ANALYSIS OF ALTERNATIVES Public version

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1 ANALYSIS OF ALTERNATIVES Public version Legal name of applicant(s): Grupa Azoty S.A. Submitted by: Grupa Azoty S.A. Substance: Trichloroethylene Use title: Industrial use as a process chemical in Use number: 1 caprolactam purification

2 Disclaimer This report has been prepared by Risk & Policy Analysts Ltd and Forschungs- und Beratungsinstitut Gefahrstoffe GmbH, with reasonable skill, care and diligence under a contract to the client and in accordance with the terms and provisions of the contract. Risk & Policy Analysis Ltd and Forschungsund Beratungsinstitut Gefahrstoffe GmbH will accept no responsibility towards the client and third parties in respect of any matters outside the scope of the contract. This report has been prepared for the client and we accept no liability for any loss or damage arising out of the provision of the report to third parties. Any such party relies on the report at their own risk.

3 Table of contents 1 Summary Background to this analysis of alternatives Overview of Grupa Azoty S.A. supply chain Potential alternatives for TCE Suitability of potential alternatives for TCE Feasibility of potential alternatives for TCE Actions needed to improve the suitability and availability of potential alternatives Analysis of substance function Caprolactam synthesis Description of the extraction process Conditions of use and technical comparison criteria Summary of technical feasibility criteria Annual Tonnage Identification of possible alternatives List of possible alternatives Description of efforts made to identify possible alternatives Screening of identified alternatives Suitability and availability of possible alternatives Alternative 1: Toluene Alternative 2: 60% 1-octanol in cyclohexane Overall conclusions on suitability and availability of possible alternatives for TCE Alternatives substances and technologies considered Conclusions on comparison of alternatives to TCE Overall conclusion and future research and development References Annex Justifications for confidentiality claims Appendix 1 Literature search terms... 91

4 10 Appendix 2 Comparative hazard and risk characterisation of alternatives to trichloroethylene for caprolactam purification Background Hazard considerations for chlorinated solvents Reference values (DNELs, PNECs) for trichloroethylene and alternative substances Exposure Assessment Comparative Risk Characterisation Excursion: Comparison of the evaporation time from gloves References for Appendix

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7 1 Summary 1.1 Background to this analysis of alternatives The substance of concern is trichloroethylene (hereafter referred to as TCE), EC No , CAS No , and its use for which Authorisation is sought is as its industrial use as a process chemical (extraction solvent) in the purification of caprolactam in a closed system. This Analysis of Alternatives (AoA) constitutes part of the Application for Authorisation (AfA) submitted by Grupa Azoty S.A., a Polish downstream user of TCE. Grupa Azoty S.A. manufactures caprolactam utilising TCE as an extraction solvent at their plant in Tarnów, Poland, in a plant situated within a large site. TCE does not itself participate in the reactions that lead to the formation of caprolactam; it only acts as a processing agent within a closed system. Caprolactam (IUPAC name: azepan-2-one, EC No , CAS No ) is an organic chemical; it is an intermediate product used in the manufacturing of polyamide 6 (otherwise known as Nylon 6, hereafter referred to as PA6). It is produced mainly from phenol and benzene (Grupa Azoty Group, 2014), and is used almost exclusively for the production of PA6. PA6 is the leading product in engineering plastics. It is a high-quality engineering thermoplastic, which is produced in granular form for injection processing. The product has a wide range of beneficial properties, and this means that it is used in a range of industries, including automotive, construction, electrical engineering, household goods, and the food and textile industries. Grupa Azoty S.A. s very popular brands of PA6 are Tarnamid and Alphalon TM (Grupa Azoty Group, 2014). Tarnamid plastics are produced at Tarnów, and Alphalon TM plastics are produced at a facility in Guben, Germany. TCE is a part of an extensive chain of integration for the production of caprolactam at the Tarnów site, and the plant has been designed and built with TCE specifically to be used as the extraction solvent. The caprolactam production process produces ammonium sulphate as a co-product and the quality of this product is also maintained by the use of TCE. As it stands, TCE is a critical element in the commercial viability of not only the caprolactam plant and ammonium sulphate plants, but also PA6 plants owned by Grupa Azoty S.A. at Tarnów and Guben. Due to the specific plant design, a feasible alternative for TCE will have to have very similar qualities; otherwise, the plant s design would have to be significantly altered. The Authorisation is applied for so that TCE will continue to be used at Tarnów until a technically and economically feasible alternative is available for this site. The argumentation in this Application for Authorisation (AfA) is based on two pillars: The lack of a technically and economically feasible alternative for TCE in the purification of caprolactam in Tarnów, and The demonstration that the socio-economic benefits from the continued use of the substance significantly outweigh the risks to human health from the use of TCE at the Tarnów plant, as shown in Section 4 of the accompanying Socio-economic Assessment (SEA) document. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 1

8 1.2 Overview of Grupa Azoty S.A. supply chain Grupa Azoty S.A. is a member of Grupa Azoty, a significant chemical holdings company in Europe. At present, the Grupa Azoty Group comprises Grupa Azoty S.A., and eight subsidiaries (Grupa Azoty Group, 2014) and offers its customers a diversified portfolio of products from mineral fertilisers and engineering plastics to oxo alcohols, plasticisers and pigments. Grupa Azoty S.A. itself is active in manufacturing, service and commercial operations relating to mineral fertilisers, engineering plastics and the raw materials needed for their production. Grupa Azoty S.A. is also an experienced manufacturer and supplier of highly specialised catalysts used in the chemical industry. Grupa Azoty S.A. is Europe s fifth-largest integrated manufacturer of PA6, and the leading producer of PA6 in Poland (Grupa Azoty, undated). Manufacture of PA6 takes place within the group at two companies: Grupa Azoty S.A. in Tarnów, Poland and Grupa Azoty ATT Polymers GmbH in Guben, Germany, owned by Grupa Azoty S.A. The Tarnów facility manufactures the Tarnamid PA6 plastics (of which there are 12 varieties), and the Guben facility manufactures the Alphalon TM PA 6 plastics (of which there are 17 varieties). For the manufacture of PA6, caprolactam needs to be used as a raw material. The only supplier of caprolactam to both Tarnów and Guben is Grupa Azoty S.A. itself. The manufacture of the substance, which utilises TCE, takes place at the Tarnów plant. A small proportion of the caprolactam manufactured at Tarnów is currently sold to downstream users for external use. Grupa Azoty Group also manufactures caprolactam at a plant in Puławy, Poland (Grupa Azoty Puławy S.A.). The Puławy plant uses toluene instead of TCE for the purification of caprolactam. A schematic diagram of relevant production is shown in Figure 1-1. The diagram includes current and planned production capacities. The caprolactam production capacity of Tarnów is 100 kt per year. Both Tarnow and Guben produce PA6 (45 kt at each site). A new PA6 plant is being commissioned at Tarnów that will increase the PA6 capacity by 80 kt. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 2

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13 2 Analysis of substance function 2.1 Caprolactam synthesis Caprolactam was first synthesised in 1899 by Gabriel & Maas by heating ε-aminocaproic acid. However, commercial interest in the material developed in 1937, when it was recognised that the substance could be used and a precursor for PA6 (Gunardson, 1997). Since then, caprolactam has gained importance and large scale production has increased rapidly (Ritz, et al., 2002). There are several industrially relevant synthetic routes for caprolactam derived from different raw materials. The function of TCE within the context of this AfA concerns the extraction of caprolactam and not its synthesis. Therefore, an extensive review of production methods is not relevant to this AoA. Nevertheless, the synthetic route does influence the impurities that are present in the crude caprolactam, and as such, a brief overview of the most important synthetic routes is given below. Details of further relevant methods have been described by van Delden (2005) and Ritz et al. (2002). The main routes can be summarised according to their main raw material: Via cyclohexanone oxime from the condensation of hydroxylamine, and cyclohexanone derived from the hydrogenation (reduction) of phenol or oxidation of cyclohexane (derived from benzene) (EIPCCB, 2003) From a photochemical reaction of cyclohexane with nitrosyl chloride (Toray, undated) (Chemsystems, 2009) Without an intermediate oxime from adiponitrile derived from butadiene, acrylonitrile or adipic acid (developed by DuPont/BASF and DSM/Shell) (ICIS, 1996) (Chemsystems, 2006). These main routes are substantially different to each other. The latter two are generally unavailable for most manufacturers as the technologies required are proprietary. The first route accounts for the vast majority of worldwide production capacity (Alessi, et al., 1997). This synthesis proceeds by Beckmann rearrangement of cyclohexanone oxime in the presence of a strong acid catalyst such as oleum. The applicant uses this conventional route and produces their caprolactam from cyclohexanone oxime. Their production uses benzene and phenol to make cyclohexanone and sulphur and ammonia to make oleum, hydroxylamine sulphate. In other words, they are fully integrated in their production from very common feedstock substances. Ammonium sulphate is also produced at three stages of production: during hydroxylamine sulphate production, cyclohexanone oxime formation and Beckmann rearrangement (see Figure 2-1). The ammonium sulphate coproduct is generally viewed as an unwanted side-product (Thomas & Raja, 2005); however, it is an important additional source of revenue for the applicant at the Tarnów plant. This AoA will only evaluate alternatives that are relevant to this synthetic route as the adoption of another route would require the construction of not only a new caprolactam extraction and synthesis unit but potentially an entirely new plant. This is considered an entirely unrealistic scenario and has not been considered further. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 7

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16 Extraction columns have limited or no moving parts, and require minimal maintenance in comparison to mixer-settler or centrifugal contactors. The use of continuous extraction is necessary to increase the rate of production, reduce production costs and also to limit the waste of extraction solvents. To do this, the extraction is coupled to a continuous solvent recycling and purification operation Asymmetric Rotating Disk Contactor (ARDC) columns Caprolactam extractions are generally carried out in extraction columns and this is the case for the applicant. Their exact designs vary depending on the requirements of the process and the company operating it. An extraction column consists of the column housing, baffles or packing material and various inlet and outlet ports. The purpose of the internal baffles or packing material is to mix the extraction solvent and the feed in a controlled manner. Packed extraction columns have no moving parts and rely on carefully selected packing material to ensure effective extraction of the feed. These types of column may also be pulsed where the feed is pushed back-and-forth to increase the mixing through the packing material. In addition to static extraction columns, there are many types of agitated columns (KMPS, 2013). In these types of column, the feed and solvent are typically mixed by various internal baffles. Typically, these consist of a moving element (a rotor) and a static element (stator). The type of column that is most relevant to caprolactam for the applicant is an Asymmetric Rotating Disc Contactor (ARDC) column. It is common to have several extraction steps. After the initial extraction of caprolactam from the aqueous lactam oil using an organic solvent, organic impurities remain. These are separated from caprolactam by back-extraction of the organic solvent with water (as illustrated in Figure 2-3). This results in an aqueous solution of caprolactam. The water must then be distilled off to form a concentrated solution of caprolactam that is crystallised and further purified. The organic extracts may also be re-extracted (using either TCE or water) to decrease the level of impurities. This can be carried out either in separate columns or they can be re-introduced at an earlier stage of the process to flow into the same columns. Alessi et al. (1997) compare two extraction plant layouts that use benzene as the extraction solvent: a simple extraction layout that uses two columns, and a complex layout that uses four columns. The applicant utilises three separate columns: While caprolactam extraction can be carried out using alternative solvents in other plants (such as toluene used at Puławy), the existing extraction plant used by the applicant requires the use of TCE and cannot be adapted to use other extraction solvents. The reasons for this are elaborated below and in Section 2.3. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 10

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18 requires a complex extraction arrangement (Alessi, et al., 1997) which alternative solvents should be able to serve Extraction layout A general description of liquid-liquid extraction technology is given above. The specific situation at the extraction plant operated by the applicant is described below and is illustrated in Figure 2-4. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 12

