane
 1,1,1 – trichloroethane
 1,1,2 – trichloroethane
 1,1,2 – trichloroethylene

1,1 – dichloroethylene

1,2 – dichloroethane

1,2 – dichloroethylene
 1 – heptanol
 2 – ethylhexanol
 2 – heptanone
 2 – methylcyclohexanol
 alkyl phenols
 benzen
 bis (2 – ethylhexyl) hydrogenphosphate
 cyclohexane
 diethylether
 dichloromethane
 dichlorobenzene
 chloroform
 ligroine
 methylcyclohexane
 n-heptane
 n-hexane
 nitrobenzene
 octanol
 tetrachloroethylen
 tetrachloromethane
 toluene
 xylene
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ANALYSIS OF ALTERNATIVES
1,1-dichloroethane
CAS Number:1
EC Numer:1
Synonym:2
Molecular formula:1
Physical and Chemical Properties
Boiling Point6: 57.25 °C
Melting Point2: -97 °C
Vapour Pressure2: 230 Torr (25 °C)
Water Solubility5: 5.04 g/l
Partition Coeff.3: log Kow = 1.79
Density6: 1.25 g/cm3
Flammability: Yes
Hazards Identification
75-34-3
200-863-5
ethylidene chloride
C2H4Cl2
According to Regulation (EC) No. 1272/2008:
(index No. 602-011-00-1)
Flam. Liq. 2 (H225)
Acute. Tox. 4 (H302)
Eye Irrit. 2 (H319)
STOT SE 3 (H335)
Aquatic Chronic 3 (H412) 4
Registration documentation:
Not registered.
Potential Acute Health Effects:
Potential Chronic Health Effects:
Sources
1
www.chemspider.com
2
www.caslab.com
3
Hansch C., Leo A., Hoekman D., Exploring QSAR, Hydrophobic, Electronic, and Steric
Constants, ACS Professional Reference Book, Washington DC (1995)
4
en.chembase.cn/substance-363010.html
5
Horvath A., Getzen F.W., Maczynska, IUPAC-NIST Solubility Data, Series 67, Halogenated
Ethanes and Ethenes, Journal of Physical and Chemical Reference Data, 28, p. 395-507
(1999)
6
Večeřa M., Gasparič J., Churáček J., Borecký J., Chemické tabulky organických sloučenin,
Státní nakladatelství technické literatury (SNTL), Praha (1975)
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ANALYSIS OF ALTERNATIVES
1,1,1-trichloroethane
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties
Boiling Point:1 74.1 °C
Melting Point:1 -30.4 °C
Vapour Pressure:1 16.4 kPa (20 °C)
Density1: 1.34 g/cm3
Water Solubility:1 1.25 g/l
Partition Coeff.:1 log Kow = 2.49
Flammability: No
Hazards Identification
71-55-6
200-756-3
C2H3Cl3
According to Regulation (EC) No. 1272/2008:
(index No. 602-013-00-2)
Acute Tox. 4 (H332)
Ozone 1 (H420)
Registration documentation:
Skin Irrit. 2 (H315)
Eye Irrit. 2 (H319)
Potential Acute Health Effects:
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
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ANALYSIS OF ALTERNATIVES
1,1,2-trichloroethane
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties
Boiling Point:1 114 °C
Melting Point:1 -36 °C
Vapour Pressure:1 22.3 hPa (20 °C)
Density1: 1.44 g/cm3
Water Solubility:1 3.5 g/l
Partition Coeff.:2 log Kow = 1.89
Hazards Identification
79-00-5
201-166-9
C2H3Cl3
According to Regulation (EC) No. 1272/2008:
(index No. 602-014-00-8)
Acute Tox. 4 (H302+H312+H332)
Carc. 2 (H351)
Registration documentation:
There are two different classifications with different levels of impurities.
Potential Acute Health Effects:
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
2
Hansch C., Leo A., Hoekman D., Exploring QSAR, Hydrophobic, Electronic, and Steric
Constants, ACS Professional Reference Book, Washington DC (1995)
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ANALYSIS OF ALTERNATIVES
1,1,2-trichloroethylene
CAS Number:1
EC Numer:1
Synonym:2
Molecular formula:1
Physical and Chemical Properties
Boiling Point: 86.7 °C
Melting Point: -84.8 °C
Vapour Pressure: 9.9 kPa (25 °C)
Density: 1.46 g/cm3
Water Solubility: 1.1 g/l
Partition Coeff.: log Kow = 2.53
Flammability: No
Hazards Identification
79-01-6
201-167-4
1,1,2-trichloroethene,
1,1-Dichloro2-chloroethylene,
1-Chloro-2,2dichloroethylene, Acetylene trichloride,
TCE, Trethylene, triclene, tri, Trimar,
trilene, HCC-1120
C2HCl3
According to Regulation (EC) No. 1272/2008:
(index No. 602-027-00-9)
Skin Irrit. 2 (H315)
Eye Irrit. 2 (H319)
STOT SE 3 (H336)
Muta. 2 (H341)
Carc. 1B (H350)
Aquatic Chronic 3 (H412)
Registration documentation:
Skin Irrit. 2 (H315)
Eye Irrit. 2 (H319)
Skin Sens. 1B (H317)
STOT SE 3 (H336)
Carc. 1B (H350)
Aquatic Chronic 3 (H412)
Potential Acute Health Effects:
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
2
htp://www.cdc.gov/niosh/NLG/npgd0629.html
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ANALYSIS OF ALTERNATIVES
1,1-dichloroethylene
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 31.56 °C
Melting Point: -122.5 °C
Water solubility: 2.5 g/l
Vapour Pressure: 665 hPa (20 °C)
Partition coeff.: log Kow = 2.13
Density: 1.21 g/cm3
Flammability: Yes
Hazards Identification
75-35-4
200-864-0
sym. dichloroethylene
C2H2Cl2
According to Regulation (EC) No. 1272/2008:1
(index No. 602-025-00-8)
Flam. Liq. 1 (H224)
Acute Tox. 4 (H332)
Carc. 2 (H351)
Registration documentation:
Same as harmonized classification.
Acute Tox. 4 (H302)
Eye Irrit. 2 (H319)
STOT RE 2 (H373)
Aquatic Chronic 2 (H411)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
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ANALYSIS OF ALTERNATIVES
1,2-dichloroethane
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 83.6 °C
Melting Point: -36 °C
Water solubility: 7.9 g/l
Vapour Pressure: 10.247 kPa
Partition coeff.: log Kow 1.45
Density: 1.25 g/cm3
Flammability: Yes
Hazards Identification
107-06-2
203-458-1
C2H4Cl2
According to Regulation (EC) No. 1272/2008:
(index No. 602-012-00-7)
Flam. Liq. 2 (H225)
Acute Tox. 4 (H302)
Skin Irrit. 2 (H315)
Eye Irrit. 2 (H319)
STOT SE 3 (H335)
Carc. 1B (H350)
Registration documentation:
Same as harmonized classification.
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
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ANALYSIS OF ALTERNATIVES
1,2-dichloroethylene
CAS Number:1
EC Numer:1
Synonym1:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point2: 55 °C
Melting Point1: -57 °C
Water solubility3: 3.5 g/l
Partition coeff.4: log Kow = 2.00
Density5: cca 1.28 g/cm3
Flammability: Yes
Hazards Identification
540-59-0
208-750-2
Dioform, Dichloracetylene,
Dichloroethylene, acetylenedichloride
C2H2Cl2
According to Regulation (EC) No. 1272/2008:
(index No. 602-026-00-3)
Flam. Liq.2 (H225)
Acute Tox. 4 (H332)
Aquatic Chronic 3 (H412)
Registration documentation:
Not registered.
