Document Emy3j7KYdDyoOQ130Jdzg5VB0

chLai 17. Brussels, 20 September 2023 Europe's chlor-alkali producers support Cefic's request for an exemption for the use of PFAS in the chemical industry's industrial settings. Like many chemical industry processes, the production of chlorine, sodium/ potassium hydroxide and hydrogen (chlor-alkali) involves the use of materials that meet the EU PFAS definition in the current EU REACH restriction proposal. In Cefic's contribution (more specifically, the Inventory study on the use of PFAS in chemical plant equipment), mention is made of PFAS membranes and diaphragms in electrolysers for which no alternatives to PFAS have been identified'. As our industry uses this type of equipment, this document provides additional details on the use of fluoropolymers in chlor-alkali production. Historically, such equipment used mercury or asbestos-based materials, but these have been phased out under EU regulation and have energy efficiency considerations. In the search for alternatives to mercury and asbestos, PFAS-based membrane/ diaphragm technologies (BAT) were selected because of the substances' unique properties. These include chemical stability at temperatures up to 95C, low diffusion rates for hydrogen and chlorine, the capability to transport sodium or potassium ions efficiently and low electrical resistance to maintain energy efficiency. The requested exemption is indispensable in enabling the continued combined European production of chlor-alkali. These chemicals are at the basis of products vital for medication, clean drinking water, modern strategic metals/ polymers and more. Contents 1 The importance of the chlor-alkali sector 2 2 The link between our sector and PFAS materials 6 3 The use of PFAS materials in the chlor-alkali process and possible alternatives 7 4 Implementation of alternatives 14 5 Waste management 14 6 Summary 16 Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org A sector group of Cefic . European Chemical Industry Council - Cefic aisbl EUTransparency Register n 61879112323-90 Page 1 of 19 0 chlor 17. 1 The importance of the chlor-alkali sector The chlor-alkali industry typically produces chlorine, sodium/ potassium hydroxide and hydrogen through electrolysis of water and salt (sodium or potassium chloride). The annual production in Europe is approximately 10 million tonnes of chlorine, 11million tonnes of sodium/ potassium hydroxide and 270,000 tonnes of hydrogen. This industry is represented in Europe by the trade association Euro Chlor. Whilst this industry directly employs 7,000 people in the production process across Europe generating 13bn worth of chlor-alkali per year, the resulting chemicals form the basis of around 55% of Europe's entire chemical value chain which employs 1.2 million people across the continent at a value of 600bn per year. Chlorine and sodium/ potassium hydroxide are also the foundation of a dedicated, extensive downstream value chain leading to many critical products that are relied upon by Europe's workforce for safety and efficiency. Chlor-alkali chemicals also find use in the production of 88% of all modern medicines, the disinfection of the majority of Europe's drinking water, the purification of strategic metals, the recovery of precious metals from waste electronics as well as producing materials for batteries, windmills and solar panels. Many chlor-alkali products are also themselves alternatives to certain PFAS (e.g. PVC, polyurethane etc.). Additionally, chlor-alkali is the source of 4% of Europe's hydrogen and may play a role in kick-starting Europe's hydrogen economy. It is also important to note that, for safety reasons, there are specific challenges associated with the import and storage of chlorine meaning a local European chlor-alkali industry is vital. This value chain is estimated at around 113bn. The links above lead to more detailed information on the uses of these important products but these are summarised for convenience in the figures below. More information on the chlor-alkali process and its downstream usage can also be found in the chlor-alkali BREF2 and on the Euro Chlor website3. Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org A sector group of Cefic European Chemical Industry Council - Cefic aisbl EUTransparency Register rt. 61879112323-90 Page 2 of 19 chide 17. Chlorine Hydrogen Caustic Soda - 0 - 4..soi nOWSO 0. le Ma arm...am a am 2.0 2a, li. 1011" WC, Figure 1: Simplified overview of chlor-alkali production Figure 2: The main downstream chlorine applications Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org A sector group of Cefic European Chemical Industry Council - Cefic aisbl EUTransparency Register e 64879142323-90 Page 3 of 19 chide Figure 3: The main downstream caustic applications Figure 4: The main downstream hydrogen applications Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org A sector group of Cefic European Chemical Industry Council - Cefic aisbl EUTransparency Register n 61879112323-90 Page 4 of 19 chLai 17. The following describes the approximate quantities of chlor-alkali and their usage areas: For chlorine o PVC (32% of the chlorine) used in (e.g.) door/ window frames, pipes, flooring, medical supplies, clothing, electrical cables and potential alternatives to PEAS; o Polyurethanes and propylene