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20 Tarnów operates three ARDC columns. The two product streams, lactam oil and ammonium sulphate, are separated before they enter the extraction plant. These are fed through the extraction columns and each column produces an organic and an aqueous output stream. The role of each column is explained below. Column 1 Column 2 Column 3 Finally, the aqueous caprolactam solution is concentrated to 90% caprolactam which is then crystallised and purified further using vacuum distillation. No TCE is added after the final column for any process. 2.3 Conditions of use and technical comparison criteria Approach to information collection The development of technical comparison criteria for TCE and its potential alternatives has been based on a combination of consultation between the independent third party that has authored this AoA and the applicant, and a review of available scientific literature. Consultation with the applicant regarding the plant layout and the current technologies employed was used to identify technical details that affect the selection of alternatives. The applicant s Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 14

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23 economic reasons, as more energy is required to distil (vaporise) the solvent for recovery or purification. Threshold value Boiling point of solvent: C. Boiling points that are higher than TCE (87 C) require a larger amount of energy to recycle. Solubility of caprolactam Importance of the technical criterion A minimum solubility of caprolactam in the extraction solvent is required for any effective extraction process. However, the maximum solubility of caprolactam in a solvent is a less useful criterion than the achievable concentration of caprolactam in the extract. The concentration in the extract is a more suitable measure of solubility for the evaluation of continuous extraction because a lower solubility can be compensated for by running the extraction for longer (in effect using a larger volume of solvent) which increases both the cost of plant construction as well as operating costs through the need to circulate and evaporate more solvent. However, a solvent with lower caprolactam solubility will also require a higher selectivity for caprolactam over any process impurities. Therefore, it is deemed more appropriate to use a measure of achievable concentration in the extract (i.e. in the output of the extraction column) rather than a measure of solubility based on maximum concentration at a given temperature in the solvent because this reflects the process in practice. However, this type of data is less commonly described in the literature than solubility. In its absence, a measure of maximum solubility could be used as a proxy. Threshold value At least 15% in the extraction feed or ideally above 19% caprolactam in solvent at 20 C. Lower solubility values can only be tolerated at increased extraction solvent volumes or times. Recyclability of solvent Importance of the technical criterion The use of the solvent currently operated in a closed-system that continually circulates the extraction solvent. There are currently some tonnes of TCE in circulation in the extraction system; if this was not recycled, the total flow of solvent through the extraction columns would amount to up to 1,000,000 tonnes per year. Taking into account the annual consumption of TCE of 100-1,000 tonnes per year each tonne of solvent is recycled in the region of 1,000-10,000 times before it is replaced. Threshold value Current value using TCE for comparison: annual process throughput/annual consumption = = value in the range 1,000-10,000. Higher values are preferable. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 17

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25 cannot be used would then contribute to the emissions of the plant or require additional disposal actions and associated costs. Threshold value The value achieved by the applicant at Tarnów is 4.3 t/t caprolactam of high quality (low COD) material must be met. Any reduction would not be technically feasible because it would require new facilities and compromise the production of fertilisers at the Tarnów plant. Any reduction in the quality of ammonium sulphate would be directly proportional to the increased generation of waste, i.e. any un-extracted ammonium sulphate would remain in waste streams with a potentially detrimental environmental and economic effect. Water consumption Importance of the technical criterion Water is used both for back-extraction and for cooling during the process. The purified water used in the extraction process is recycled, where the condensate from concentration of the back-washing extract is passed back into the extractor. The majority of the water used is cooling water that is required in condensers at various distillation stages for the recovery of both TCE and extractionwater and to cool concentrated caprolactam prior to crystallisation. The majority of the water is also recirculated but some is lost during the process and is topped up from a local river. Threshold value The current process uses tonnes of river water per tonne of caprolactam produced. Based on the Tarnów caprolactam plant nameplate capacity of 100 kt of caprolactam, a maximum cooling water consumption o kt of water can be estimated as the value of current consumption. No specific threshold can be identified but equal or lower water consumption is clearly preferred in order to reduce the consumption of natural resources and any associated costs. Energy consumption Importance of the technical criterion The extraction process uses both electricity and steam to provide heat. The majority of the energy is used as steam. Heat is mainly required during concentration and distillation but also to maintain a constant temperature during the extraction process. Electricity is used to drive pumps to circulate the solvent, extract, cooling water and raffinate streams and to run the ARDC columns. Threshold value No specific threshold can be identified but lower energy consumption is clearly preferred in order to reduce the consumption of natural resources and to reduce production costs. The current consumption figures can be used for the purposes of comparison but the figures are considered confidential. Current value of electricity consumption - for extraction and condensation plants: GJ/t CL Current value of steam consumption: GJ/t CL Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 19

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29 3 Annual Tonnage Confidential average tonnage of TCE in caprolactam extraction: tonnes per year. Annual tonnage band for TCE in caprolactam extraction: 100-1,000 tonnes per year. Grupa Azoty S.A. consumes TCE in the range t (, which was used exclusively in the purification of some 100 kt kt, in 2013) of caprolactam produced at the plant. The solvent is recycled in closed systems; however, TCE is known to thermally decompose during the recovery process (Glazko, et al., 2007; Dow, 2008). Therefore, continued input of additional solvent is required to replenish spent TCE (Smallwood, 2002). The addition of TCE happens periodically via a storage tank. Over a year the entire volume of the extraction solvent in circulation is replaced (approximately of TCE is in circulation at any one time). Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 23

30 Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 24

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34 cyclohexane/benzene and cyclohexane/cyclohexanol, and Gong et al. proposed 60% 1-octanol in cyclohexane. The combined results from these studies describe a range of different potential alternatives. Unfortunately, these investigations used different methodologies and did not compare the mixtures proposed by other researchers. On the other hand, the investigation by Glazko et al. is particularly useful as the researchers compared their proposed mixture with pure solvents, including TCE. Their aim was to establish industrially relevant extraction solvents or mixtures that could improve the overall process, but they did not specifically seek to reduce overall risk to workers. The overall outcome identified benzene the most feasible solvent due to its easy of recycling in comparison to the mixed solvent systems. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 28

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37 The following can be concluded on the feasibility of mixed solvent systems: Advantages: Extraction capacity: according to all three articles mentioned above, mixed systems may have increased extraction capacity compared to pure solvents by the addition of a more polar solvent (such as 1-octanol), at the cost of increased solubility of the solvent in the aqueous fraction resulting in losses of the solvent to water. These research projects investigated the relationship between these two factors. Disadvantages: R&D requirements: There is still a lack of detailed knowledge on the use of these alternatives in commercially relevant systems. It is likely that for full-scale implementation to a commercial caprolactam manufacturing operation, considerable R&D to optimise solvent ratios and conditions of use would be needed Extraction column issues: use of mixed solvent systems would result in complications in the selection and operation of extraction columns; on this aspect, very limited publicly available information is available Recycling issues: the recovery and recycling of the mixed solvent is likely to be considerably more complex than for single solvent systems and will require further research (van Delden, 2005). Ketones, esters and ethereal solvents have also been considered as solvents in the research by van Delden (2005) and Gong et al. (2007; 2008), but the mixed aliphatic and alkyl alcohol systems were deemed more suitable. Therefore, it is unlikely that these solvents would be feasible alternatives without very extensive further R&D. The R&D of the other potential alternatives, described above, is more likely to yield a feasible alternative faster than ketone, ester or ethereal solvents. Alternative techniques A number of potential alternative techniques have been identified in the electronic literature and their relevance to the applicant is discussed below. We may distinguish these techniques into the following categories : Alternative caprolactam extraction techniques Alternative PA6 manufacturing techniques that eliminate the use of fossil fuel-derived caprolactam. Alternative extraction: water extraction of caprolactam using an task-specific ionic liquid This method is proposed in academic research by Gui et al. (2004). In this method, cyclohexanone oxime is treated with an imidazolium-based ionic liquid bearing sulphonyl chloride functionality. This essentially combines the roles of acid catalyst and reaction solvent for the Beckmann rearrangement step of the synthesis. This method has only been tested with very small quantities, and problems occur when attempting to recycle the ionic liquid: there is a large drop in conversion to caprolactam. This technique is clearly not yet commercially viable and it does not concern the issues of continuous extraction processes. Alternative PA6 manufacturing techniques that eliminate the use of fossil fuel-derived caprolactam The use of L-lysine for the synthesis of caprolactam has been described in a patent application from 2005 which elaborates the process to manufacture caprolactam from various forms of lysine (Frost, Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 31

38 2005). In comparison to established industrial routes to caprolactam (e.g. via cyclohexanone oxime), this method has several limitations; for example, it has only been demonstrated in relatively small scale (at the mmol scale), it produces relatively low yields (around 70% per step, cyclisation and deamination) and it involves cryogenic conditions (-50 to -200 C). Cryogenic reaction conditions are particularly costly to achieve on a large scale and justifying their use for a large volume organic commodity chemical is very challenging. The amino acid lysine itself can be derived from renewable resources, such as sugar, which could conceivably replace the starting material for caprolactam benzene. However, this would require a bio-refinery, which has been defined in the patent description as a facility that integrates biomass conversion processes and equipment to produce fuels, power and chemicals from biomass. Carbohydrates (e.g. glucose) have also been proposed as potential precursors for caprolactam in a recent patent (Murphy, et al., 2012). This patent describes the synthesis of 6-aminocaproic acid, which is an intermediate to PA6. A crucial limitation is that only very low yields (<22%) of 6- aminocaproic acid are described in the examples. Clearly, these yields are not of commercial relevance for a raw material critical to a commodity chemical such as PA6 when compared to conventional synthesis of caprolactam. Further techniques that employ recovery of caprolactam or PA6 from waste sources have also been proposed. These include The Econyl Regeneration System developed by the Aquafil Group. With regard to caprolactam recovery, they claim the ECONYL caprolactam we produce has the same chemical and performance characteristics as caprolactam from fossil raw material. Hence, the process and chemical methods of transforming the ECONYL caprolactam into nylon 6 polymers what is known as polymerization are identical to polymerization of virgin caprolactam (Aquafil, 2013). Techniques focused on recovery of recycled materials are not considered feasible for the applicant, as the applicant does not have the infrastructure to collect large volumes of waste for conversion. Relevance of alternative techniques to Grupa Azoty S.A. The applicant manufactures caprolactam from cyclohexanone oxime using oleum. Other industrially relevant caprolactam syntheses routes would require an entirely new business model and production plant. Therefore, these are not considered relevant to the applicant and only alternative extraction solvents may be considered as realistic prospects for the elimination of TCE in the context of this AfA Information from consultation Consultation with the applicant The independent third party consultant that has prepared this AoA, conducted extensive consultation with the applicant to determine the current state of the company s knowledge on alternatives, and collect information on past and planned R&D research on a suitable replacement for TCE. The information collected has formed a solid basis for the analysis presented throughout this AoA. Consultation with the applicant s supply chain TCE is not present in any of the chemicals that are associated with the process using TCE and which Grupa Azoty S.A. is selling to its customers, namely caprolactam, PA6 and ammonium sulphate. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 32