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://www.chemicalbook.com/
2
Boublík T., Fried V., Hála E., The Vapour Pressures of Pure Substances, Elsevier,
Amsterodam (1984)
3
Yalkowsky S.H., Dannenfelser R.M., AQUASOL database of aqueous solubility, version 5
(PC version), College of Pharmacy, University of Arisona, tucson (1992)
4
Hansch C., Leo A., Hoekman D., Exploring QSAR, Hydrophobic, Electronic, and Steric
Constants, ACS Professional Reference Book, Washington DC (1995)
5
The Merck Index - An Encyclopedia of Chemicals, Drugs, and Biologicals, O'Neil M.J.
(editor), Royal Society of Chemistry, Cambridge, UK, p. 17 (2013)
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
1-heptanol
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 184,44 °C
Melting Point: -34,6 °C
Water solubility: 1,63 g/l
Vapour Pressure: 70 Pa (20 °C), 100 Pa (25 °C)
Partition coeff.: log Kow = 2,2
Density: 0.82 g/cm3
Flammability: No
Hazards Identification
111-70-6
203-897-9
Heptan-1-ol
C7H16O
According to Regulation (EC) No. 1272/2008:
Not classified
Registration documentation1:
Eye Irrit. 2 (H319)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
75
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ANALYSIS OF ALTERNATIVES
2-ethylhexanol
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 184 °C
Melting Point: -89 °C
Water solubility: 0,9 g/l
Vapour Pressure: <1 hPa (20 °C)
Partition coeff.: log Kow = 2,9
Density: 0.83 g/cm3
Flammability: No
Hazards Identification
104-76-7
203-234-3
2-ethylhexan-1-ol
C8H18O
According to Regulation (EC) No. 1272/2008:
Not classified
Registration documentation1:
Skin Irrit. 2 (H315)
Eye Irrit. 2A (H319)
Acute Tox. 4 (H332)
STOT SE 3 (H335)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
76
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ANALYSIS OF ALTERNATIVES
2-heptanone
CAS Number:1
110-43-0
EC Numer:1
203-767-1
3
Synonym:
heptan-2-one; methyl n-amyl ketone
Molecular formula:1
C7H14O
1,2
Physical and Chemical Properties
Boiling Point2: 151.2 °C
Water solubility: 4.21 g/l (20 °C)
Slightly soluble in water. Soluble in alcohol, propylene glycol, ether.
Vapour Pressure1: 918 Pa (25 °C)
Vapour Density: 3.94 (Air = 1)
Density1: 0.814 g/cm3
Partition Coeff.: log Kow = 2.26
Flammability: No
Hazards Identification
According to Regulation (EC) No. 1272/2008:
(index No. 606-024-00-3)
Flam. Liq. 3 (H226)
Acute Tox. 4 (H302+H332)
Registration documentation:
Same as harmonized classification.
STOT SE 3 (H336)
Potential Acute Health Effects:
Potential Chronic Health Effects:
Sources
1
http:// echa.europa.eu/
2
Večeřa M., Gasparič J., Churáček J., Borecký J., Chemické tabulky organických sloučenin,
Státní nakladatelství technické literatury (SNTL), Praha (1975)
3
pubchem.ncbi.nlm.nih.gov/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
2-methylcyclohexanol
CAS Number:1
583-59-5
EC Numer:1
209-512-0
Synonym:
Molecular formula:1
C7H14O
Physical and Chemical Properties
Boiling Point:1 166 °C
Melting Point: 1-45 °C
Water solubility:1 15.6mg/l
Vapour Pressure:1 4 hPa (20 °C)
Partition coeff.:2 log Kow = 1.83 (average value of cis- (1.84) and trans-isomers (1.82)
Density: 0.93 g/cm3
Flammability: No
Hazards Identification
According to Regulation (EC) No. 1272/2008:
(index No. 603-010-00-9)
Acute Tox. 4 (H332)
Registration documentation:
Same as harmonized classification.
Acute Tox. 4 (H302)
Eye Irrit. 2 (H319)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
2
Funasaki N., Hada S., Neya S., Prediction of retention times in reversed-phase highperformance liquid chromatography from the chemical structure, Journal of
chromatography, 361, p. 33-45 (1986)
Use number: 1
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ANALYSIS OF ALTERNATIVES
alkyl phenols
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:
Physical and Chemical Properties
Boiling Point2: 300-350 °C
Water solubility3: 0.002 g/l
Partition coeff.3: log Kow = 7.17
Density2: 0.93 g/cm3
Flammability: No
Hazards Identification
27193-86-8
248-312-8
n/a
According to Regulation (EC) No. 1272/2008:
Not classified
Registration documentation:
Not classified
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://www.chemicalbook.com/ChemicalProductProperty_EN_CB8499183.htm
2
Brooke D., Mitchell R., Watts C., Dungey S., Environmental risk evaluation report: paraC12-alkylphenols (dodecylphenol and tetrapropenylphenol), Environment Agency, Bristol,
United Kingdom (2007) (available 1.5.2014 at:
https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/290856/scho06
07bmvn-e-e.pdf)
3
Proposal of identification of a substance as a CMR, PBT, vPvB or a substance of an
equivalent level of concern, ECB - Summary fact sheet, PBT working group, List No. 55
(available 1.5.2014 at: http://esis.jrc.ec.europa.eu/doc/PBTevaluation/PBT_sum055_CAS_27193-86-8.pdf)
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
benzene
CAS Number:3
71-43-2
EC Number:3
200-753-7
1
Synonym:
Benzol; Benzine
Molecular formula:3
C6H6
1
Physical and Chemical Properties
Boiling Point: 80.1 °C (176.2°F)
Melting Point: 5.5 °C (41.9°F)
Critical Temperature: 288.9 °C (552°F)
Density: 0.8787 (15 °C) (Water = 1)
Vapour Pressure: 10 kPa (20 °C)
Vapour Density: 2.8 (Air = 1)
Water Solubility3: 1.8 g/l
Odor Threshold: 4.68 ppm
Partition Coeff.: log Kow = 2.1
Solubility: Miscible in alcohol, chloroform, carbon disulfide oils, carbon tetrachloride, glacial
acetic acid, diethyl ether, acetone.
Very slightly soluble in cold water
Flammability: Yes
Hazards Identification
According to Regulation (EC) No. 1272/2008:
(index No. 601-020-00-8)
Flam.Liq. 2 (H225)
Asp. Tox. 1 (H304)
Skin Irrit. 2 (H315)
Eye Irrit. 2 (H319)
Muta. 1B (H340)
Carc. 1A (H350)
STOT RE 1 (H372)
Registration documentation:
Same as harmonized classification.
Potential Acute Health Effects:1
Very hazardous in case of eye contact (irritant), of inhalation. Hazardous in case of skin
contact (irritant, permeator), of ingestion. Inflammation of the eye is characterized by redness,
watering, and itching.
Potential Chronic Health Effects1:
CARCINOGENIC EFFECTS: Classified A1 (Confirmed for human.) by ACGIH, 1
(Proven for human.) by IARC.