oxide (31% of the chlorine) used in (e.g.) upholstery, insulation, footwear, plastics, pesticides, car paints and potential alternatives to PEAS; o Inorganics (13% of the chlorine) used in (e.g.) disinfectants, water treatment, paint pigments, solar panels; o Solvents and epichlorohydrin (11% of the chlorine) used in (e.g.) epoxy resins, printed circuits, wind turbines, metal degreasing, dry cleaning; o Other organics (9% of the chlorine) used in (e.g.) detergents, paints, lubricants, adhesives, herbicides, insecticides; o Chloromethanes (4% of the chlorine) used in (e.g.) medicine production, silicon rubbers, decorating supplies, cosmetics, polymers. For sodium hydroxide (caustic soda) o Miscellaneous (32% of the caustic) used in (e.g.) neutralisation of acids, gas scrubbing, pharmaceuticals, rubber recycling, textiles, disinfectants, cosmetics, greases, fuel additives, detergents; o Organics (28% of the caustic) used in (e.g.) modern/ medical textiles, safety equipment, stationary, smartphones; o Other inorganics (13% of the caustic) used in (e.g.) paint, glass, modern ceramic materials, fuel cells, water electrolysis for hydrogen production, (precious) metal and electronics recycling; o Pulp, paper and cellulose (11% of the caustic) used in (e.g.) adhesives, printing; o Food (6% of the caustic) used in (e.g.) fruit peeling, ice cream, thickeners, wrappings; o Aluminium/ other metal purification (5% of the caustic) used in (e.g.) greenhouses, automobiles and aerospace, steel hardening; o Water treatments (5% of the caustic) used in (e.g.) waste treatment, acidity control. For hydrogen o Energy applications (44% of the hydrogen) such as steam production, heating and electricity production, transport fuels; o Chemical application (30% of the hydrogen) such as hydrogen chloride production, aniline, ammonia, hydrogen peroxide; o Miscellaneous (15% of the hydrogen) such as hydrocracking, balloons; o Venting (11% of the hydrogen) where no economical outlets are available. Whilst many chlor-alkali products contribute to healthier lives (medicines/ safe drinking water/ waste water purification etc.) and energy saving (insulation and construction materials etc.), some (e.g. components of wind-turbines, solar panels, batteries, etc.) may even play a critical role in the European transition to climate neutrality by 2050. Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium cefic.be www.eurochlor.org A sector group of Cefic European Chemical Industry Council - Cefic aisbl EUTransparency Register e 61879112323-90 Page 5 of 19 0 chliii 2 The link between our sector and PFAS materials The European chlor-alkali industry doesn't produce PFAS materials in its own chlor-alkali process. Nevertheless, the sector makes use of PFAS-containing or PFAS-coated materials for the safe and efficient combined production of its four key products. The chlor-alkali industry uses fluorinated materials, mainly as fluoropolymers, in its production process with the main uses being indicated in Figure 5 below and in Appendix 1. It should be noted though that the use of these materials is not unique to the chlor-alkali industry as such uses also apply for the entire chemical industry and many other industry sectors. Figure 5: Indication of the PFAS uses in the European chlor-alkali industry based on an investigation by Euro Chlor members PFAS (fluorinated) materials are used in many cases as (albeit more costly) replacements for alternatives that are no longer allowed to be used in Europe (e.g. asbestos in gaskets, sealings, asbestos membranes/ diaphragms in the electrolysis cells or mercury in the electrolysis cell) under the conditions of the EU chlor-alkali BREP. Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org A sector group of Cefic III European Chemical Industry Council - Cefic aisbl EUTransparency Register e 61879112323-90 Page 6 of 19 0 chliii 17. 3 The use of PFAS materials in the chlor-alkali process and possible alternatives Figure 6 shows a simplified scheme of the main process units of the chlor-alkali membrane system. The alternative diaphragm process contains fewer units (e.g. fewer brine purification steps) but the options for alternative materials are similar to those of the membrane process (the major process in Europe). wale demin water preparation residue Salt Chemicals HCI NaOH Catholyte circul tion ill & cooling 1 Catholyte concentration & coo ing caustic storage and transport Brine saturation 4 i precipitation 1 brine filtration P 1 ion-exchange 1 Electrolysis purge sludge/waste sulfate emovalH. Na 2SO4 waste brine dechlorination Chlorate destruction Hydrogen cooling Chlorine cooling Hydrogen compression Hydrogen storage and transport H2SO4 chlorine compression chlorine liquefaction w chlorin storage and tr nsport Hydrochloric acid production Hydrochloric acid storage and transport sodium hypochlorite production sodium hypochlorite storage and Figure 6: A simplified block scheme of the chlor-alkali production process The following is based on the combined experience of Euro Chlor members in the safe and efficient production of chlor-alkali. Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org A sector group of Cefic 41 European Chemical Industry Council - Cefic aisbl EU Transparency Register n 61879112323-90 Page 7 of 19 0 chLai 17. Demin water preparation In this unit, water is treated to remove impurities in order to produce the very pure (demineralised) water that is required for safe and efficient production. This can be done by evaporation (requiring more energy), ion-exchange (requiring more chemicals and resulting in chemical waste) or reverse osmosis (the preferred/ most widely used option). Depending on the starting water quality, pretreatment may be needed (such as chlorination) to prevent biological fouling or filtration to remove particles (via things such as carbon filters). The membranes used in reverse osmosis do not contain fluorinated materials but construction materials (such as pumps, gaskets, sealings in valves etc.) may do as they are standard equipment for such a process. For these materials, 'non-PFAS' containing materials are available (e.g. rubber) and could be used. Brine saturation, brine precipitation, brine filtration and ion-exchange ('brine purification') Brine purification is needed to reduce the concentration of undesirable components (e.g. sulphate, Ca/ Mg/ Ba cations and other metal-ions) that could damage the membrane/ diaphragm and increase the energy consumption or decrease the safety of the process. Fluorinated materials (mainly fluoropolymers such as PTFE, PVDF, ECTFE, FEP, VITFEP (FEP-FKM), FKM, PFA) are used for lining in piping, valves and gaskets and seals in valves, pumps, instrumentation and as a filtration medium. Alternative construction materials exist for these process sections but fluorinated materials contribute to longer operational lifetimes of the equipment with less waste and increased installation safety performance. Depending on how the process is configured, the brine could still contain some chlorine. The use of fluorinated materials in such situations is highly advantageous as these materials are much more resistant against chlorine at the elevated temperatures (50-90 C) at which the brine circuit is operating. By using fluorinated materials in this section, higher resilience against operational incidents is achieved, with longer operational times and fewer unexpected shutdowns and leakages. This primarily improves the overall safety performance of the installation and (secondly) lowers the overall operational costs. The electrolysis unit This is the most critical section where PFAS materials are required due to a specific set of necessary properties. Without this unit, chlor-alkali production is impossible as this is where water and salt are split into chlorine, caustic and hydrogen. For the production of chlor-alkali several technologies are available: Membrane technology (83% of the total European chlorine production capacity) with sodium hydroxide or potassium hydroxide as a co-product and also hydrogen as a by-product; Diaphragm technology (11 % of the total European chlorine production capacity) with sodium hydroxide and also hydrogen as a by-product; Other technologies including HCI electrolysis, HCI oxidation, chlorine and sodium hydroxide production without hydrogen as a by-product (ODC), the production of chlorine and alcoholates and the production of chlorine and solid sodium (6% of the European chlorine capacity) Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org A sector group of Cefic* European Chemical Industry Council - Cefic aisbl EUTransparency Register e 61879112323-90 Page 8 of 19 0 chLae In the membrane electrolysis unit, a sulfonated fluoropolymer-copolymer (containing PFSA/PFCA/PTFE, see Figure 7 below) is used due to the following specific requirements: Safe chemical stability against raw materials and products (salt water, sodium hydroxide, potassium hydroxide, chlorinated brine, chlorine and hydrogen) at temperatures up to 95 C; Low diffusion rates for hydrogen and chlorine to avoid explosive mixtures; The capability to safely and efficiently transport the sodium or potassium ion; Low electrical resistance to keep energy consumption as low as possible; Safe separation of the products from each other to maintain efficiency; Preparation of high quality sodium/ potassium hydroxide with minimal contaminants for safe use by the supply chain. During the development of the membrane electrolysis technology in the early 1970s several other materials for the membrane were tested. Whilst we rely on the manufacturers of such materials to explain the development/ potential alternatives in detail as part of this consultation, the current information we collected suggests: Polyetheretherketone (PEEK) could be an alternative for the PTFE in the membrane as it is temperature and alkali stable up to 90 C. Unfortunately it is not an option here as PEEK begins to break down in the acidic, chlorine-rich conditions found at the chlor-alkali process anode. The same is true for its use in gaskets and in the hypochlorite loop as leakages would be more likely and environmental release/ personnel safety would be a concern; Aramid fibres could be used as replacement for the PTFE which are strong in acidic conditions but break down in the alkali conditions found at the chlor-alkali process cathode leading to leakages which share the same concerns as PEEK; Hydrocarbon membranes will chlorinate and produce potentially hazardous wastes so are not desirable alternatives. Such wastes may even be illegal under various international conventions that EU Member States are party to; We are unaware of any specific alternative for the sulphonate and carboxylate layer that share the same functional properties (i.e. being able to transport sodium/ potassium-ions while preventing the transport of the hydroxyl-ion with a reasonable lifetime of 3-6 years in the acid/ active chlorine/ caustic environment at 90 C of the electrochemical cell); Electrochemical production of EDC which may not produce free chlorine for other uses in sufficient quantities. As far as we are aware the metal chloride used may react with certain (nonPFAS) membrane materials. We are also uncertain if membranes used in this electrochemical process contain PFAS or of the operational readiness and magnitude of the chemicals produced. 