39 None of the customers of the applicant is familiar with the caprolactam extraction process or indeed has an interest in what solvent Grupa Azoty S.A. is used, as the solvent itself is not present in the products sold to them. Therefore, no need for consultation with the applicant s customers was identified and thus no such consultation was undertaken. Nevertheless, some customers of Grupa Azoty S.A. would be affected by a change to the extraction solvent used Tarnów and the SEA related to this AfA explores the details of such impacts. For each of Grupa Azoty S.A. s products the following considerations apply: Caprolactam: it is not envisaged that the use of an alternative extraction solvent or technique would affect the quality of caprolactam because any new plant would have to avoid this impact for it to be considered feasible. PA6: similarly to caprolactam, the use of an alternative solvent would not affect the quality of the applicant s PA6 products. As is the case for caprolactam, any alternative would have to ensure that there would be no change in the quality or quantity of PA6 produced for it to be considered feasible. Ammonium sulphate: the quality of ammonium sulphate co-product is an important consideration. The applicant sells the highest grade of the ammonium sulphate co-product to downstream users as a slow-release fertiliser. Some of the ammonium sulphate is further processed by the applicant into multi-component (ASN) fertiliser products to be sold to downstream users. The use of an alternative may decrease the quality of ammonium sulphate. A reduction in quality would deprive the applicant of some of the high-grade ammonium sulphate, and this would therefore result in lower sales volumes and affect the production of ASN fertilisers, unless a new plant for ammonium sulphate crystallisation were built. 4.3 Screening of identified alternatives Overview The previous section describes both the literature sources and the consultation with the applicant that has been used to identify a large number of potential alternatives. It is however clear that many of these are not suitable alternatives due to their toxicity or lack of technical feasibility for the production of a bulk commodity chemical such as caprolactam. It is also clear that there are some strong candidates for alternative solvents. A systematic review of the identified alternative substances has been undertaken in order to eliminate those that are clearly unsuitable or infeasible and to create a shortlist of the most promising alternatives that would be assessed in the required level of detail Screening by suitability for risk reduction TCE has been identified as requiring authorisation due to its Carc. 1B classification. Substances that fulfil REACH Article 57 criteria cannot be considered suitable alternatives as they may not reduce the overall risks. 5 5 ECHA guidance on AoA states: If an alternative substance is already on Annex XIV, it will normally not make sense to transfer to it. If the substance is on the candidate list, then a very close consideration on the Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 33

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42 Many of the alternative solvents that carry CMR hazard classifications can be excluded from further consideration due to their SVHC or other hazard properties and consideration for the technical feasibility criteria identified in Section A more detailed discussion of the relative hazards and risks posed by alternatives to TCE is given in a separate support document 6. In general, the range of solvents identified can be summarised in terms of their solvent class. Each of these classes is discussed below. Halogenated solvents Several halogenated solvents other than TCE also carry carcinogenic hazards (with harmonised classifications Carc. 2 or above) and these solvents are likely to be identified as SVHCs and are therefore considered unsuitable alternatives. Two halogenated solvents, 1,2-dichloroethene and 1,1,2,2-tetrachloroethane do not currently have harmonised CMR classifications 7. In a recent evaluation of their carcinogenic properties, the International Agency on the Research on Cancer concluded for 1,1,1,2-tetrachloroethane and 1,1,2,2-tetrachloroethane that there is sufficient evidence in experimental animals for the carcinogenicity. The overall conclusion for both substances was possibly carcinogenic to humans (Group 2B) (IARC, 2013). Therefore, these substances can be considered as suspected carcinogens, similar to Carc. 2 classified substances. Aromatic solvents Some aromatic solvents are also known carcinogens. Benzene is a very well-known occupational carcinogen (Carc. 1A) and it is currently known to be used in caprolactam extraction as well as being an important feedstock to a caprolactam precursor (EIPCCB, 2003). Under the Existing Substances Regulation, it was identified alongside TCE as requiring further risk reduction measures 8. Despite its evident technical feasibility (due to its current commercial application), benzene cannot be considered a suitable alternative from a risk reduction perspective as it carries a more severe hazard classification than TCE. Nitrobenzene is not only a suspected carcinogen (Carc. 2) but also has recently been classified by RAC as a reproductive toxin (Repr. 1B) and should therefore be excluded from potential alternatives. Alkyl-phenols refer to a broad class of compounds. A typical example of an alkyl-phenol would be nonylphenol (CAS ; EC Number ). Nonylphenol is a Repr 2. substance that is persistent and bioaccumulative and is listed as a priority hazardous substance under the Water Framework Directive due to its potential impact on the aquatic environment, and so its emissions See the attached support document: Comparative hazard and risk characterisation of alternatives to trichloroethylene for caprolactam purification (Appendix 2) (Date of search: 14 May 2014). See Commission Communication and the Commission Recommendation for the substance benzene, available at accessed 14 May Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 36

43 need to be eliminated. Nonylphenol has also been shown to be an endocrine disruptor in living organisms, meaning it has the potential to mimic hormones - in this case, oestrogen. Although the use in this context would be in closed industrial processes, it is unlikely that the use of alkyl-phenols would represent a significant reduction of the overall risk to human health and environment due to suspected bioacculumative and endocrine disrupting properties of this class of compounds. Xylene has some indications for reproductive toxicity but it has no harmonised CMR classifications. Toluene is classified as Repr. 2 but it is also not classed as carcinogenic, making it a more suitable candidate for AoA from a risk reduction perspective than benzene. Aliphatic solvents Many of the aliphatic solvents do not generally have CMR properties associated with them. Cyclohexane and methylcyclohexane are quite similar solvents with no harmonised classification of concern; however, both solvents have been classified as having aquatic hazards. Out of the two, methylcyclohexane could be considered as having a lower environmental hazard (Aquatic Chronic 2, H411) in comparison to cyclohexane (aquatic acute 1, H400 and Aquatic Chronic 1, H410). Ketones, esters, ethereal solvents and ionic liquids Ketones, esters and ethereal solvents, as well as ionic liquids, are wide classes of potential solvents. In general, some of the potentially suitable alternatives identified do not have harmonised hazard classifications and would not be excluded from further consideration on the basis of their hazard profile Screening of the identified alternatives against the technical feasibility criteria and commercialisation status The potential alternative solvents that were not identified to be unsuitable from a risk reduction perspective are evaluated below in terms of their technical feasibility. Halogenated solvents TCE is the only known commercially-used halogenated solvent for caprolactam extraction. The high density of other halogenated solvents would make them potentially compatible with the existing plant equipment used by the applicant, and would be attractive alternatives from a technical perspective. However, it is unlikely that 1,2-dichloroethene will be a suitable process solvent due to its very low boiling point of 32 C which is below a typical extraction temperature of C (Grupa Azoty Group, 2007), flammability and potential to form acetylene chloride (an explosive) in the presence of strong base (Sax, 1979 and ATSDR, undated). 1,1,2,2-tetrachloroethane would fulfil the high density technical criteria, which would potentially allow its use at the existing plant operated by the applicant. On the other hand, this solvent has a relatively high boiling point of 145 C that would hinder its recyclability to some extent. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 37

44 Notably, neither of these substances are registered 9. Therefore, they may not currently be available on a sufficient scale (> tonnes per year). Overall, halogenated solvents other than TCE would in general not be suitable alternatives for the applicant. Aromatic solvents Toluene and benzene are known to be commercially used as caprolactam extraction solvents. An advantage of toluene over xylene is that toluene has a significantly lower boiling point. This would indicate that the recovery of the solvent after the extraction of caprolactam is likely to be easier than recovery of xylene. Benzene has a lower boiling point (80 C) than TCE (87 C) or toluene (111 C). It also has a similar extraction capacity to toluene and a higher efficiency (Glazko, et al., 2007). Therefore, benzene could be considered the most technically feasible aromatic solvent for the extraction of caprolactam; however, in light of its hazard classifications, it is being replaced by toluene in commercial caprolactam extractions (van Delden, 2005). Aliphatic solvents None of the aliphatic solvents have a high enough density to allow them to be used by the applicant without constructing a new extraction plant unit. Out of the two cycloalkanes, cyclohexane and methylcyclohexane, cyclohexane has a similar boiling point to TCE and lower than that of methylcyclohexane, making it potentially less energy intensive to recycle. In terms of selectivity and solubility of caprolactam, both of these solvents lack feasibility, as shown by van Delden (2005), Glazko et al. (2007), and Gong et al. (2008). Chiefly, this is because of the poor solubility of caprolactam in aliphatic solvents. In the study by Glazko et al. (2007), pure cyclohexane was shown to result in very low (3.7% by weight, at 20 C) concentrations of caprolactam in the extract with respect to TCE (which achieved 16% by weight at 20 C). To overcome the inherent solubility and selectivity limitations of pure aliphatic solvents, the use of both cyclohexane and methylcyclohexane have been proposed in research as part of mixed solvent systems. Therefore, aliphatic solvents are not considered further as pure solvents. Mixed solvent systems consisting of an aliphatic solvent and an additional, generally more polar, solvent have been proposed as more technically feasible alternatives to the use of pure aliphatic solvents. Various solvent systems have been proposed and are listed in Table 4-7 alongside with an evaluation of their technical feasibility. 9 Registered substances database, accessed at date of last search 14 May Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 38

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46 4.3.4 Summary of the screening process for alternatives The selection of a shortlist of alternatives to be addressed in detail in Section 5 of this AoA was carried out based on consideration for the CMR properties of alternative solvents and the technical criteria identified during the consultation. An overview of the screening process is given in Table 4-8 overleaf. Only one of the identified solvents fulfils the density criteria used to identify potential alternatives. An overview of important exclusions and inclusions of solvents from the shortlist is highlighted here: Other halogenated solvents: excluded as likely SVHCs due to CMR properties 1,2-dichloroethene was excluded due to a very low boiling point and potential process risks 1,1,2,2-tetrachloroethane was excluded due to lack of availability and potential carcinogenicity Aromatic solvents: Benzene and nitrobenzene were excluded as SVHC substances of comparable hazard profile to TCE (CMR substances with carcinogenic properties, respectively reproductive toxicity) Toluene considered the best in the aromatic class without prohibitive hazards. Unlike other aromatic solvents such as xylene, it is also a known commercially used caprolactam extraction solvent that is potentially feasible to the applicant. Aliphatic solvents: Cyclohexane and other pure alkanes were excluded due to a lack of caprolactam solubility and poor extraction performance according to literature sources Pure 1-octanol and 1-heptanol alcohol solvents were excluded due to evidence of limited potential concerning issues of water solubility and potential for solvent recovery Mixed solvent systems: 60% 1-octanol in cyclohexane was identified as the best mixed solvent system by Gong et al. (2008) and was selected for further evaluation. This mixture also possesses lower hazard classes for its components in comparison to 1-heptanol in heptane. This process of screening has considered 32 alternative solvents or mixtures and four alternative techniques to the use of TCE as an extraction solvent. None of the techniques are considered relevant alternatives to the applicant. Their use would require a complete rebuild of all existing infrastructure operated by Grupa Azoty S.A. Out of the potential alternative solvents, toluene and 60% 1-octanol in cyclohexane have been identified as relevant and potentially suitable alternatives. These two potential alternatives are assessed from the perspective of the applicant in detail in Section 5. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 40

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56 sulphate). As a result, toluene cannot be deemed to be a technically feasible alternative for TCE from the applicant s perspective. Required steps to allow use of toluene as an alternative for TCE To overcome the issues of compatibility with impurities of aqueous ammonium sulphate solution and the reduction in the quantity of high quality ammonium sulphate obtained using current technology, the ammonium sulphate from the synthesis of hydroxylamine sulphate and from caprolactam synthesis would need to be kept separate. This would require either a separate facility for temporarily storing and crystallising the ammonium sulphate from caprolactam synthesis or the generation of unacceptable amounts of waste ammonium sulphate (some 180 kt per year). Neither of these options is judged to be realistic by the applicant. Instead, a R&D campaign is proposed by the applicant as described below. Figure 5-2 illustrates the proposed measures that may be able to overcome some of the identified limitations of toluene subject to a planned R&D campaign and is considered strictly confidential. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 50