MUTAGENIC EFFECTS: Classified POSSIBLE for human. Mutagenic for mammalian
somatic cells. Mutagenic for bacteria and/or yeast.
DEVELOPMENTAL TOXICITY: Classified Reproductive system/toxin/female
[POSSIBLE].
The substance is toxic to blood, bone marrow, central nervous system (CNS).
The substance may be toxic to liver, Urinary System.
Repeated or prolonged exposure to the substance can produce target organs damage.
Sources
1
http://www.clpchemicals.com/msds/Benzene %20MSDS %20CLP %20Chemicals.pdf
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
2
http://www.eurisotop.com/_files/uploads/MSDS/benzene %20d6.pdf
http://echa.europa.eu/
Reference
Stratula C., Mihai T., Cheta I., Oprea F., Comparative study of caprolactam purification with
two solvents, Revista de Chimie (Bucharest), 43(7), p. 372-81 (1992)
Dsinter de Hondt M.L.Ch., Groot Zevert L.A., Lemmens J.A.W., Process for recovering and
purifying caprolactam from an organic solvent, WO 02070475, DSM N.V., Netherland (2002)
3
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
bis(2-ethylhexyl)hydrogen phosphate
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 240 °C (decomposition)
Melting Point: -50 °C
Water solubility: 0,182 g/l
Vapour Pressure: < 0,1 hPa (20 °C)
Partition coeff.: log Kow = 2,67
Density: 0.98 g/cm3
Flammability: No
Hazards Identification
298-07-7
206-056-4
diisooctyl phosphate
C16H35O4P
According to Regulation (EC) No. 1272/2008:
Not classified.
Registration documentation1:
Acute Tox. 4 (H302)
Skin Corr. 1C (H314)
Eye Dam. 1 (H318)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
cyclohexane
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 80.7 °C
Melting Point: 6.5 °C
Water solubility: 0.052 g/l
Vapour Pressure: 12.7 kPa (20 °C)
Partition Coeff.: log Kow = 3.44
Density: 0.78 g/cm3
Flammability: Yes
Hazards Identification
110-82-7
203-806-2
C6H12
According to Regulation (EC) No. 1272/2008:
(index No. 601-017-00-1)
Flam. Liq. 2 (H225)
Asp. Tox. 4 (H304)
Skin Irrit. 2 (H315)
STOT SE 3 (H336)
Aquatic Acute 1 (H400)
Aquatic Chronic 1 (H410)
Registration documentation:
Same as harmonized classification (without Aquatic Chronic (H410)).
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
cyclohexanol
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 161 °C
Melting Point: 25.9 °C
Water solubility: 37.6 mg/l
Density: 0.94 g/cm3
Vapour Pressure: 97 Pa (25 °C)
Partition coeff.: log Kow = 1.25
Flammability: No
Hazards Identification
108-93-0
203-630-6
C6H12O
According to Regulation (EC) No. 1272/2008:
(index No. 603-009-00-3)
Acute Tox. 4 (H302+H332)
Skin Irrit. 2 (H315)
STOT SE 3 (H335)
Registration documentation:
Same as harmonized classification.
Eye Irrit. 2 (H319)
Potential Acute Health Effects:
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
cyclohexene
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 83 °C
Melting Point: -103.5 °C
Water solubility: 0.16 g/l
Density: 0.81 g/cm3
Vapour Pressure: 119 hPa (25 °C)
Partition coeff.: log Kow = 2.99
Hazards Identification
110-83-8
203-807-8
C6H10
According to Regulation (EC) No. 1272/2008:
Not classified
Registration documentation:
Flam. Liq. 2 (H225)
Acute. Tox. 4 (H302)
Asp. Tox. 1 (H304)
Aquatic Chronic 2 (H411)
Potential Acute Health Effects:
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
dichloromethane
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 40 °C
Melting Point: -95 °C
Water solubility: 13.2 g/l
Vapour Pressure: 58.400 kPa (25 °C)
Partition Coeff.: log Kow = 1.25
Density: 1.33 g/cm3
Flammability: No
Hazards Identification
75-09-2
200-838-9
methylene chloride, Freon 30
CH2Cl2
According to Regulation (EC) No. 1272/2008:1
(index No. 602-004-00-3)
Carc. 2 (H351)
Registration documentation1:
Skin Irrit. 2 (H315)
Eye Irrit. 2 (H319)
STOT SE 3 (H336)
Carc. 2 (H351)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
chlorobenzene
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 132 °C
Melting Point: –45 °C
Water solubility: 0.5 g/l
Density: 1.11 g/cm3
Vapour Pressure: 11.7 hPa (20 °C)
Partition coeff.: log Kow = 2.84
Hazards Identification
108-90-7
203-628-5
monochlorobenzene, phenyl chloride
C6H5Cl
According to Regulation (EC) No. 1272/2008:
(index No. 602-033-00-1)
Flam. Liq. 3 (H226)
Acute Tox. 4 (H332)
Aquatic Chronic 2 (H411)
Registration documentation:
Currently it is proposed tighter classification which is the same as self-classification specified
in registration dossier.
Flam. Liq. 3 (H226)
Skin Irrit. 2 (H315)
Acute Tox. 4 (H332)
Aquatic Chronic 2 (H411)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
Chloroform
CAS Number:1
EC Numer:1
Synonym:1
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 62 °C
Melting Point: -63,5 °C
Water solubility: 8 g/l
Density: 1.48 g/cm3
Vapour Pressure: 211 Pa (20 °C)
Partition coeff.: log Kow = 1,97
Flammability: No
Hazards Identification
67-66-3
200-663-8
trichloromethane
CHCl3
According to Regulation (EC) No. 1272/2008:
(index No. 602-006-00-4)
Acute Tox. 4 (H302)
Skin Irrit. 2 (H315)
Carc. 2 (H351)
STOT RE 2 (H373)
Registration documentation:
Same as harmonized classification.
Acute Tox. 4 (H322)
Eye Irrit. 2 (H319)
Repr. 2 (H361)
STOT SE 3 (H336)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
88
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ANALYSIS OF ALTERNATIVES
diethylether
CAS Number:1
EC Numer:1
Synonym:1
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 34.6 °C
Melting Point: -116.3 °C
Water solubility: 64.9 g/l
Density: 0.71 g/cm3
Vapour Pressure: 589.6 kPa (20 °C)
Partition coeff.: log Kow = 0.83
Flammability: Yes
Hazards Identification
60-29-7
200-467-2
1,1'-oxydiethane, ether
C4H10O
According to Regulation (EC) No. 1272/2008:
(index No. 603-022-00-4)
Flam. Liq. 2 (H225)
Acute Tox. 1 (H302)
STOT SE 3 (H336)
EUH019
Registration documentation1:
Same as harmonized classification.
Potential Acute Health Effects:
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
Ligroin
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties1
Boiling Point: 20 – 260 °C
Melting Point: < -60 °C
Water solubility: n/a (UVCB substance)
Vapour Pressure: > 240 kPa (37.8 °C)
Partition Coeff.: n/a (UVCB substance)
Density: 0.62-0.88 g/cm3
Flammability: No
Hazards Identification
8032-32-4
232-453-7
n/a (UVCB substance)
According to Regulation (EC) No. 1272/20081:
(index No. 649-263-00-9)
Asp. Tox. 1 (H304)
Muta. 1B (H340)
Carc. 1B (H350)
Registration documentation1:
(There are several registered classification differing according to composition.)