2018 laboratory-scale tests of a membrane-free process that decouples chlorine from alkali production (published by Hou et al. in Nature Communications) appear to use 60% more electricity than current processes and may only produce low concentration sodium hydroxide. We are also uncertain on the technological readiness, safety and efficiency of the sodium hydroxide production given the electrode treatment steps involved. Many of these alternatives also suffer from the fact that they are not considered BAT under the BREF process2 and, given that such possible alternatives have been explored now for several decades, it may take several more to find, test and approve alternatives. Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium cefic.be www.eurochlor.org A sector group of Cefic European Chemical Industry Council - Cefic aisbl EUTransparency Register e 61879112323-90 Page 9 of 19 0 chide 17. Some other alternatives have already been phased out for several years. The development of membrane technology was initiated after the Minamata disaster as mercury was previously the basis for chlor-alkali production. Since 2017, mercury-based technology for chlor-alkali production has been banned in Europe (and will be phased out in the rest of the world by 2025). It should be noted that, the European chlor-alkali industry voluntarily invested approximately 3bn over the last 25 years to convert its old mercury and asbestos-based diaphragm assets to the membrane or asbestos-free diaphragm technologies. This conversion also resulted in a 23.5% decrease in electricity consumption across Europe for our sector'. In Europe approximately 200,000m2 of membrane area is operational with a membrane being replaced (approximately) every 3-6 years. Sulphonate layer iCTI--CFMTFvCF-4- ICI--CFrillri-O--CFT- CFN.... / 0 CF3 Cit Anodic element Sulohonate lava mechanical strength high electrical co.ducovity PTFE Arid tear strength high mechanical resistance stiffness Hydrophilic coating CI, gas release reduced cell voltage :olno 13 BASF :0101r:4 Cathodic element CAHICUpgatelgtel Inn selective ion permeability prevention of OH-migration thigh current efficiency) prevention of CI-diffusion pow content of NCI in NaOH) Kase, 2O0111 lagalgittbfeadigt&ObIteft) oonsrstently good brine distribution ni_lHydrophilic coating H,gas release reduced cell voltage Carboxylate layer F FF FF FF F OH F FF FF FF F Figure 7: A schematic overview of a membrane (from the EU chlor-alkali BREF2) PTFE (polytetrafluorethylene) is also used in chlor-alkali production's diaphragm technology. Diaphragms fulfil a similar function and must meet the same requirements to those of the membranes described above. In this diaphragm technology, PTFE is used as an alternative to asbestos which, as previously mentioned, is no longer allowed in Europe2. In another chlor-alkali production technology that is available on the market (Oxygen Depolarised Cathode (ODC)), specific fluoropolymers are used in the gas diffusion electrodes (N.B. these do not produce hydrogen). A similar process is also used in the electrolysis of hydrogen chloride to chlorine (which also does not produce hydrogen). These technologies represent approximately 2% of the total installed capacity. The hoses which transport the electrolytes to/ from the electrochemical cells, as well as those collecting the produced gases, are made from transparent fluorine-containing polymers that would also meet the EU definition of PFAS. Here, chemical resistance, alongside transparency, is needed for safe operation and monitoring (e.g. to check for blockages and colour changes that indicate potentially dangerous sidereactions). Several types of fluoropolymers are also used in the gaskets and sealings that join connections to avoid leakages of liquids and gases. These gaskets must be flexible, tight and resistant to the chemicals used in the process. Historically, asbestos-based gaskets had this unique combination but, due to the phase out of asbestos, alternatives had to be found. Fluoropolymers (such as PTFE etc.) were therefore used. Alternatives (such as EPDM) have drawbacks including shorter lifetimes and result in chlorinated organic wastes. Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org A sector group of Cefic * European Chemical Industry Council - Cefic aisbl EUTransparency Register n 64879142323-90 Page 10 of 19 chlor 17. Chlorate destruction and brine dechlorination section To ensure product purity, fluorine-containing materials (mainly fluoropolymers) are used as lining in pipes, equipment, gaskets, valves, packing materials in stripping columns and as sealants. Such materials need to be chemically resistant at temperatures up to 100 C. Alternatives for such fluorinecontaining equipment in chlorate destruction could be based on glass but this tends to be more fragile, is less chemically resistant and still requires the use of fluoropolymer gaskets. The process itself could be replaced by chemical and/ or catalytic destruction of the chlorate but this would increase the need for brine purging to the environment (which may not be environmentally desirable). For dechlorination, titanium, FRP or PVC-C lined FRP could be used as an alternative construction material. This could increase costs by up to 20% (in the case of titanium) or require replacement twice as often (in the case FRP or PVC-C). Neither of these alternatives can be produced without chlor-alkali chemicals either. For the gaskets and sealings, rubber could be used but this carries a shorter lifespan (around 1/3 of the fluorinated material) and would increase the amount of resulting organochlorine waste. Reliability of such alternative products is also a concern as they carry an increased failure rate. Sulphate removal Sulphate comes from the salt used and must be addressed as it can precipitate/ block the membrane if it is present in too high quantities. Sulphate can be removed via brine purge, precipitation (both of which carry the challenges described before) or nanofiltration. For the nanofiltration, a membrane is used which is made (e.g.) of polyethylene terephthalate or polyamide. None of these processes involve specific PFAS but this removal step is included for completeness. Catholyte circulation and cooling To improve process performance, circulation and cooling are required. Fluorinated materials here are found in equipment, piping, gaskets, valves etc. Alternatives include high nickel steel, PVC-U and polypropylene. Whilst polypropylene has been used for many years in pipework for this process section, several chlor-alkali producers have recently identified some safety concerns that are not shared by fluorinated alternatives. For gaskets and sealing systems in this specific area, EPDM or graphite could be used although the resulting products may not be used in food applications (especially caustic) as they are not approved for such uses. Chlorine cooling To begin removing any residual water from the chlorine, a cooling step is required. Fluorinated materials here include equipment, piping, valves, gaskets and column internals. Alternative materials are available including titanium (for specific applications), PVC lined FRP and Hastelloy (for specific applications). For gaskets and sealing systems, EPDM could be used but this has shorter lifetimes (around 1/3 of the fluorinated material) and leads to more organochlorine waste. Reliability of such products is also a concern as they carry an increased likelihood of failure and a resulting decreased safety performance. Chlorine drying To remove water that could cause problems elsewhere in the process, chlorine is dried. Fluorinated materials here include equipment, piping, valves, gaskets and column internals. Alternative materials Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium cefic.be www.eurochlor.org A sector group of Cefic .4"a European Chemical Industry Council - Cefic aisbl EUTransparency Register r 61879112323-90 Page 11of 19 chLae 17. are available including Hastelloy (for specific applications), PVC lined FRP, and steel (for specific applications). For gaskets and sealing systems, EPDM could be used but this has shorter lifetimes (around 1/3 of fluorinated materials) and leads to more organochlorine waste. Reliability of such products is also a concern as they carry an increased likelihood of failure and a resulting decreased safety performance. Chlorine compression and liquefaction section Depending on the use of the chlorine it may be compressed and liquefied. The main applications of fluorinated chemistry here are in greases, gaskets and sealing systems. For the gaskets, metals could be an alternative but for the greases there are no real alternatives as they need to be both chemically inert and resistant. In some cases fluorinated gases may be used as refrigerants but alternatives such as high pressure operation, combined with water cooling, CO2 and NH3 are suggested to be acceptable alternatives (see also the chlor-alkali BREF2 where this is already required for new installations). Chlorine storage, evaporation and transport Fluorinated materials are used in gaskets and greases that are used in loading/ unloading equipment. Alternatives for gaskets involved in liquid/ dry chlorine gas could be aramid fibres with rubber binders (e.g. NBR) however they cannot be used at higher temperatures (> 50 C in liquid chlorine and 100 C for gaseous chlorine). Other options include spiral wound gaskets with Graphite/1.4541/St33, with supporting/ centering rings. Unfortunately, unless the design can avoid direct contact, graphite is not stable in the presence of chlorine. Alternatives for greases, as previously mentioned, are currently unavailable due to the chemical stability requirements. Chlorine absorption This unit is used as a safety measure. Fluorinated materials (mainly fluoropolymers) are