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65 5.1.4 Reduction of overall risk due to transition to the alternative Assessment of risks to human health from the use of toluene as an extraction solvent The appendix on the relative risk assessment of TCE and the alternatives indicates that due to the very low DMEL used for TCE, RCRs for TCE are higher compared to toluene, as expected. RCRs for toluene are below 1 under the conditions of use assumed here. In this regard, the substance could be considered a suitable alternative for TCE in the purification of caprolactam. Assessment of risks to the environment from the use of toluene as an extraction solvent Risk assessment results Appendix 2 on the comparative risk assessment of TCE and the alternatives indicates that despite a PNEC in the same range as toluene, RCRs obtained for TCE are higher, due to higher tonnage used and absence of biodegradability. It must be emphasised that the release and exposure calculations in the appendix are theoretical, using a standardised exposure scenario, which allows for comparison of the various substances. They do not represent real conditions at the applicant s site. Actual releases of TCE to wastewater have been demonstrated to be negligible. It can be concluded that toluene as an alternative substance is beneficial with regard to human health considerations and is at least not more critical than TCE with regard to environmental risks. It should be noted that the analysis in appendix 2 only addresses the relative hazards from toluene and estimates the likely exposure from its potential use by the applicant. It does not take into account other notable environmental impacts that might arise. Externalities from increased energy consumption The higher boiling point of toluene results in an increased energy consumption of steam (see Section 5.1.2). The whole process can be expected to result in an additional 177,840 GJ/year of energy due to the use of toluene in the place of TCE 16. This amount of energy may be converted into GWh using one of several available online calculators 17. The equivalent amount is 49.4 GWh/year. Using greenhouse gas emission factors available from UK Department for Environment, Food and Rural Affairs 18, it can be calculated that the consumption of natural gas capable of producing 49.4 GWh/year would result in the release of an additional 49,400, = ca. 10,150 tonnes CO 2 (eq) per year on a net calorific value basis. Monetisation of greenhouse gas emissions is based on the methodology developed by the UK government for carbon valuation in public policy appraisal (DECC, 2011). A central short-term traded Current energy (steam + electricity) consumption using TCE: GJ/year. This can be compared to energy consumption using toluene of GJ/year. A difference of 177,840 GJ/year. The one used is here: accessed 6 June Available at: accessed 6 June Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 59

66 price of carbon of 29 per tonne CO 2 -equivalent in 2014 can be found. The present day exchange rate ( 1 = 1.25) was used to convert the value in to. Therefore, the externalities of the increased energy consumption and concomitant CO 2 emissions would be 10, = ca million per year Availability As noted in Section 5.1.1, the substance has been registered under REACH, with an indicated tonnage of between 1,000,000 and 10,000,000 tonnes per annum. Toluene is a high production volume chemical and it is widely used as an industrial solvent and as a precursor in the synthesis of many other chemicals. The substance occurs naturally in crude oil and this is isolated in the production of gasoline. It is also produced in the manufacture of coke from coal (Landrigan & Etze, 2014). Taking this into consideration, the substance is considered to be available to the applicant. On the other hand, the current toluene-based technology is not technically or economically feasible and further R&D would be required to improve its technical feasibility. The basic R&D and pilot plant campaign is expected to take several years (at least six to ten years). Even if this has been successfully completed, a new plant would need to be constructed. The construction alone would take around three years. Therefore, the alternative cannot be implemented by the applicant before the Sunset Date Conclusion on suitability and availability of toluene The above discussion has explained that although toluene is a proven extraction solvent for caprolactam for some manufacturers (including Grupa Azoty S.A. s Puławy plant), its inherent shortcomings (density, impurities and quality of ammonium sulphate) in relation to the specifications of the existing plant make this substance technically infeasible with the current state of knowledge (i.e. as is applied at the applicant s Puławy plant). A significant amount of R&D would be required to adapt the existing technology to address the identified shortcomings in a way that would allow it to be used within Grupa Azoty S.A. s existing infrastructure. When considering economic feasibility, the construction of new facilities would entail a very significant cost ( million). It not possible for the applicant to obtain the required finance by the Sunset Date, nor is it possible to complete construction of the new facilities in time. Therefore, the use of toluene cannot be considered economically feasible for the applicant. It is hoped that the additional R&D would be able to deliver technology improvements which would make the operation of a plant converted to toluene extraction sufficiently profitable (in terms of ammonium sulphate related products). This is likely to entail an additional cost to the applicant of around million. The use of toluene as an alternative to TCE would result in reduced risk to human health but whilst the use of toluene at the applicant s plant has been shown by modelling not to raise concerns, the use of toluene under the current knowledge of technology would result in increased energy consumption with the associated increase in greenhouse gas emissions. Additionally, the existing toluene-based technology would result in a considerable amount of ammonium sulphate that is not compatible with the existing plant. It would therefore be considered waste unless additional crystallisation plant(s) could be constructed. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 60

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72 smaller amount of the mixture would be required perhaps half that of toluene. This would mean that some tonnes of 60% 1-octanol in cyclohexane tonnes of 1- octanol and tonnes cyclohexane) would be required per year Compatibility with impurities of aqueous ammonium sulphate solution: currently available information does not allow an adequate comparison to TCE (or toluene). The preliminary results from Gong et al. (2008) investigated the effect of this extraction mixture on the quality of caprolactam but not on ammonium sulphate solution Quantity of high quality ammonium sulphate obtained: the effect of using mixed solvents on the quality of ammonium sulphate is not known. The available research on alternative extraction solvents for caprolactam has not investigated their effect on the quantity of high quality ammonium sulphate obtained, presumable because it is viewed as an unwanted by-product by some researchers (Thomas & Raja, 2005) Water consumption: currently available information does not allow a comparison to TCE (or toluene) Energy consumption: the additional processing and the distillation of a high-boiling solvent such as 1-octanol (195 C) may require reduced pressure distillation, and the process is likely to require considerably more energy than the recovery of toluene. Therefore, with respect to TCE, the additional energy consumption of the process is likely to exceed the energy increase of 177,840 GJ/year, which was calculated for toluene, above. While the energy increase for toluene may be tolerated from a technical and economic perspective, an even greater increase for the mixture may not be technically feasible. Additional data would be required to determine if this is the case Maintenance requirements: currently available information does not allow a comparison to TCE (or toluene). It is clear that there are significant knowledge gaps that preclude the full comparison of technical characteristics of this solvent mixture to TCE. In conclusion, 60% 1-octanol in cyclohexane is not a technically feasible alternative to TCE, chiefly due to its reduced density that would require the construction of a new extraction plant. Toluene is a more technically feasible alternative than this mixture, and if a new plant were to be constructed, the applicant would employ toluene rather than the mixture. Considerable R&D would be required to establish whether 1-octanol in cyclohexane can be employed at all. If it could, it would more likely that it would be implemented as a second generation alternative in the more distant future Economic feasibility This 1-octanol in cyclohexane mixed solvent has limited technical feasibility using the present state of knowledge available to the applicant. It has only been proposed in academic research and, according to the knowledge available to the applicant, it has not found commercial use in the extraction of caprolactam. Therefore, it can only have very limited economic feasibility as its use is currently unproven. As is the case for toluene, it would require the construction of a new extraction facility, but unlike toluene, it is not certain how effectively it would operate or how it would best be Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 66

73 configured. In order to evaluate this, an extensive R&D campaign would be required. The level of effort required is likely to substantially exceed what is required for toluene. Given that the achievable yields and the cost of the process using 1-octanol and cyclohexane as extraction solvent is unknown, only a limited assessment of economic feasibility can be carried out. It is possible to say with some certainty that, at least in the short term, the costs associated with the construction of a new facility would be at least the same as toluene. In order to secure the necessary investment to allow the construction of a new facility, the technical feasibility of the technology would need to be demonstrated first. This is not possible using the current state of knowledge. Therefore, it is not possible to finance the construction of the new plant and this alternative is not considered to be economically feasible for the applicant Reduction of overall risk due to transition to the alternative Assessment of risks to human health from the use of the mixture of 1-octanol and cyclohexane as an extraction solvent The appendix on the relative risk assessment of TCE and the alternatives indicates that due to the very low DMEL used for TCE, RCRs for TCE are higher compared to the other solvents, as expected. RCRs for the mixture of 1-octanol and cyclohexane are below 1 under the assumed conditions of use. Assessment of risks to the environment from the use of the mixture of 1-octanol and cyclohexane as an extraction solvent Appendix 2 on the comparative risk assessment of TCE and the alternatives indicates that despite a PNEC for cyclohexane higher than that of TCE, RCRs obtained for TCE in the comparative exposure assessment are higher, due to higher tonnages used and absence of biodegradability. RCRs for all compartments are in a similar range for the 1-octanol/cyclohexane mixture. It should be noted that the release and exposure calculations performed in appendix 2 are theoretical, using a standardised exposure scenario, which allows comparison of the various substances. They do not represent real conditions at the applicants site. Actual releases of TCE to wastewater have been demonstrated to be negligible. It can be concluded that the alternative solvent 1-octanol/cyclohexane is beneficial with regard to human health considerations. Given the unproven nature of this alternative, it is not possible to fully evaluate the likely changes in energy requirement or other impacts associated with its use. The boiling point of 1-octanol is considerably higher than that of TCE or toluene and its recycling is likely to require considerably more energy to purify and recover, as described in Section Availability The component substances of the mixture could be considered available to the applicant. The applicant is not aware of a suitable supplier for 1-octanol, but it could be expected that this substance would be available on the EU market in sufficient quantity and quality. Cyclohexane is readily available as the applicant is a manufacturer of the substance. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 67

74 The process for using 1-octanol in cyclohexane has not yet been developed. Both the extraction process and the recycling of the mixture would need to be investigated, developed and commercialised before this mixture can be employed. This would require a full R&D programme that is likely to take considerably longer than for toluene. This technology will not be developed sufficiently to allow commercial operation before the Sunset Date and therefore cannot be considered available Conclusion on suitability and availability for 60% 1-octanol in cyclohexane The technical feasibility of 1-octanol in cyclohexane as a closed-loop extraction solvent is highly uncertain. So far, its use has been proposed only in academic journals and its use is commercially unproven. Nevertheless, its feasibility has been evaluated using the technical feasibility criteria defined in Section 2.3. Under this comparison, this solvent mixture has been found to be technically infeasible for the applicant; it is incompatible with existing plant facilities due to its low density. The alternative has been found to be a promising candidate for extraction in the future due to its high extraction capacity (solubility) but many technical hurdles remain and require R&D to investigate. The experimental nature of the alternative severely limits its economic feasibility at present. It is not known whether or not this mixture is a true alternative and as such it is not possible to justify investment in a new extraction facility to employ it. Therefore, it cannot be considered economically feasible for the applicant. Instead, toluene represents a more feasible and thus realistic alternative. If the issue of technical feasibility could be overcome after future R&D, it would be likely that this alternative would result in reduced risks to human health. The component substances carry less severe hazards and a smaller risk to both human health and the environment, but the impact of the whole process on the environment cannot be evaluated at present. It could be expected that higher energy consumption due to the recycling of the mixture could occur, though this may be offset by a lower consumption rate of the alternative substances in comparison to TCE. The substances comprising the alternative can be expected to be readily available to the applicant before the Sunset Date for TCE but the technology to use them is not. This is because of the lack of knowledge to employ 1-octanol in cyclohexane as a technically feasible alternative. The R&D process to gain the necessary expertise is likely to substantially exceed that required for toluene. Therefore, this alternative could be considered a potential alternative to toluene or a second generation alternative to TCE. Overall, this alternative is not considered a feasible alternative to TCE for the applicant. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 68