Flam. Liq. 2 (H225)
Asp. Tox. 1 (H304)
Skin Irrit. 2 (H315)
STOT SE (H336)
Muta. 1B (H340)
Carc. 1B (H350)
Repr. 2 (H361)
Aquatic Chronic 2 (H411)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
Methylcyclohexane
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 100.93 °C
Melting Point: -126.6 °C
Water solubility: 14 mg/l
Density: 0.77 g/cm3
Vapour Pressure: 6.18 kPa (25 °C)
Partition coeff.: log Kow = 3.88
Flammability: Yes
Hazards Identification
108-87-2
203-642-3
C7H14
According to Regulation (EC) No. 1272/2008:
(index No. 601-018-00-7)
Flam. Liq. 2 (H225)
Asp. Tox. 1 (H304)
Skin. Sens. 2 (H315)
STOT SE 3 (H336)
Aquatic Chronic. 2 (H411)
Registration documentation:
Same as harmonized classification.
Aquatic Acute 1 (H400)
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
n-heptane
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 98,2 °C
Water solubility: 2,4 g/l (20 °C)
Vapour Pressure: 6,09 kPa (25 °C)
Partition coeff.: log Kow = 4,5
Flammability: Yes
Hazard Identification
142-82-5
205-563-8
Heptane
C7H16
According to Regulation (EC) No. 1272/2008:
(index No. 601-008-00-2)
Flam. Liq. 2 (H225)
Asp. Tox. 1 (H304)
Skin Irrit. 2 (H315)
STOT SE 3 (H336)
Aquatic Acute 1 (H400)
Aquatic Chronic 1 (H410)
Registration documentation1:
Same as harmonized classification.
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
n-hexane
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 68,73 °C
Melting Point: -95,35 °C
Water solubility: 0,01 g/l
Vapour Pressure: 10 kPa (9,8 °C)
Partition coeff.: log Kow = 4
Flammability: Yes
Hazards Identification
110-54-3
203-777-6
Hexane
C6H14
According to Regulation (EC) No. 1272/2008:
(index No. 601-037-00-0)
Flam. Liq. 2 (H225)
Asp. Tox. 1 (H304)
Skin Irrit. 2 (H315)
STOT SE 3 (H336)
Repr. 2 (H361f)
STOT RE 2 (H373)
Aquatic Chronic 2 (H411)
Registration documentation1:
Same as harmonized classification.
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
nitrobenzene
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 210.8 °C
Melting Point: 5.26 °C
Vapour Pressure: 20 Pa (20 °C)
Water Solubility: 1.9 g/l
Partition Coeff.: log Kow 1.86
Density: 1.2 g/cm3
Flammability: No
Hazards Identification1
98-95-3
202-716-0
C6H5NO2
According to Regulation (EC) No. 1272/2008:
(index No. 609-003-00-7)
Acute Tox. 3 (H301+H311+H331)
Canc. 2 (H351)
Repr. 2 (H361f)
STOT RE 1 (H372)
Aquatic Chronic 2 (H411)
Registration documentation:
Same as harmonized classification.
Potential Acute Health Effects:
Potential Chronic Health Effects:
Sources
1
www. http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
octanol (mixed isomers)
CAS Number:1
EC Numer:1
Synonym:
Molecular formula1:
Physical and Chemical Properties
Boiling Point3: 196 °C
Water solubility2: 0.586 g/l
Density3: 0.82-0.83 g/cm3 (individual isomers)
Flammability: No
Hazards Identification
29063-28-3
249-405-6
C8H18O
According to Regulation (EC) No. 1272/2008:
Not classified
Registration documentation:
Not classified
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://www.chemnet.com/cas/cz/29063-28-3/Octyl-alcohol,-mixed-isomers.html
2
Hansch C., Quinlan J.E., Lawrence G.L., Linear free energy relation between partition
coefficients and the aqueous solubility of organic liquids, Journal of Organic Chemistry,
33, p. 347 (1968)
3
OECD QSAR Toolbox database (ver. 3.1)
Use number: 1
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ANALYSIS OF ALTERNATIVES
tetrachloroethylene
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 121.4 oC
Melting Point: -22 °C
Water solubility: 0.15 g/l
Partition coeff.: log Kow = 2.53
Density: 1.62 g/cm3
Flammability: No
Hazards Identification
127-18-4
204-825-9
C2Cl4
According to Regulation (EC) No. 1272/2008:
(index No. 602-028-00-4)
Carc. 2 (H351)
Aquatic chronic 2 (H411)
Registration documentation:
Same as harmonized classification.
Skin Irrit. 2 (H315)
Eye Irrit. 2 (H319)
Skin sens. 1B (H317)
STOT SE 3 (H336)
Sources
1
http://echa.europa.eu/
Use number: 1
Legal name of the applicant(s) SPOLANA, a.s.
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ANALYSIS OF ALTERNATIVES
tetrachloromethane
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 76.8 °C
Melting Point: -22.62 °C
Water solubility: 0.85 g/l
Density: 1.59 g/cm3
Vapour Pressure: 15.2 kPa (25 °C)
Partition coeff.: log Kow = 2.83
Flammability: No
Hazards Identification
56-23-5
200-262-8
carbon tetrachloride
CCl4
According to Regulation (EC) No. 1272/2008:
(index No. 602-008-00-5)
Acute Tox. 3 (H301+311+331)
Carc. 2 (H351)
STOT RE 1 (H372)
Aquatic Chronic 3 (H412)
Ozozne 1 (H420)
Registration documentation:
Same as harmonized classification.
Skin Sens. 1B (H317)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
http://echa.europa.eu/
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ANALYSIS OF ALTERNATIVES
Toluene
CAS Number:1
EC Numer:1
Synonym:
Molecular formula:1
Physical and Chemical Properties 1
Boiling Point: 110.6 °C
Melting Point: -95 °C
Water solubility: 0.58 g/l
Density: 0.87 g/cm3
Vapour Pressure: 29.3 hPa (20 °C)
Partition coeff.: log Kow = 2.73
Flammability: Yes
Hazards Identification
108-88-3
203-625-9
methylbenzene
C7H8
According to Regulation (EC) No. 1272/2008:
(index No. 601-022-00-9)
Flam. Liq. 2 (H225)
Asp. Tox. 1 (H304)
Skin Irrit. 2 (H315)
STOT SE 3 (H336)
Repr. 2 (H361d)
STOT RE 2 (H373)
Registration documentation:
Same as harmonized classification.
Eye Irrit. 2 (H319)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
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ANALYSIS OF ALTERNATIVES
xylene (mixed isomers)
CAS Number:1
1330-20-7
EC Numer:1
215-535-7
Synonym:
dimethylbenzene
Molecular formula:1
C8H10
1
Physical and Chemical Properties
Boiling Point: cca 140 °C (according to composition)
Melting Point: 13.2 - –95,0 °C (according to composition)
Water solubility: 0.15 - 0.18 g/l (according o composition)
Density: 0,86 - 0,88 g/cm3
Vapour Pressure: 88 Pa/25 oC
Partition coeff.: log Kow = 3.1 - 3.2 (according to composition)
Flammability: No
Hazards Identification
According to Regulation (EC) No. 1272/2008:
(index No. 601-022-00-9)
Flam. Liq. 3 (H226)
Acute Tox. 4 (H312+H332)
Carc. 2 (H351)
Skin Irrit. 2 (H315)
Registration documentation:
Same as harmonized classification.
