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ANALYSIS of ALTERNATIVES Public Version 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 caprolactam purification Use number: 1 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 Forschungs- und 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. Table of contents 1 Summary..............................................................................................................................1 1.1 Background to this analysis of alternatives ....................................................................................1 1.2 Overview of Grupa Azoty S.A. supply chain....................................................................................2 1.3 Potential alternatives for TCE .........................................................................................................3 1.4 Suitability of potential alternatives for TCE....................................................................................4 1.5 Feasibility of potential alternatives for TCE....................................................................................4 1.6 Actions needed to improve the suitability and availability of potential alternatives.....................6 2 Analysis of substance function ..............................................................................................7 2.1 Caprolactam synthesis....................................................................................................................7 2.2 Description of the extraction process.............................................................................................8 2.3 Conditions of use and technical comparison criteria ...................................................................14 2.4 Summary of technical feasibility criteria ......................................................................................20 3 Annual Tonnage ................................................................................................................. 23 4 Identification of possible alternatives.................................................................................. 25 4.1 List of possible alternatives...........................................................................................................25 4.2 Description of efforts made to identify possible alternatives ......................................................26 4.3 Screening of identified alternatives..............................................................................................33 5 Suitability and availability of possible alternatives............................................................... 43 5.1 Alternative 1: Toluene ..................................................................................................................43 5.2 Alternative 2: 60% 1-octanol in cyclohexane................................................................................61 6 Overall conclusions on suitability and availability of possible alternatives for TCE ................ 69 6.1 Alternatives substances and technologies considered.................................................................69 6.2 Conclusions on comparison of alternatives to TCE.......................................................................69 6.3 Overall conclusion and future research and development ..........................................................70 7 References ......................................................................................................................... 73 8 Annex – Justifications for confidentiality claims................................................................... 77 9 Appendix 1 – Literature search terms.................................................................................. 91 10 Appendix 2 – Comparative hazard and risk characterisation of alternatives to trichloroethylene for caprolactam purification............................................................................ 93 10.1 Background ...................................................................................................................................93 10.2 Hazard considerations for chlorinated solvents ...........................................................................94 10.3 Reference values (DNELs, PNECs) for trichloroethylene and alternative substances ..................95 10.4 Exposure Assessment .................................................................................................................127 10.5 Comparative Risk Characterisation.............................................................................................129 10.6 Excursion: Comparison of the evaporation time from gloves ....................................................133 10.7 References for Appendix 2..........................................................................................................135 1 Summary 1.1 Background to this analysis of alternatives The substance of concern is trichloroethylene (hereafter referred to as TCE), EC No. 201-167-4, CAS No. 79-01-6, 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. 203-313-2, CAS No. 105-60-2) 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 AlphalonTM (Grupa Azoty Group, 2014). Tarnamid® plastics are produced at Tarnów, and AlphalonTM 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 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
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