75 6 Overall conclusions on suitability and availability of possible alternatives for TCE 6.1 Alternatives substances and technologies considered A total of 32 alternative solvents and several technologies were originally considered in Section 4 of this AoA. The many of the solvent systems carry SVHC properties (such as benzene or other halogenated solvents) or have not been proposed as commercially applicable alternatives by available research. Out of all identified potential alternative substances, only two were deemed potentially feasible. The alternative technologies that were considered are not applicable to the applicant, as they would require a completely new supply chain for them to be implemented. Toluene and a proposed mixed extraction solvent system consisting of 1-octanol in cyclohexane were considered the most promising alternatives. Toluene is used in other commercial caprolactam extraction plants (including one that is part of the Grupa Azoty Group), while mixed solvent systems such as 1-octanol in cyclohexane have been proposed in the scientific literature as alternatives to the use of toluene. These two represent the most feasible alternatives to the applicant and were evaluated in detail in Section Conclusions on comparison of alternatives to TCE Conclusions on technical feasibility Neither toluene nor 1-octanol in cyclohexane were identified as technically feasible alternative to TCE. This is because their densities are too low to allow their use in the existing plant of the applicant. Therefore, both of these alternative solvent systems would require the construction of a new plant. Were this to take place, it is known with certainty that toluene could be used to extract caprolactam; however, this would result in a reduction in the quality of the ammonium sulphate coproduct. This also leads to an incompatibility of the ammonium sulphate with other integrated plant processes and would require the construction of separate crystallisation facilities to allow its continued use or it would lead to the generation of unacceptable amounts of waste. In addition, it would also require considerably more steam energy to operate the process due to the higher boiling point of toluene in comparison to TCE. The mixed solvent system is a potentially superior extraction medium to toluene based on the results of academic research (Gong, et al., 2008), but it has not been used commercially in the purification of caprolactam, and therefore its performance is uncertain. Its recycling also has potential issues due to both increased complexity (separation of water, cyclohexane and 1-octanol rather than just water and TCE) and because of the high boiling point of 1-octanol. Its performance with regard to yield and purity of ammonium sulphate is also unknown. Considerable R&D would be required to investigate the use of this system. Taking into account the current state of knowledge, toluene is clearly the most feasible alternative out of those considered but nevertheless it is not feasible from the perspective of the applicant. Considerable R&D is required in order to address the issue of ammonium sulphate purity and Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 69

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78 plant s useful life of approximately years. While a new extraction plant would need to be constructed, it would avoid the need to replace existing crystallisation facilities. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 72

79 7 References Alessi, V., Penzo, R., Slater, M. J. & Tessari, R., Caprolactam Production: a Comparison of Different Layouts of the Liquid-Liquid Extraction Section. Chem. Eng. Technol., Volume 20, pp Aquafil, THE ECONYL REGENERATION SYSTEM. [Online] Available at: regeneration process.pdf [Accessed 1 March 2014]. Burdick, D. L. & Leffler, W. L., Petrochemicals in nontechnical language. Oklahoma: Pennwell Books. Chemsystems, PERP Program Caprolactam New Report Alert, July [Online] Available at: abs.pdf [Accessed 4 March 2014]. Chemsystems, Nylon 6 and Nylon 6,6 Process Technology, Production Costs, Regional Supply/Demand, Forecasts, and economic comparison of Alternative Production Routes are presented - Report Abstract. [Online] Available at: abs.pdf [Accessed 4 March 2014]. Chen, D.-x.et al., Liquid liquid extraction of caprolactam from water using room temperature ionic liquids. Separation and Purification Technology, Volume 104, pp DECC, A brief guide to the carbon valuation methodology for UK policy appraisal. [Online] Available at: data/file/48184/3136- guide-carbon-valuation-methodology.pdf [Accessed 25 June 2014]. Dow, Product Safety Assessment Trichloroacetylene. [Online] Available at: 00d8/0901b803800d88b4.pdf?filepa th=productsafety/pdfs/noreg/ pdf&frompage=getdoc [Accessed 17 April 2014]. EIPCCB, BREF Large Volume Organic Chemicals. [Online] Available at: bref 0203.pdf [Accessed 4 March 2014]. Fisher, G., DSM's 50 years in caprolactam. Fibres & Textiles in Eastern Europe, Issue October/December, p. 82. Frost, J., Synthesis of caprolactam from lysine. EU, Patent No. EP B1. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 73

80 Glazko, I. L., Druzhinina, Y. A. & Levanova, S. V., Performance and Selectivity of Organic Solvents in Extraction of Caprolactam from Lactam Oil. Russian Journal of Applied Chemistry, 6( ), p. 80. Gong, X. et al., Selection and Evaluation of a New Extractant for Caprolactam. Chinese Journal of Chemical Engineering, 16(6), pp Gong, X., Lü, Y. & Luo, G., Distribution coefficient of caprolactam and methyl caprolactam using benzene toluene as extractants: experiments and predictions. Chinese Journal of Chemical Engineering, 15(4), pp Grupa Azoty Group, Sposób wytwarzania ε-kaprolaktamu. Poland, Patent No. PL Grupa Azoty Group, Grupa Azoty Strategy [Online] Available at: azoty strategy pdf [Accessed 25 July 2014]. Grupa Azoty Group, Directors' Report on the Operations of the Grupa Azoty Group for the 12 months ended December 31st [Online] Available at: m/nb/biznes/ /064526/director s report on the operations of th e grupa azoty group 2013.pdf [Accessed ]. Gui, J., Deng, Y., Zhide, H. & & Sun, Z., A novel task-specific ionic liquid for Beckmann rearrangement: a simple and effective way for product separation. Tetrahedron Letters, Volume 45, pp Gunardson, H., Industrial Gases in Petrochemical Processing: Chemical Industries, s.l.: Marcel Dekker. IARC, IARC Monographs on the Evaluation of Carcinogenic Risks to Humans. Vol Trichloroethylene, Tetrachloroethylene and Some Other Chlorinated Agents., Lyon: World Health Organization. ICIS, DuPont/BASF take new route to caprolactam. [Online] Available at: [Accessed 4 March 2014]. KMPS, Koch Modular Process Systems, LLC - Liquid extraction. [Online] Available at: [Accessed 28 May 2014]. Landrigan, P. J. & Etze, R. A., Textbook of Children's Environmental Health. Oxford: Oxford University Press. Law, J. D. & Todd, T. A., Liquid-Liquid Extraction Equipment, s.l.: s.n. Murphy, V. et al., Production of caprolactam from carbohydrate-containing materials. EU, Patent No. EP A1. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 74

81 OECD, Ammonium sulfate SIDS Initial Assessment Report for SIAM 19. [Online] Available at: [Accessed 13 May 2014]. Pajak, M. et al., METHOD OF CONTINUOUSLY EXTRACTING E-CAPROLACTAM. Poland, Patent No Ritz, J., Fuchs, H., Kieczka, H. & Moran, W., Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release. Caprolactam. [Online] Available at: ullmann [Accessed 11 March 2014]. Smallwood, I. M., Solvent Recovery Handbook. Second edition ed. Oxford: Blackwell Science Ltd. Thomas, J. M. & Raja, R., Design of a green one-step catalytic production of ε-caprolactam (precursor of nylon-6). PNAS, 102(39), pp Toray, undated. Chemistry. [Online] Available at: [Accessed 11 March 2014]. van Delden, M. L., Caprolactam extraction in a pulsed disc and doughnut column with a benign mixed solvent, Twente: University of Twente. Zbigniew Wadach, J. S., Dilemmas over industrial power engineering - Combined heat and power plant in Azoty Tarnów. Chemik, 66(10), pp Zimowski, A. et al., Caprolactam Production Method. Poland, Patent No Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 75

82 Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 76

83 8 Annex Justifications for confidentiality claims As Grupa Azoty S.A. has a status of the issuer listed on the Warsaw Stock Exchange (Giełda Papierów Wartościowych w Warszawie S.A.), the submitted document cannot be made public as a whole, due to the fact that it contains confidential information within the meaning of Article 154 of the Act of 29 July 2005 on Trading in Financial Instruments (Journal of Laws ), i.e. the ones defined in a precise manner, referring directly or indirectly to one or more Issuers of financial instruments, one or more of such financial instruments or acquisition or sale of such instruments which have not been made public and which after such submission could considerably affect the price of those financial instruments or the price of related derivative financial instruments. In particular, the publication of the submitted document must not cover items which were not made public by the Company, i.e. financial plans and financial forecasts, sales plans, and other relevant information that may have an impact on the share price of the Company. In accordance with the regulations of the Polish capital market, the breach of disclosure obligation results in administrative and penalty sanctions as set out in the Act on Trading in Financial Instruments and related legislation. Particular care has been taken to minimise the presence of confidential information in the AoA document and thus the confidentiality claims made by the applicant. However, it is necessary to include some confidential information to provide the rapporteurs and Committees the necessary information to fully evaluate this AfA in more quantitative terms. The justifications of confidentiality are given in the table below. The table of justifications (pages 78 to 89) has been removed as they are themselves confidential page numbers have been amended to reflect this Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 77

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87 10 Appendix 2 Comparative hazard and risk characterisation of alternatives to trichloroethylene for caprolactam purification 10.1 Background Article 60 (5) of REACH requires the applicant to investigate whether the use of the alternative substance would result in reduced overall risks to human health and the environment (as compared to the Annex XIV substance). In order to comply with this requirement in this Appendix the hazard profiles of those substances selected to be evaluated in detail are presented and suitable reference values for a quantitative comparison (DNELs for human health assessment, PNECs for an assessment of environmental toxicity) are either identified or (if no such reliable basis could be found in the public domain) derived. Some substances from an initial list of potential alternatives were deselected due to CMR properties similar or worse than TCE (e.g. benzene and nitrobenzene). Further to that, in the next few pages hazard considerations are presented for several solvents from the group of chlorinated aliphatic compounds, which led to the conclusion that these substances are not suitable alternatives for TCE (Section 10.2). In conclusion, three substances/mixtures were selected for in-depth analysis 21 Toluene, Cyclohexane, 1-octanol. Literature searches (up to April 2014) were performed for alternative substances in bibliographic databases as appropriate (after consultation of existing assessments) and assessments available from echemportal and other sources were screened. As not only a comparison of hazard profiles is required but a comparison of substance properties on a risk basis, a human health and environmental exposure scenario is developed (Section 10.4). Exposure within this scenario is estimated using the Tier I tool ECETOC TRA v.3. This approach is different to that used in the CSR, as it should be applicable in a similar way for all substances assessed and therefore does not rely on the specific data (e.g. measured data) available for TCE. Section 10.5 presents the comparative risk characterisation and the overall conclusions on risks from using the alternative substances. 21 For the hazard analysis cyclohexane and 1-octanol are considered on their own, but their use as a mixture is taken into account in the exposure assessment. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 93

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89 flammability and potential to form acetylene chloride in presence of strong base, a substance with explosive properties (ATSDR, 1996). 1,1,1,2-Tetrachloroethane and 1,1,2,2-Tetrachloroethane In a recent evaluation of their carcinogenic properties, the International Agency on the Research on Cancer concluded for both substances that there is sufficient evidence in experimental animals for the carcinogenicity. The overall conclusion for both substances was possibly carcinogenic to humans (Group 2B) (IARC, 2013). Therefore, these substances can be considered as suspicious carcinogens, similar to Carc. 2 classified substances. In addition to the concern for carcinogenic properties, there is a general tendency to substitute chlorinated solvents. As further regulatory pressure can be expected to replace these substances, this group of substances does not constitute a valid long-term alternative for TCE. In conclusion, these chlorinated solvents are excluded from an in-depth comparison with TCE Reference values (DNELs, PNECs) for trichloroethylene and alternative substances Introduction In the following Sections, DNELs and PNECs are discussed, which can be used for a comparative assessment. Available monographs, data from registration dossiers as available at ECHA-CHEM (ECHA, 2014) as well as published data (in case of inconsistencies or data gaps) are used for this purpose. If no DNELs/PNECs or similar reference values are available, which are compliant with requirements according to ECHA Guidance (ECHA, 2008; 2012b) (or if there is not enough information available on the rationales for deriving the values, which is often the case with the values reported in ECHA CHEM), then based on available data tentative DNELs/PNECs are derived to be used in this comparative assessment, this way giving emphasis to a harmonised approach for all substances. The tentative values should not be considered as a final evaluation of the effects of the substances. These values are used for this comparative assessment only and are not intended to represent a full assessment of the substances concerned. For human health considerations DNEL long-term inhalation workers for all alternative substances are used. For trichloroethylene the inhalation concentration associated with a risk level of 10-5 (DMEL) is used for comparison with the alternative substances. Dermal exposure is considered only for 1-octanol. In agreement with the approach used in the Chemical Safety Report of this Application for Authorisation, an approach has been developed to consider the evaporation of highly volatile solvents (the approach is detailed in Section 10.6). Based on these exposure considerations and calculations, it can reasonably be assumed that the substance evaporates from the workers gloves before any dermal exposure can occur. Therefore, a respective tentative DNEL long-term, dermal, workers is derived for1-octanol, but not for the more volatile solvents, which evaporate within seconds. For the environmental assessment, the following reference values are used for the comparative assessment: Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 95