Asp. Tox. 1 (H304)
Eye Irrit. 2 (H319)
STOT RE 2 (H373)
Potential Acute Health Effects:1
Potential Chronic Health Effects:
Sources
1
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ANALYSIS OF ALTERNATIVES
Appendix 2: Alternative technologies of caprolactam production study
Synthesis of caprolactam from cyclohexanone oxime
Cyclohexanone oxime is the key intermediate and it is produced mainly via oximation of
cyclohexanone with hydroxylamine but can also be made from phenol or toluene. Several
alternative oximation processes are in commercial operation. The oldest approach is the Rashig
process, developed in the 1940s and 1950s, which leads to the highest yields of ammonium
sulphate.
Synthesis of cyclohexanone oxime from cyclohexanone by ammoximation reaction
The reaction of cyclohexanone with hydroxylamine sulphate is well known method for production
of cyclohexanone oxime. The hydroxylamine is manufactured by the oxidation of ammonia to
nitrous oxide, followed by hydrogenation in the presence of sulphuric acid. The hydroxylamine
sulphate is then reacted with cyclohexanone to produce cyclohexanone oxime (Caprolactam: A
Techno-Commercial Profile, 2009).
Some manufactures produce hydroxylammonium by the modified Rashig process using ammonium
salts as starting materials. Oximation is then carried out with aqueous hydroxylammonium sulphate
solution containing ammonium sulphate. The sulphuric acid liberated is neutralized with ammonia
to form ammonium sulphate. The amount of ammonium sulphate formed during the oximation is
about 2.7 tons per ton of cyclohexanone oxime (Jubb, 1971).
This formation of cyclohexanone oxime by ammoximation method was attempted by different
ways. The main process methods are described below.
Beckman rearrangement to caprolactam
Cyclohexanone oxime is converted to caprolactam mainly via process known as the Beckmann
rearrangement. A solution of cyclohexanone in oleum/sulphuric acid is heated and maintained at a
temperature of around 100 °C, and within a few minutes the oxime is rearranged to the lactam
sulphate. The crude caprolactam is removed in a separator drum and fed to an extractor.
Caprolactam is extracted with solvents such as benzene, toluene or chlorinated hydrocarbons
(Heese, 2011),(Ritz, Fuchs, Kieczka, & Moran, 1986).
The reaction is tremendously exothermic, which necessitates large recycles of ammonium sulphate
and large equipment sizing. This incurs considerable cost in cooling the reaction, even if the heat is
removed for use in downstream caprolactam purification (Caprolactam: A Techno-Commercial
Profile, 2009).
Sumitomo rearrangement
Cyclohexanone sulphate is also converted to caprolactam in some commercial processes by another
route known as the Sumitomo rearrangement. This involves direct conversion of the oxime to the
lactam using a modified zeolite catalyst at elevated temperature in the vapour phase (Heese, 2011).
Sumitomo has successfully commercialized a process for the Beckmann rearrangement free of
oleum and ammonium sulphate. The process uses a liquid bed reactor operating at around 350 °C
with a small positive pressure and a methanol „promoter“ (Caprolactam: A Techno-Commercial
Profile, 2009).
The process has clear advantages when the whole cyclohexane to caprolactam train is considered
and leads to certain savings in capital investment. However, liquid bed processes tend to be more
capital intensive in terms of reactor cost. A combination of ammoximation and liquid bed
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Beckmann provides zero ammonium sulphate co-product (Caprolactam: A Techno-Commercial
Profile, 2009).
BASF process
The BASF process for production of hydroxylammonium sulphate solution generates about 0.7 tons
of ammonium sulphate per ton of cyclohexanone oxime. A similar process has been developed by
Inventia (Caprolactam Supplement, May 2, 1969). BASF and Inventia obtain the
hydroxylammonium sulphate solution by the hydrogenation of nitric oxide over a platinum catalyst
in the presence of dilute sulphuric acid. The hydroxylammonium sulphate solution is reacted with
cyclohexanone and ammonia in an oxime reactor. This reaction is conducted at 85 – 90 °C with
through mixing in a weak acidic solution. Cyclohexanone oxime is obtained as a moist melt. It is
separated from the aqueous solution in a separator drum. The purified aqueous ammonium sulphate
solution is free of substances that would be undesirable in fertilizer- or technical-grade salt uses
(Figure 1)
Figure 1: The BASF process (Mettu, 2009).
A second process developed by BASF is the acidic oximation process. The first step of this process
is the catalytic hydrogenation of nitric oxide in an ammonia hydrogen sulphate solution over
platinum or graphite. In a second step cyclohexanone is reacted to cyclohexanone oxime with
ammonium hydroxylammonium sulphate. Complete conversion of cyclohexanone is achieved with
a classic after-oximation reaction. In this process 0.1 ton of ammonium sulphate per ton of
cyclohexanone oxime is formed as a by-product (Weissermal, 1994).
Figure 2: Acidic oximation process (Mettu, 2009).
A disadvantage of existing technology is that large amounts of ammonium sulphate (up to 4.5
tons/ton of caprolactam) are produced. Much development work is concentrating or reducing or
even eliminating this by-product.
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Both method used for caprolactam production by BASF are finished by extraction of caprolactam
with commonly used organic solvents (e.g. benzene, toluene, chlorinated hydrocarbons, etc.).
Hydroxylamine-phosphate Oxime process (HPO process of DSM)
DSM Company developed the HPOplus process. In this process the ammoximation reaction is
conducted in a hydroxylamine phosphoric acid buffer solution.
The first step is the reduction of the phosphoric acid/ammonium nitrate buffer solution with
hydrogen and the formation of hydroxylammonium phosphate. This reaction is catalyzed with
palladium on graphite or alumina carrier. The second step is the formation of the oxime. In the third
step, after separation of the cyclohexanone oxime, the nitrite ions consumed are replaced by the
addition of 60 % nitric acid solution (Figure 3).
Figure 3: HPO process of DSM (Mettu, 2009)
The hydroxylamine formed by catalytic hydrogenation of nitrate ions reacts with free phosphoric
acid in the buffer solution at pH 1.8 to form a hydroxylammonium phosphate solution. The reaction
takes place in special columns. The unreacted hydrogen is separated from the catalyst suspension in
a separator, and is recycled to the reaction via a compressor. After catalyst has been filtered and
recycled, the hydroxylamine buffer solution reacts with cyclohexanone in the oximation reactor to
produce cyclohexanone oxime. Toluene is used as the solvent and phosphoric acid is liberated.
Oximation takes place in a cascade of mixers and separators with a countercurrent process at pH 2.
Conversion is 98 % (Weissermal, 1994).
Photonitrosation
In the 1950s, Toray industries developed a photochemical process for the production of
caprolactam. Photonitrosation (PNC) converts cyclohexanone oxime dihydrochloride followed by
Beckman rearrangement.
The cyclohexane is reacted with nitrosyl chloride to give cyclohexanone oxime hydrochloride. The
first step is preparation of nitrosylsulphuric acid from nitrous gases obtained from combustion of
ammonia, and sulphuric acid. The second step is preparation of nitrosyl chloride by reaction with
hydrogen chloride. The third step is photochemical reaction (Figure 4)
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The industrial photonitrozation process is based on the development of efficient photoreactors.