90 PNEC STP PNEC freshwater Values for PNEC Soil and PNEC Sediment are calculated with ECETOC TRA using the equilibrium partitioning method for all three substances. No PNECs for marine water and marine sediment were derived, as these compartments are not relevant for the production facilities of the applicant. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 96

91 10.3.2Trichloroethylene Classification According to Annex VI of the CLP Regulation TCE is classified as follows: Ecotoxicity Existing reference values Predicted no effect concentrations as derived according to ECHA-CHEM and EU-RAR (ECB, 2004b; ECHA, 2014) are given in Table There is full agreement between IUCLID and EU RAR regarding freshwater aquatic toxicity studies and PNEC derivation. Based on reliable chronic studies for fish and algae, PNEC freshwater was derived by applying an assessment factor of 50 on the chronic NOEC determined for freshwater fish (Jordanella floridae, 28 days, flow through) of 5.76 mg/l, which was lower than the EC 10 determined for algae (Chlamydomonas reinhardtii, 72 h: 12.3 mg/l). This results in a PNEC freshwater of 115 µg/l. Thus, PNEC derivation follows the recommendations given by REACH guidance on information requirements and chemical safety assessment, Part R.10. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 97

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93 Human Health A DMEL long-term, inhalation workers of 3.0 mg/m 3 associated with a risk level of 1 x 10-5 is derived in the Chemical Safety Report of this Application for Authorisation. This DMEL is based on epidemiological data describing the association of kidney cancers in workers with trichloroethylene exposure. An exposure-risk relationship leading to slightly higher risk was derived by RAC (2014), resulting in an excess risk of 1.2 x 10-5 per 1 mg/m 3 and a workplace concentration of 0.83 mg/m 3 at a risk level of 1 x The DMEL derived in the CSR is used for the RCR calculations in the tables in Section , but both values are taken further for discussion and comparison of trichloroethylene with alternatives. As discussed above (Section ), no DMEL for dermal exposure is derived, as percutaneous absorption is considered negligible in the case of the highly volatile solvents (trichloroethylene, toluene, cyclohexane; see Annex 1 of this report) Toluene, CAS Classification According to Annex VI of the CLP Regulation Toluene is classified as follows: Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 99

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101 Poland described an 8 hour limit value of 100 mg/m³ and the Netherlands published a limit value of 150 mg/m³. Short-term limit values, not mentioned in the table above, range from 40 ppm (Latvia, factor 2) to 300 ppm (USA, OSHA). In most cases a factor 2 to 4 is considered. The latest assessment report for toluene evaluated here was dated from 2005 and the literature search included literature up to the End of January The more recent report by Anses (2011) conducted a literature search until 2009 but focused on neurotoxic and ototoxic effects and thus performed a selected literature search only. In order to include all relevant data which would potentially lead to a more stringent assessment, a PubMed literature search (NLM, 2014) was performed for the publication dates in between 2005 and Only one relevant experimental study was identified. Roberts et al., 2007 exposed pregnant rats via whole body inhalation o 0, 250, 750, 1500 or 3000 ppm of toluene for 6 hours per day on gestation days The maternal and developmental NOAEL was identified at 750 ppm (maternal effects: reduced body weight, ataxia and hyper-responsivity; foetal effects: significant dose-related effects on body weights). The LOEAL reported was 1500 ppm (Roberts et al., 2007). Discussion of suitability of reference values for comparative assessment Inhalation reference value The inhalation DNELs presented in ECHA-CHEM most certainly represent existing OELs. As there are no further details provided, these reference values according to ECHA-CHEM cannot be used for comparative assessment without a full understanding of their origin. In the EU RAR no definite value for risk assessment is provided. Instead, based on the effect assessed (e.g. general systemic toxicity after repeated exposure) and the quality of the available dose descriptor (e.g. adequacy of study duration) a minimal margin of safety (MOS min ) was determined for each specific case. The RfC provided by the U.S. EPA, the MRL of ATSDR, the Chronic REL of the Cal- EPA as well as the VTR presented by French Anses and the German TRD value represent reference values for general population and thus cannot be used for worker assessment required here. However considerations leading to the POD of reference value establishment, in particular of RfC and VTR, are helpful and are thus considered when deriving a DNEL for systemic toxicity after inhalation exposure. Between OELs reported above and critical NOAECs identified there is only a little gap, when compared to assessment factors usually chosen for DNEL derivation according to ECHA Guidance on IR and CSA Chapter R.8 (ECHA, 2012b). Thus these OELs are not adequate to be used for comparative assessment. Taken together, there is a need for DNEL derivation according to the procedure laid down in the ECHA Guidance R.8. In a literature search only one relevant experimental study was determined after the latest data of an assessment report (cf. Roberts et al., 2007). As effect levels are above the ones reported in the critical study identified for this specific endpoint in the EU RAR (ECB, 2003) this experimental result is not further considered for deriving a reference value. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 107

102 Dermal reference value The dermal DNEL presented in ECHA-CHEM cannot be used for comparative assessment without a full understanding of its origin. As there are no data on repeated dose toxicity by dermal exposure the oral NOAEL of 625 mg/kg bw/d was used in the EU RAR to evaluate risk for general toxicity by repeated dermal exposure in the EU RAR. No other relevant dermal reference values could be identified. Conclusions: tentative DNELs for comparative assessment Worker tentative DNEL Inhalation systemic effects long term exposure In the EU RAR (ECB, 2003) a NOAEC of 1125 mg/m³ (300 ppm) for general systemic toxicity was identified in a 2-year study with rats. Rats were exposed to 0, 30, 100 or 300 ppm of toluene for 6.5 hours per day on 5 days per week. In high concentration group no effects were observed and thus a NOAEC of 300 ppm was reported. According to ECHA REACH Guidance R.8 the following assessment factors are used: AF for difference in duration of exposure: 1 (chronic exposure duration) AF for other interspecies differences: 2.5 remaining differences (default); 0 allometry (not required); AF for intraspecies differences: 5, leading to an Overall Assessment Factor: 10 With the correction of starting concentration based on differences in between experimental and human conditions: Corrected NOAEC = 1125 * 6.5 h/d / 8 h/d * 6.7 mg/m³ / 10 mg/m³= mg/m³ finally leads to a tentative DNEL of 61.2 mg/m³ (= 16 ppm). In the EU RAR a further LOAEC of 88 ppm is reported for increased risk of spontaneous abortions. The LOAEC was identified via a questionnaire to female workers from Singapore (Ng et al., 1992) (12.4% abortions in high exposure group compared to 2.9% in low exposure group and 4.5% of control group (not exposed); with spontaneous absorption ranging in between 5 to 10% when evaluated via questionnaires). As human exposure is assumed to be chronic a rough estimate for a DNEL based on this study would lead to a value of 17.6 ppm (using an assessment factor for intraspecies differences only). This value is similar as the above presented value calculated on basis of the experimental data obtained for general systemic effects in rats. However, without confirmation of the effects and the associated exposure levels by another study, the study by Ng is not qualified enough to serve as basis for final DNEL derivation. This opinion is shared with other evaluating bodies like the German Permanent Senate Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area (MAK Commission, DFG; Greim, 1993) or as stated in the review of Bukowski (2001). E.g. MAK Commission states that effects observed in the Ng-study are surprising as such effects have not been observed in studies on women exposed to high concentrations due to toluene abuse ( sniffing ). In these studies developmental delays were reported consistently rather than Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 108

103 embryolethal effects. Thus indicating the relevance of the NOAEC identified in studies identified with experimental animals. As mentioned above the RfC provided by the U.S. EPA represents a reference value for general population and thus cannot be used for worker assessment required here. However the identified POD for RfC derivation is helpful in assessing the adequacy of the reference value derived from the 2- year study identified in the EU RAR. The POD identified by U.S. EPA was 128 mg/m³ (34 ppm). This value represents the arithmetic mean of NOAECs identified in various adequate epidemiological studies for neurological/neurobehavioural effects. As only occupational studies were used no adjustment of exposure conditions needs to be performed and no assessment factor for interspecies differences has to be applied. Furthermore, as chronic studies were used only no assessment factor for difference in exposure duration has to be applied either. Thus, only the assessment factor for intraspecies effects is required. Due to the large database with a variety of occupationally exposed cohorts an assessment factor of 2 is considered sufficient, leading to a value similar to that derived from experimental data. Overall this derivation would lead to a tentative DNEL of 64 mg/m³ (17 ppm). In conclusion, derived DNELs are comparable in their height and a DNEL of 16 ppm is used for comparative assessment of alternatives. Worker tentative DNEL Dermal systemic effects long term exposure As discussed in Section , no DMEL for dermal exposure is derived, as percutaneous absorption is considered negligible in the case of the highly volatile solvents (trichloroethylene, toluene, cyclohexane) (see Section 10.6). Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 109

104 10.3.4Cyclohexane, CAS Classification According to Annex VI of the CLP Regulation cyclohexane is classified as follows: Classification according to the joint entry (classification proposed in the joint registration dossier) differs insofar, as environmental classification is confined to acute aquatic toxicity, while no classification for chronic effects was performed. This is justified according to CLP criteria due to ready biodegradability combined with a low bioconcentration potential (log Kow < 4) together with an aquatic dataset confined to acute data. Ecotoxicity Existing reference values Predicted no effect concentrations as derived according to ECHA-CHEM and EU-RAR (ECB, 2004a) are given in Table Values according to ECHA-CHEM deviate considerably from those derived within EU RAR despite the fact that key studies are identical: For freshwater, acute toxicity results for fish, invertebrates and algae are available, with invertebrates being the most sensitive trophic level (Daphnia magna, 48 h, immobilization, static, measured; EC 50 : 900 µg/l). Within the EU risk assessment (ECB, 2004a) a nonspecific mechanism of Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 110

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107 In the EU RAR (ECB, 2004a) the most critical endpoints used for risk assessment were the result from the acute exposure study of humans leading to a NOAEL of 250 ppm (highest tested dose) and which is supported by animal data (NOAEL 500 ppm for neurotoxic effects). For assessing chronic systemic effects the NOAEL of 2000 ppm was used, which was established in studies with mice and rats and in which slight hepatotoxic effects were observed. As the effects observed (increase in absolute and relative liver weight, centrilobular hypotrophy, increase in mitotic index) are hardly adverse this assessment is stated to be very conservative by the authors. In the EU RAR no definite value for risk assessment is provided, but instead relevant exposure scenarios are established comparing the most critical effect with the expected exposure and thus determining a margin of safety (MOS; experimental NOAEL / estimated relevant exposure value = MOS) for this specific situation. Relevant effects and established exposure scenarios for workers are Acute neurobehavioural effects (NOAEC 250 ppm MOS in the range of 0.25 to 12.5) Chronic hepatic effects (NOAEC 2000 ppm MOS in the range of 2 to 100) For non-threshold effects such as irritation, sensitisation, and mutagenicity no concern was identified Further there was no concern regarding carcinogenicity and reproductive toxicity. In the SIDS initial assessment profile for cyclohexane (OECD, 2000) no reference values (DNELs) are derived, but NOAEL(C)s for most important studies are summarised, including acute human data. The same toxicity profile as described in other assessment reports is identified and thus further supports the reference value chosen. It is further stated that cyclohexane is not genotoxic in vitro, this was demonstrated in a series of studies including Ames test, mouse lymphoma assays, sister chromatid exchange assay, Unscheduled DNA synthesis assay and DNA binding to Ecoli. An in vivo rodent bone marrow cytogenetic assay was considered negative and a weak tumour promoting activity was mentioned. In 2003, the U.S. Environmental Protection Agency published its Toxicological review of cyclohexane (EPA, 2003). Data reported are basically the same as summed up in the other assessment reports available. US EPA derived a Reference concentration for Chronic Inhalation Exposure (RfC for the general population) of 6 mg/m³ (i.e. 1.7 ppm). The basis for RfC derivation was the reduced pup weight in the F1 and F2 generations of the valid two-generation inhalation study with rats. This effect was chosen by the authors as drastically reduced bodyweight in pups is associated with developmental delays and lifelong mental and physical deficiencies. The NOAEC identified was 2000 ppm (i.e mg/m³). Parental animals also had reduced bodyweights at this exposure level, however these effects were less severe (less than 10% difference from controls) and somewhat reversible during the experiment. The effects observed in the 90-day studies (hepatic changes; diminished response to audio stimuli) were not used for assessment as they either were not accompanied by pathological changes or were of low quality for quantification of an RfC as these data are subjectively measured clinical observations. Thus for RfC derivation the BMCL 1sd (Benchmark concentration limit with benchmark response as one standard deviation from controls) was established from the raw data concerning the statistically reduced pup body weight (using U.S. EPA s Benchmark Dose Software (BMDS) version 1.3; model chosen was quadratic with constant variance), a human equivalent concentration was calculated (i.e mg/m³) and used as Point of Departure. The RfC was then obtained using an uncertainty factor of 300 (3 interspecies differences, 10 intraspecies variability, 10 database deficiencies). EPA further states that Data are inadequate for an Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 113

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110 Discussion of suitability of reference values for comparative assessment Inhalation reference value The inhalation DNELs presented in ECHA-CHEM most certainly represent existing OELs. As there are no further details provided, these reference values according to ECHA-CHEM cannot be used for comparative assessment without a full understanding of their origin. Between OELs reported above and critical NOAECs identified there is only a small difference, when compared to assessment factors usually chosen for DNEL derivation according to ECHA Guidance on IR and CSA Chapter R.8 (ECHA, 2012b). Thus these OELs are not adequate to be used for comparative assessment. Within the EU RAR no definite value for risk assessment is provided, but instead relevant exposure scenarios are established comparing the most critical effect with the expected exposure and thus determining a margin of safety (MOS) for this specific situation. As for comparative assessment of alternative substances a concrete reference value is needed this type of assessment (MOS) is not adequate for the purpose. The RfC provided by the U.S. EPA represents a reference value for general population and thus cannot be used for worker assessment required here. Taken together, there is a need for DNEL derivation according to the procedure laid down in the ECHA Guidance R.8. Dermal reference value The dermal DNEL presented in ECHA-CHEM cannot be used for comparative assessment without a full understanding of its origin. No other dermal reference values could be identified, thus indicating the need for DNEL derivation according to the procedure laid down in the ECHA Guidance R.8. As there are no relevant experimental toxicity data with repeated dermal exposure a route-to-route extrapolation will have to be performed on basis of the systemic NOAEC of 2000 ppm, which was identified in 90-day studies with mice and rats. For dermal absorption there is one reliable study available (cf. ECB, 2004a; ECHA, 2014; EPA, 2003). Within this study Fischer F344 rats were exposed dermally (occluded) to 14C-cyclehexan at concentrations of 1 mg/m³ or 100 mg/m³. The study authors mentioned that in the first experiment exposure was primarily as cyclohexane vapour whereas in the second set with 100-fold dermal loading exposure was primarily as cyclohexane liquid. With 1 mg/cm³ dermal burden approximately 40 to 60% of the applied dose was absorbed. In case of 100 mg/m³ exposure only 4% of the applied dose was absorbed. It is worth mentioning, that in the EU RAR in all exposure scenarios considered the modelled dermal exposure (with 5% dermal absorption from liquid phase in rats, cf. above) is negligible compared to inhalation exposure. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 116

111 Conclusions: Tentative DNELs for comparative assessment Worker tentative DNEL Inhalation systemic effects long term exposure In line with the conservative assessment of the EU RAR a NOAEC of 2000 ppm is used as basis for DNEL derivation according to ECHA Guidance R.8. This NOAEC was identified in the EU RAR in the 90- day inhalation toxicity study with rats for systemic effects (slight hepatic effects; which could be adaptive physiological changes (see ECHA-CHEM) but might also be first signs of a potential liver toxicity that would only become apparent with long-term exposure to cyclohexane (according to U.S. EPA)). As mentioned above other organisations also identified this NOAEC as key value for evaluation. It is further supported in its height by the relevant NOAEC identified by U.S. EPA for effects on body weight of pups in the two generation toxicity study. In this 90-day repeated inhalation toxicity study Crl:CD BR rats were exposed to 0, 500, 2000 or 7000 ppm (i.e. 0, 1720, 6880 or mg/m³) of cyclohexane vapour for 6 hr/day, 5 days/week for 14 weeks. According to ECHA REACH Guidance R.8 the following assessment factors are used: AF for difference in duration of exposure: 2 (subchronic to chronic extrapolation) AF for other interspecies differences: 2.5 remaining differences (default); 0 allometry (not required); AF for intraspecies differences: 5, leading to an Overall Assessment Factor: 25 With the correction of starting concentration based on differences in between experimental and human conditions: Corrected NOAEC = 6880 * 6 h/d / 8 h/d * 6.7 mg/m³ / 10 mg/m³= mg/m³ finally leads to a tentative DNEL of mg/m³ ( 40 ppm). Worker tentative DNEL Dermal systemic effects long term exposure As discussed in Section , no DNEL for dermal exposure is derived, as percutaneous absorption is considered negligible in the case of the highly volatile solvents (trichloroethylene, toluene, cyclohexane) (see Section 10.6). Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 117

112 Octanol, CAS Classification No Harmonised Classification according to Annex VI of the CLP Regulation is available for 1-octanol. The classification according to the joint entry in the C&L inventory database is as follows: Ecotoxicity Existing reference values Predicted no effect concentrations as derived according to ECHA-CHEM, SIDS initial assessment report (OECD, 2006b) and MOE Japan 24 are given in Table Values according to ECHA-CHEM deviate considerably from those derived within the SIDS assessment as well as the assessment by MOE Japan. 24 Ministry of the Environment, Japan, Profiles of the Initial Environmental Risk Assessment of Chemicals, erac/ - 1-octanol Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 118

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114 The assessments performed by OECD and MOE Japan proceeded according to option 1, i.e. choosing AF 100 while regarding the chronic study on Daphnia magna as the sole reliable chronic result (PNEC 10 µg/l). PNEC sediment and PNEC soil according to ECHA-CHEM were derived by equilibrium partitioning method (not verified here). No corresponding values are available from other assessments. Concerning STP microorganism toxicity, the only PNEC reported is from ECHA-CHEM (55.5 mg/l). According to the information provided, an AF of 100 has been used to derive this value. However, reviewing the study summaries published by ECHA-CHEM yields a multitude of non-assignable data (RL4) obviously used in a weight of evidence approach. The only endpoint study record with reliability 2 rating refers to the protozoon Entosiphon sulcatum (Euglenida) with probably very limited relevance for STPs (EC 3 72 h: 44 mg/l). Further study results with organisms of higher relevance for STPs are all reliability 4. They generally refer to secondary sources and obviously two to three study summaries are based on the same original study. Most relevant results are (without duplicates): Tetrahymena pyriformis: EC 50 (48 h) mg/l Vibrio fisheri (MICROTOX test, regarded to be of low relevance for STP microorganisms): mg/l Activated sludge respiration inhibition (OECD 209), EC 50 (3h) 350 mg/l. According to REACH guidance R.7b, (ECHA, 2012a) results with vibrio fishery are of low relevance for STP microorganisms and should at best be used together with other data in a weight of evidence approach. In view of the experimental results outlined above it is not clear what study result was the basis for derivation of the PNEC STP according to ECHA-CHEM: The assessment factor 100 would imply an effect concentration of 5.55 g/l, whereas reported effect concentrations are much lower. Discussion of suitability of reference values for comparative assessment The PNEC freshwater as given by ECHA-CHEM is not appropriate for comparison of hazard of 1-octanol as an alternative to TCE due to the low assessment factor used for derivation. No justification is available in the published IUCLID data set in ECHA-CHEM. On the other hand, PNECs for freshwater derived according to SIDS and according MOE Japan, largely ignore data for other trophic levels in their assessment and the resulting value of 10 µg/l may be too conservative. As an alternative, data are newly assessed considering a further study on fish, which is available. It was performed according to US-EPA guideline Fathead minnow (Pimephales promelas) larval survival and growth test method by US-EPA and published (Pickering et al., 1996). Deviating from US-EPA test method , instead of fish larvae not older than 24 hours, in addition larvae aged 4 and 7 days were exposed to 1-octanol for 7 days in a semi-static test (daily renewal). In effect, the test is similar to OECD 212 ( Fish, Short-term Toxicity Test on Embryo and Sac-fry Stages ), rated as a chronic test under REACH. In the SIDS assessment the test was rated as the most reliable sub-chronic test available (RL 2). A study summary was also prepared under REACH (ECHA-CHEM, RL2), but the study was not chosen as key study for risk assessment. Analytical determination of grab samples of old media however showed a drastic decline to approximately 10% at the highest concentration of 11.9 mg/l, approximately 1% at 6 mg/l and below LOQ (0.05 mg/l) at 3 mg/l (lowest test item concentration: 0.75 mg/l). The most sensitive endpoint was growth, with the lowest NOEC-values determined in the 3 parallel exposure groups of 4-day old larvae, i.e. 1.5, 0.75, and 3.0 mg/l. Considering the decline in Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 120

115 actual exposure concentration, it seems to be reasonable to choose the lowest value for assessment, i.e mg/l as the NOEC for (sub)chronic fish toxicity. Taking into consideration chronic data for aquatic invertebrates, algae and fish, an AF of 10 seems to be justified according to REACH guidance R.10. The lowest NOEC / EC 10 of the data-set is the NOEC from the 7-day study on Pimephales promelas larvae of 0.75 mg/l. With an AF of 10 a PNEC of 75 µg/l results. Derivation of PNEC STP according to ECHA-CHEM is unclear, as study results do not fit to the assessment factor of 100 and the size of the PNEC (55.5 mg/l). The most relevant study would be the respiration inhibition test with a determined EC 50 of 350 mg/l. This is at the same time the one study of those with some relevance for STP microorganisms with the highest effect concentration. Taking an AF of 100 according to the standard, a PNEC STP of 3.5 mg/l results. Conclusions: tentative PNECs for comparative assessment The tentative aquatic PNEC of 75 µg/l derived by reassessing relevant available aquatic toxicity data for 1-octanol is appropriate for comparative assessment as an alternative to TCE. For STP microorganissms, a tentative PNEC STP of 3.5 mg/l as derived by reassessing available study summaries from ECHA-CHEM according to accepted methodology will be used in the assessment of alternatives to TCE. Human toxicity Existing reference values 1-octanol was registered according to Regulation (EC) No 1907/2006 in 2010 (ECHA, 2014). In 2006 an assessment of the OECD was published (OECD, 2006a; b; c) as well as a national (German) occupational exposure level (OEL, AGS, 2006; IFA, 2014). In all assessments, 1-octanol was included in a category of Long Chain Alcohols (definition taken from OECD: C6-22 primary aliphatic alcohols; subgroup linear alcohols) 26. There are only limited data available for 1-octanol itself (cf. the above mentioned sources): 26 OECD category justification: The category must be justified firstly on the basis of structural features, and physicochemical, environmental (degradation, toxicity) and health properties. Whilst this set exhibits a wide range of values for some of the properties, they share common modes of degradation and biological action, as well as many uses in common. The long chain aliphatic alcohol family has at its centre a homologous series of increasing carbon chain length.. All components of all commercial products relevant to this category are primary alcohol structures. The hydroxyl group in alcohols confers upon the hydrocarbon chain a considerable degree of polarity, and hence affinity for water. It is susceptible to oxidation by metabolic processes. Linear or essentially linear hydrocarbon chains are also readily oxidised metabolically. No highly branched structures are proposed for inclusion in the Category. Substances that contain a number of homologous components can be expected to behave in a way consistent with the carbon number distribution present. Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 121