Toray designed an immersion lamp with a radiation efficiency and capacity as well as long life. In
order to remove the shortwave radiation below 365 nm, which contributes to tar formation on the
lamps, an absorbent is added to the cooling water, or the light source is surrounded by a glass filter.
The cyclohexanone oxime produced by photonitrozation of cyclohexane is separated as the
dihydrochloride in the presence of excess hydrogen chloride. This compound exists in the form of
oil droplets and forms a heavier lower phase in cyclohexane. This lower phase is subjected to
Beckmann rearrangement with excess sulphuric acid or oleum to give caprolactam (Ritz, Fuchs,
Kieczka, & Moran, 1986).
In the PNC Torray process 1.5 tons of ammonium sulphate is produced per ton of caprolactam. The
major drawback of this process is the highly energy consumption (Weissermal, 1994), (Turner,
1969).
Figure 4: Photonitrosation process (Mettu, 2009).
EniChem process
EniChem recently developed a new environmentally benign process for synthesis of cyclohexanone
oxime from cyclohexanone over TS-1 catalyst in presence of H2O2 and NH3. This reaction operates
in the liquid phase under mild conditions and proceeds very high yield. Moreover, this process has
100 % theoretical atom economy.
In the EniChem process two reaction pathways have been proposed for formation of cyclohexanone
oxime.
1) According to Reddy et al. (Reddy, Sivasanker, & Rathnasamy, 1991) ammonia reacts in a
first step with ketone, forming the corresponding imine, the latter is then oxidized by
hydrogen peroxide imide the pores of TS-1, giving rise to the formation of the oxime.
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ANALYSIS OF ALTERNATIVES
2)
Figure 5: Ammoximation process 1st (Reddy, Sivasanker, & Rathnasamy, 1991).
3) According to Tozzola et al. (Tozzola, a další, 1998) ammonia reacts imide the pores of TS-1
forming the hydroxylamine that reacts immediately with the ketone, resulting in the
formation of oxime.
Figure 6: Ammoximation process 2nd (Tozzola, a další, 1998).
Synthesis of caprolactam without cyclohexanone oxime as an intermediate product
In order to find new synthesis routes for production of caprolactam without cyclohexanone oxime
as an intermediate, different companies have attempted for new synthesis routes. The four most
important processes are SNIA Viscosa process, the UCC caprolactam process, the TechniChem
Nitrocyclohexanone process, Cyclopol process and the BP hydrogen peroxide process.
SNIA Viscosa process
SNIA Viscosa developed a toluene-based process in 1960. Caprolactam is obtained during three
steps.
1) Catalytic oxidation of toluene with oxygen to benzoic acid,
2) Hydrogenation of benzoic acid to cyclohexanecarboxylic acid,
3) Nitrosodecarboxylation of cyclohexanecarboxylic acid to caprolactam in the presence of
oleum.
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Toluene is converted in the liquid phase to benzoic acid at 160 – 170 °C and 0.8 – 1.0 MPa on a Cu
catalyst with 30 % conversion and 92 % selectivity for benzoic acid. The benzoic acid is
subsequently hydrogenated to cyclohexanoic acid at 170 °C and 1.0 – 1.7 MPa over a Pd/charcoal
catalyst. Nitrosylsulphuric acid (NOHSO4) is then added to the carboxylic acid in cyclohexane
(80 °C). This process avoids the Beckmann rearrangement common to the previous processes.
However, some ammonium sulphate (4 tons/ton of caprolactam) is still produced.
As of 1980, it is estimated that 8 % of the world production of caprolactam proceeded by this route.
With help of nitrosylsulphuric acid in oleum, cyclohexanoic acid can be converted to a cyclic
anhydride at reaction of 80 °C (Mettu, 2009).
The caprolactam solution is purified in several stages. It is first separated from the water-soluble
byproducts by toluene extraction. An aqueous caprolactam solution is then obtained by
countercurrent extraction of the caprolactam-toluene solution with water. The toluene-soluble
byproducts remain in the organic layer. Water is removed from the aqueous caprolactam solution
and the product distilled to give pure caprolactam (Ritz, Fuchs, Kieczka, & Moran, 1986).
The UCC process
Union Carbide has developed a process for the manufacture of caprolactam based on the following
reaction sequence:
Figure 7: The UCC process (Ritz, Fuchs, Kieczka, & Moran, 1986)
This reaction can be carried out by two methods:
1) Cyclohexanone is reacted with peracetic acid in an anhydrous medium, such as acetone.
With an excess of cyclohexane, ε-caprolactone is obtained in a yield of about 90 %.
2) Oxidation can also be carried out in situ. Cyclohexanone is reacted with air at 25 – 50 °C
with the simultaneous introduction of acetaldehyde. An excess of cyclohexanone is also
used in this case. Manganese, cobalt, platinum, palladium, vanadium and zirconium salts
and their oxides on carriers are examples of suitable oxidation catalysts. The acetic acid
formed as a byproduct during the oxidation (about 1.1 kg/kg of caprolactam) is separated
from the ε-caprolactone by distillation.
The conversion of caprolactone to caprolactam with ammonia can rather be carried out in
anhydrous or aqueous medium, preferably at 350 – 425 °C at increased pressure. An excess of
ammonia is used. The caprolactone in aqueous medium is isolated by extraction. The total yield is
65 – 70 % (Ritz, Fuchs, Kieczka, & Moran, 1986), (Mettu, 2009).
The Techni-Chem Process
The Techni-Chem Company has developed a procedure for the production of 6-hexanelactam,
based on cyclohexanone. Its advantage is that no byproduct is formed in the synthesis. In spite of
this, however, the synthesis is very complicated and so far has not been applied on an industrial
scale. The main disadvantage of this process is the use of the expensive ketene. This process was
never used on an industrial scale by reason of high costs of the production of acetic anhydride and
ketene, although it was the first process free of byproduct (Mettu, 2009).
The chemistry of the process can be described by the following steps:
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1) Preparation of cyclohexenyl acetate, followed by its nitration to 2-nitrocyclohexanone.
Cyclohexanone is acetylated in an excess of acetic anhydride in the presence of ketene at
140 °C, with sulphuric acid used as the catalyst. Acetic acid thus obtained reacts with ketene
to form acetic anhydride. Cyclohexenyl acetate formed in the reaction is nitrated in acetic
anhydride with concentrated nitric acid at 30 – 50 °C to 2-nitrocyclohexanone. Acetic acid
formed in the nitration returns to the process of ketene production.
2) Ring opening of 2-nitrocyclohexanone to the ammonium salt of 6-aminohexanoic acid is
carried out using dilute ammonia at 40 – 60 °C in a quantitative yield.
3) Hydrogenation of the ammonium salt of 6-nitrohexanoic acid to 6-aminohexanoic acid
proceeds at 100 °C and hydrogen pressure 2 MPa with Raney nickel catalyst. The yield is
almost quantitative.
4) Cyclization of 6-aminohexanoic acid takes place at 300 °C and pressure 10 MPa.
Figure 8: The Techni-Chem process (Mettu, 2009).
The company Teijin Ltd. has suggested a procedure in which 6-hexanelactam is obtained from 2nitrocyclohexanone (ring opening, hydrogenation and cyclization) in one stage (Puffr & Kubanek,
1991).