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117 Basis for both systemic long-term threshold values was a NOAEL identified in a 90-day feeding study conducted with 1-hexanol. In this study no effects were observed up to the highest dose tested. Read-across was performed based on the category justification for long chain alcohols. Details on assessment factors used are mentioned. It is stated that the systemic acute threshold values was based on the systemic long-term threshold values but no further explanation is given. There was no reference value established by the OECD (2006a; b; c). However a similar toxicity profile for linear alcohols was confirmed. In general these substances are of low acute toxicity after oral, inhalation or dermal exposure. They are slightly irritating to skin and eyes, but do not possess skin sensitising properties. For some category members there is evidence that they are acting as sensory irritants. Repeated exposure does generally not lead to significant systemic toxicity and NOAELs are between approximately 200 to 1000 mg/kg bw/day after subchronic oral treatment of rats via diet. There is generally no evidence for genotoxic or carcinogenic activity, however limited evidence is available indicating slight tumour promoting activities. There were no effects on reproductive organs in repeated dose toxicity studies and no impact on pup development in developmental toxicity studies. As for national regulations there is only one OEL available. The German Committee on Hazardous Substances (AGS) stated that respiratory irritation is a critical effect for OEL derivation as the systemic toxicity after repeated dosing is very limited. It was stated that the study by Seeber (2002) is essential. Volunteers (healthy young males, but partially with self-reported odour sensitivity) were exposed either to constant low concentrations of ppm 1-octanol or to changing exposure levels in the range of 0.2 to 12 ppm for 4 hours. Mean concentration was 6.4 ppm. Odour, annoyance and eye irritation were rated by the study subjects before exposure, several times during exposure and afterwards. In the experiment with changing exposure levels slight irritating effects were observed when comparing exposure groups to control groups exposed to air. These results were then compared to experimental results for 2-ethyl hexanol - a known sensory irritant and isomer to 1- octanol. In comparable experiments with varying exposure levels and mean concentrations of 10 and 20 ppm more pronounced irritating effects were seen (van Thriel et al., 2003). Based on this comparison the Committee concluded that a value of mg/m³ (20 ppm) is sufficiently safe for an 8 h-shift (sensory irritation, local effect). The 15 minutes short term exposure values was set to mg/m³ as well (no exceedance over 8 h-shift value, as the basis for OEL was a study with varying exposure concentrations including exposure peaks up to 12 ppm; IFA, 2014). There is a Workplace Environmental Exposure Levels (WEELs, developed by the Occupational Alliance for Risk Science (OARS) which is managed by Toxicology for Risk Assessment (TERA)) of 50 ppm for 1- octanol. As per definition this reference values provide guidance for protecting most workers from adverse health effects related to occupational chemical exposures. Conformance with these guideline values does not ensure protection of all workers. Workers may have underlying health conditions which make them unusually susceptible to the adverse health effects of some chemicals Source: Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 123

118 In all assessments mentioned above (e.g. ECHA-CHEM or AGS) the data on 1-octanol were complemented with data form the other members of the long chain alcohol category. The general conclusions are similar to the ones mentioned in the OECD reports (cf. above). Discussion of suitability of reference values for comparative assessment Inhalation reference value The long-term worker systemic inhalation threshold value in ECHA-CHEM was derived from a 90-day oral feeding study conducted with 1-hexanol. As there are no repeated inhalation toxicity studies available for 1-octanol and comparability seems given based on the category establishment by various regulatory bodies, which acknowledges a similar toxicological profile for C6 to C11 alcohols, transfer of the results from the 90-day oral feeding study conducted with hexanol seems adequate. Moreover, the developmental toxicity studies available for 1-octanol are inadequate as starting point for DNEL derivation as exposure duration is limited and effects observed in the oral gavage study yielding a lower NOAEL (130 mg/kg bw/d) might be due only to gavage application of this locally irritating substance. Using the inhalation study would potentially overestimate the toxic potential of 1-octanol as the highest concentration tested revealed no toxic effects (no LOAEL identified). For derivation of reference values in ECHA-CHEM the registrant deviated from the default assessment factors mentioned in ECHA Guidance on IR&CSA R.8 with reference to ECETOC reports (ECETOC, 2003; 2010; either default or 'informed' AF). In conclusion the 90-day oral feeding study used in ECHA-CHEM for threshold derivation seems justified, however as extrapolation factors used are not in accordance with ECHA Guidance on IR & CSA R.8 and justifications for deviations from default value are insufficient a long-term systemic inhalation DNEL will be established for comparison of alternatives. Sensory irritation which was identified in studies with healthy volunteers was not accounted for when assessing inhalation exposure. However as studies are available it should be checked if an acute and/or long-term worker local inhalation threshold could be established in order to compare to the systemic threshold value. The more conservative value will then be chosen for comparative assessment of alternative substances as requested in ECHA guidance. Dermal reference value The long-term worker systemic dermal threshold value in ECHA-CHEM was derived from a 90-day oral feeding study conducted with 1-hexanol. Read-across from 1-hexanol seems justified based on the fact that no repeated dermal toxicity studies are available for 1-octanol and 1-hexanol was part of the long chain alcohols category formed by various regulatory bodies. Route-to-route extrapolation from oral studies to dermal is a usual procedure and exemplified in ECHA guidance on IR & CSA R.8 Example B.5. It is mentioned that differences in oral and dermal absorption of experimental animals and humans have to be considered. Within the REACH registration dossier the only reliable experimental data reported concluded that the percutaneous absorption rate of undiluted n-octanol was 50% (ECHA, 2014). This was concluded based on the experimental study with 2 to 4 month old hairless mice which received 1 µci, 100 µl of Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 124

119 n-[14c]octyl alcohol octan-1-ol/2 cm² (24 h occluded exposure; Iwata et al., 1987). No other definite absorption data are available and thus no differences can be considered, thus the starting point for threshold value derivation used in ECHA-CHEM (oral NOAEL = corrected dermal NOAEL) is adequate. In conclusion the basis for threshold derivation seems justified; however as extrapolation factors used are not in accordance with ECHA Guidance on IR & CSA R.8 and justifications for deviations from default value are insufficient a long-term systemic dermal DNEL will be established for comparison of alternatives. Conclusions: tentative DNELs for comparative assessment Worker tentative DNEL Inhalation systemic effects long term exposure No adequate repeated inhalation toxicity study for 1-octanol is available. In accordance with other assessments read-across from the oral repeated dose experiment with 1-hexanol was performed and a route-to-route extrapolation was carried out in order to obtain a NOAEC for dermal DNEL derivation. The available NOAEL from the 90-day rat oral study was transferred into an inhalation NOAEL based on the Example B.3 of Appendix R. 8-2 in ECHA Guidance R.8: corrected inhalatory NOAEC = oral NOAEC * 1/sRVrat * (ABS oral rat/ ABS inhal human) * (srv human/wrv) 28 As mentioned above in case of 1-octanol no definite absorption data are available and thus no differences can be considered. Therefore the following adjustment is performed. corrected inhalatory NOAEC = 1127 mg/kg bw/d * 1/0.38 m³/kg bw (8 h value) * (6.7 m³/person / 10 m³/person) corrected inhalatory NOAEC = 1987 mg/m³ According to ECHA REACH Guidance R.8 the following assessment factors are used: AF for difference in duration of exposure: 2 (subchronic to chronic extrapolation) AF for other interspecies differences: 2.5 remaining differences (default); 0 allometry (not required); AF for intraspecies differences: 5, leading to an Overall Assessment Factor: 25 This leads to a tentative DNEL of mg/m³ ( 15 ppm). The reference value for sensory irritation derived by the German Committee on Hazardous Substances (AGS) was based on studies with human volunteers and in comparison with results 2- ethyl hexanol. Within ECHA Guidance on IR and CSA R.8 it is stated that Sensory irritation is experienced by humans and when reported in sufficient extent and detail, it can be the basis for the DNEL. However, no further details are provided on how to derive such a DNEL. From our point of 28 i.e. correction for differences in breathing volume during rest or light work during an 8 hour shift Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 125

120 view experimental study results are not detailed enough and thus suitable for DNEL derivation. When comparing the reference value mentioned by the AGS (i.e. 106 mg/m³ = 20 ppm) it is obvious that the DNEL derived for systemic effects is more conservative and thus can further be used for comparative assessment of alternatives. There are two developmental toxicity studies for 1-octanol. In the oral gavage study a maternal LOAEL of 130 mg/kg bw/d is observed (clinical effects such as lateral and abdominal position, unsteady gait, salivation, piloerection, nasal discharge and pneumonia). In the inhalation developmental toxicity study a NOAEC of 400 mg/m³ was reported, which is the highest exposure concentration as no toxic effects were observed. In both studies no developmental toxic effects were observed. Conversion of the NOAEC from the inhalatory study into a NOAEL reveals that in both experiments exposure concentrations are in the same range 29. The more pronounced maternal effects in the oral gavage study might be due to or at least enhanced by the bolus administration of the locally irritating substance. As no effects were seen in the inhalation developmental toxicity study it is anticipated that the slight maternal effects observed in the oral gavage study are covered when using the DNEL derived for systemic effects from the 90-day toxicity study. In conclusion, the tentative DNEL of mg/m³ ( 15 ppm) derived for long-term systemic effects (read across from 1-heaxanol) is suitable for comparative assessment of alternatives. Worker tentative DNEL Dermal systemic effects long term exposure No adequate repeated dermal toxicity study for 1-octanol is available. In accordance with other assessments read-across from the oral repeated dose experiment with 1-hexanol was performed and a route-to-route extrapolation was carried out in order to obtain a NOAEL for dermal DNEL derivation. The available NOAEL from the 90-day rat oral study was transferred into a dermal NOAEL based on the Example B.5 of Appendix R. 8-2 in ECHA Guidance R.8: Corrected dermal NOAEL = oral NOAEL * (ABS oral rat/ ABS dermal human). As mentioned above no definite absorption data are available and thus no differences can be considered. Thus the corrected dermal NOAEL = oral NOAEL = 1127 mg/kg bw/d. According to ECHA REACH Guidance R.8 the following assessment factors are used: AF for difference in duration of exposure: 2 (subchronic to chronic extrapolation) AF for other interspecies differences: 2.5 remaining differences (default); 4 allometric scaling (default rat); AF for intraspecies differences: 5, leading to an Overall Assessment Factor: 100 This leads to a tentative DNEL of mg/kg bw/d. 29 Conversion: 400 mg/m³ * 0.38 m³/d (daily breathing volume of a female rat) * (7 h experimental exposure duration / 24 hours (whole day exposure)) / 0.35 kg (body weight of female rat) = mg/m³) Use number: 1 Legal name of applicant(s): Grupa Azoty S.A. 126

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