Alternative routes with butadiene as raw material
The use of butadiene as a starting material for the nylon synthesis is very attractive, since it is
relatively cheap and its use strongly reduces the amount of inorganic waste. Two best explored
routes so far for the synthesis of caprolactam out of butadiene are shown in Figure 9. The upper
route uses alkylcarbonylation followed by hydroformylation and reductive amination and the
bottom route applies hydrocyanation to increase the length of the alkyl chain. The
alkoxycarbonylation of the upper route is still problematic and rhodium catalyzed hydroformylation
is very expensive, which limits the potential of the upper route. Although the selective
hydrogenation of adiponitrile into 6-aminocapronitrile (ACN) is not fully optimized yet, the
chemistry is already well developed. This increases the chance for industrial application of the
bottom method appreciably (van Dijk, 2006).
Figure 9: Butadiene-based routes to caprolactam or nylon-6 (van Dijk, 2006).
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Caprolactam from butadiene: Hydroesterification
The industrially most important alternative to the heterogeneous process is the production of
caprolactam based on butadiene. According to data published by SRI consulting, it is possible to
produce caprolactam with lower cost than existing processes. That route was investigated when
market price of butadiene was low.
Figure 10: The different reaction pathways in the hydroformylation of methyl-3-pentanoate with
the desired captured by the frame (van Dijk, 2006).
In this first step hydroesterification of butadiene to methyl-3-pentenoate is performed with carbon
monoxide and methanol in presence of a cobalt complex catalyst. The next step in the descried
synthesis is the hydroformylation. The catalyst in the BASF process is the assembly the same
octacarbonitrilcobalt(0)-pyridine complex, whereas the catalyst in the DSM process is rhodiumhydride-carbonyl complex with bis-(phosphorus-triarylester). For the hydroformylation, an
isomerization of methyl-3-pentenoate is conducted. In hydroformylation step, the methyl-4pentenoate is then directly converted into methyl-5-formylvalerate, which is the starting compounds
for the next step, or the product of the hydroesterification, the methyl-3-pentenoate is directly
hydroformylated after in situ isomerization to methyl-4-pentenoate. The third step of the synthesis
is reductive amination and cyclization to caprolactam, for which two routes are described.
1) the methyl-5-formylvalerate is reductively aminated to 6-aminohexanoate be followed by a
cyclic amidation of 6-aminohexanoate to caprolactam,
2) methyl-5-formylvalerate is hydrolyzed to 5-formylvaleric acid followed by the reductive
amination to 6-aminohexanoic acid and the subsequent cyclic amidation to caprolactam.
With there, yields of 5-formylvaleric acid of 74 % are obtained over cation exchange resin catalysts,
followed by reductive amination to 6-aminohexanoic acid on Raney Ni catalyst with yields of 57 %
amination to 6-aminohexanoic acid is cyclized to caprolactam without a catalyst at 300 °C with
yields of 95 % (Mettu, 2009).
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Caprolactam form butadiene: Hydrocyanation
The hydrocyanation of butadiene is a well-established process based on homogeneous nickel
phosphate catalysts.
Figure 11: Butadiene to caprolactam: hydrocyanation (Mettu, 2009).
The first step in this process is hydrocyanation of butadiene to hexendinitrile. It was developed by
DuPont for the production of hexendinitrile, which is precursor for hexanmethylenediamine, the
monomer for nylon 6,6. In a second step, selective partial hydrogenation of hexendinitrile to 6aminohexanenitrile followed. According to DuPont, the hexendinitrile is hydrogenated with
molecular hydrogen at 6.9 MPa and 80 °C on a Raney Ni catalyst in liquid NH3. The selective
hydrogenation of hexanedinitrile to 6-aminohexaninitrile is performed over Raney Ni catalyst in the
presence of 1,6-hexanediamine and KOH with a conversion of 81 % and a 60.3 % yield. The last
step in this synthesis route is the cyclization of 6-aminohexanenitrile to obtain caprolactam.
In the butadiene based caprolactam routes several separation and recycling steps of the products and
by-products are necessary. It seems that hydrocyanation of butadiene to caprolactam is more likely
for an industrial realization than route via hydroesterification (Mettu, 2009).
Caprolactam from 6-aminocapronitrile
The production of caprolactam from 6-aminocapronitrile (ACN) by cyclization (Figure 12) in
presence of water at elevated temperature and presence or absence of a catalyst and a solvent is also
promising process.
Figure 12: Production of caprolactam from 6-aminocapronitrile (Mettu, 2009).
This process is characterized in following steps:
1) a mixture (I) containing 6-aminocapronitrile and water in the liquid phase is converted into a
mixture (II) containing caprolactam, ammonia, water, high boilers and low boilers in the
presence of a catalyst,
2) ammonia is then removed from mixture (II), leaving a mixture (III) containing caprolactam,
water, high boilers and low boilers,
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3) water is then removed from mixture (III) leaving a mixture (IV) containing caprolactam,
high boilers and low boilers,
4) a solid (V) containing caprolactam is obtained from mixture (IV) by crystallization, the
proportion by weight of caprolactam in the solid (V) being greater than in the mixture
(Bassler, Baumann, Fischer, Fuchs, Melder, & Ohlbach, 2001).
U.S. Pat. No. US2301964 A ( (Louis, 1942) discloses the production of lactams from aminonitriles
and water in a liquid –phase method. Hydrolysis and concurrent lactam formation proceed rapidly
when aminonitrile is reacted in a weak aqueous solution. Temperatures of from 200 – 375 °C are
employed. The aminonitrile and water are maintained at this reaction temperature for not more than
1 hour. The reaction is preferably catalyzed with hydrogen sulphide.
U.S. Pat. No. US 2301964 A (Louis, 1942) discloses a vapour-phase catalytic process for preparing
N-substituted amines. The process comprises passing a vaporized mixture of water and an aliphatic
aminonitrile, containing at least one aminonitrile moiety, over a dehydration-type catalyst at a
temperature of typically from 150 – 500 °C, for not more than 1 minute. When an open-chain
aliphatic aminonitrile is used, in which the amino and nitrile groups are separated by at least two
carbon atoms in contiguous relation, the product obtained is a lactam.
In recent years, inexpensive adiponitrile (ADN) has been made by the direct hydrocyanation of
butadiene. This has led to a renewed interest in process mentioned upper because inexpensive ADN
can be partially hydrogenated and refined to produce an impure product that comprises ACN. This
product may contain some by-products of the hydrogenation reaction, notably tetrahydroazepine
(THA). U.S. Pat. No. US6716977 B1 (Kirby & Ostermaier, 2004) discloses a method for making
caprolactam from ACN containing THA. Separation of ACN and THA from caprolactam requires a
considerable number of stages in the low boiler column due to the difficulty of separation. A large
number of stages in this column will cause increased pressure drop and excessively high
temperature in the base of the column. It would, therefore, be desirable to have a process to make
caprolactam from ACM on which the impurities in the crude caprolactam product were converted
into species having a higher vapour pressure, which would require fewer distillation stages.
The development on the synthesis of caprolactam from 6-aminocapronitrile, using near- and
supercritical water as the solvent, reactant and catalyst was described in (Yan, etc., 2008). The two
step reaction (hydrolysis and cyclization) to produce caprolactam is combined in a single process,
by using a continuous-flow system. Effects of pressure, temperature, residence time and the
concentration of ACN were studied. The high-temperature high-pressure environment possesses
unique properties which result in very efficient catalysis. The overall caprolactam yield reaches
90 % with a short residence time (˂2 min).
Caprolactam from cyclohexane
Several research groups have been attempted to synthesis of caprolactam from cyclohexane. In
2006, Ischii research group has reported first time in synthesis of caprolactam from cyclohexane
and tert-butyl nitrite (tBuONO) by using N-hydroxyphtalimide as key catalyst (Figure 13).
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Figure 13: Nitrozation of cyclohexane with tert-butyl nitrite (Ishii, Hashimoto, & Sakaquchi, 2006)
Cyclododecane and cyclohexane were treated with tBuONO followed by triethylamine and then
cyanuric chloride in a one-pot manner to give laurolactam and ε-caprolactam, respectively, in good
yields. The Beckmann rearrangement of oximes by cyanuric chloride was found to be accelerated
by the use of 1,1,1,3,3,3-hexafluoro-2-propanol as solvent. The method provides the first successful
environmentally benign direct synthetic route to lactams from cycloalkanes without the formation
of any salt (Ishii, Hashimoto, & Sakaquchi, 2006).
Recently, You et al. (You, Zhao, Long, Liu, Al, & Luo, 2012) reported a one-step formation of
caprolactam from cyclohexane and nitrosyl sulphuric acid catalyzed solid vanadium phosphates
composites (Figure 14).
Figure 14: The liquid phase nitrozation of cyclohexane and nitrosyl sulphuric acid (You, Zhao,
Long, Liu, Al, & Luo, 2012).
These authors have been observed 26 % cyclohexane conversion and 35 % caprolactam selectivity
over Mn and Co introduced Al-VPO composite catalysts.
Caprolactam production in laboratory scale – worldwide publication study
Thomas et al. (Thomas & Raja, 2005) describe synthesis of caprolactam in a viable laboratoryscale. This production of caprolactam is single-step and solvent-free process using bifunctional,
heterogeneous, nanoporous catalysts containing isolated acidic and redox sites, which smoothly
convert cyclohexanone to caprolactam with selectivities in the range 65–78 % in air and ammonia
at 80 °C. The catalysts are aluminophosphates in which small fractions of the AlIIIO4 5- and PVO4 3tetrahedra constituting the 4-connected open framework are replaced by CoIIIPO4 5- and SiIVO4 4tetrahedra, which become the loci of the redox and acidic centers. The catalysts may be further
optimized, and already may be so designed as to generate selectivities of 80 % for the intermediate
oxime, formed from NH2OH, which is produced in situ within the pore system.
Vapour-phase synthesis of caprolactam from cyclohexanone-oxime has been studied using
aluminosilicate SiMCM-48 and AlMCM-48(X) with Si/Al molar ratios X. As solvents was used
benzene, toluene, ethanol and 1- hexanol were utilized as solvents (Chang & Ko, 2004).
A series of transition metal-doped VPO(oxide-vanadium phosphate) composite catalysts were used
to catalyze reaction of cyclohexane with nitrosyl sulphuric acid in the presence of fuming sulphuric
acid. caprolactam was directly obtained from one-step process. While the conversion and selectivity
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are not high at this time to be commercially viable, this discovery establishes a potential new onestep process for making caprolactam from cyclohexane (You, Mao, Chen, Yin, Liu, & Luo, 2008).
Hao et al. (Hao F. , Zhong, Liu, You, Wei, & Luo, 2012) prepared metal substitued (Co, Mn, Cr)
aluminophosphate molecular sieves. Sieves are made from corner-sharing AlO4 (MeAlPOs) and
PO4 tetrahedra (SAPO). These tetrahedra form a three dimensional network containing channels
and pores, which make them particularly attractive for adsorption and catalytic reaction. Authors
were studied catalytic properties of modified molecular sieves in cyclohexane nitrozation to
caprolactam One-step synthesis of caprolactam from cyclohexane nitrozation using amorphous
SiO2-Al2O3 supported Co3O4 was investigated in work same authors (Hao F. , Zhong, Liu, You,
Wei, & Luo) The 20 % Co3O4/SiO2–Al2O3 calcinated at 500 ◦C gives the best result of conversion
of 11.2 % and caprolactam selectivity of 83.3 %, which is the best result since one step synthesis of
caprolactam from cyclohexane nitrozation was developed.
Gui et al. (Gui, Deng, Hu, & Sun, 2004) study Beckmann rearrangement of ketoximes was
performed in a novel task-specific ionic liquid consisting sulfonyl chloride. The reaction was under
mild conditions and without any additional organic solvents. This method is suitable for the
conversion of cyclohexanone oxime to caprolactam, because caprolactam has good solubility in
water while the task-specific ionic liquid is immiscible with water, therefore, caprolactam could be
easily separated from the reaction system by water extraction.
In literature (Vilas & Tojo, 2010) was caprolactam obtained by The Beckmann rearrangement of
cyclohexanone oxime using p-toluenesulfonyl chloride and a new salt, [TMG][TsO], as the
promoter. [TMG][TsO] is 1,1,3,3-tetramethylguanidine p-toluenesulfonate. This reaction requires
mild reaction conditions (60 °C) and affords high levels of conversion of 100 % and selectivity
(99 %) to obtain pure caprolactam in a 98 % yield. In this same work was studied also the
Beckmann rearrangement of several ketoximes using by treatment with tosyl chloride, using ionic
liquids as both solvent and catalyst, without the need of any other promoter. High levels of
conversion and selectivity were observed for aryl ketoximes. Caprolactam was isolated in high
yields.
The gas-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam was catalyzed
using niobium oxide supported on SiO2, SiO2AAl2O3, TiO2, and ZrO2. A cyclohexanone oxime
conversion of about 100 % and up to 98 % caprolactam selectivities were achieved in the presence
of Nb2O5/SiO2 as catalyst (Anilkumar & Hoelderich, 2012)
Synthesis of caprolactam from D-glucose- derived L-lysine was investigated in the study of Yang J.
(Yang, 2007) This method involves the cyclization of L-lysine and subsequent deamination of the
resulting α-amino-Ɛ-caprolactam. Deamination of α-amino-Ɛ-caprolactam was explored using
hydroxylamine-O-sulfonic acid and catalytically over Pt on carbon.
The group of authors around Gaussand (Gaussand, Pukin, & Frassen, 2007-2010) described
preparation of caprolactam from lysine in potato. Synthesis is based on this principle: accumulation
of 6-amino-2-ketocaproic acid, an intermediate in a potential Ɛ-caprolactam synthesis, may be
achieved in potato tubers that already accumulate lysine and contain an extra enzyme for the
conversion. By introduction of the enzyme lysine oxidase from a micro-organism into potato, lysine
will be converted, leading to accumulation of 6-amino-2-ketocaproic acid. This is then isolated
from potato by, e.g., ion exchange chromatography. Amino-ketocaproic acid can then be
transformed to 6-aminocaproic acid. The initial reduction may be achieved chemically (e.g.
H2/catalyst) or enzymatically (e.g. alcohol dehydrogenase). Dehydration should be carried out under
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conditions so as not to cause elimination of the amino group. Here the use of (modified) alumina
may be appropriate. The final reduction step is expected to be similar to conventional
hydrogenation technology. The resultant 6-aminocaproic acid can then be readily converted to
Ɛ-caprolactam by known technology.
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