used as lining in equipment, piping and valves, column internals and gaskets. For this, alternative construction materials such as titanium or PVC-U lined FRP are available, but PVC-U shows much lower lifetimes (requiring replacement twice as often as the fluorinated material) in the reaction section than more regularly used fluorinated materials. For gaskets and sealing systems, EPDM could be used but this has shorter lifetimes and leads to more organochlorine waste. Reliability of such products is also a concern as they carry an increased failure rate. Sodium hypochlorite storage and transport Fluorinated components can be found in gaskets, pumps and fittings. For such storage and transport though alternative materials are available but carry lower lifetimes and the aforementioned organochlorine formation risk. Hydrogen cooling and compression No issues as specific PFAS are not really used here. Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium cefic.be www.eurochlor.org A sector group of Cefic' European Chemical Industry Council - Cefic aisbl EUTransparency Register 61879112323-90 Page 12 of 19 chloir 17. Hydrochloric acid production (i.e. controlled chlorine and hydrogen burning) The main issue here is for the gaskets that are needed to seal the graphite equipment. Whilst there might be an alternative available (unreinforced expanded graphite), it is not recommended as it carries safety problems (such as embrittlement, cracking and potential emission of toxic, corrosive gas). Hydrochloric acid storage and distribution Fluorinated components can be found in gaskets, pumps, fittings etc. In the majority of the cases, alternative materials are available but come with lower lifetimes (requiring replacement twice as often as the fluorinated material). Caustic-concentration, cooling, storage and distribution Expanded PTFE gaskets are largely used for metallic caustic piping and plate heat-exchangers. Alternative for the gaskets in the piping could be spiral wound gaskets stainless steel/ graphite but their use lifetime is much shorter due to the migration of caustic into the graphite layer leading to leakage and failure (i.e. safety) risks. As previously mentioned, as caustic is also used in food applications, authority approval may be needed prior to any replacement with new materials. Analysers/ analytical equipment A lot of analytical equipment, especially in the chlorine part, is equipped with fluorine- (fluoropolymer) containing elements such as sample pumps, valves and tubing. Whilst this is similar to the process equipment in the chlorine area, the tubing and valves have particularly small size and flexibility requirements. The additional need for chemical resistance makes fluoropolymers the predominant practical choice. Temporary connections In some loading and unloading applications, hoses are used for the transfer of chemicals. In these cases the benefit of fluorinated materials (fluoropolymers) include the associated high chemical resistance, mechanical capabilities and flexibility. Such properties are vital here for safety reasons making fluoropolymers the optimal material to use. Hose connections are also often used in emergency situations where there is a need to be able to completely and quickly rely on the chemical robustness of the construction material without a need to delay emergency response to take time to discuss which material might be used. Fluoropolymers have such reliable performance characteristics in such circumstances. Gaskets general Gaskets based on fluoropolymers show good tightness at comparably low surface pressure. They also display good chemical resistance across the range of temperatures experienced in chlorine production. It is also noteworthy that there are often specific and recommended national emission reduction regulations to minimise diffuse emissions (e.g. T.A.-Luft). Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium cefic.be www.eurochlor.org A sector group of Cefic' European Chemical Industry Council - Cefic aisbl EUTransparency Register rt. 61879112323-90 Page 13 of 19 chliii 17. 4 Implementation of alternatives For a few cases identified in the previous section (apart from the electrolysis unit), alternative materials to PFAS are available. It should be made clear though that any replacement might still require time to implement, especially when equipment or piping is involved, as often this is not a direct, or simple 'oneto-one' replacement. These cases often require new or re-designed installations and may even require a change of the environmental/ operational permit. Delays may also be expected due to ordering and delivery and the need to factor in the physical installation during the normal maintenance schedule of the plant and its down-stream users. This could result in an implementation period of more than five years. In those cases where an alternative has to be developed, more time will be required to account for research and development of the alternative. The required time needed for this is impossible to estimate but can be many years (even if such an alternative can be found at all). When a potential material is identified it has to be confirmed that there are no regrettable environmental/ health and safety effects, which can also take several years. This is then followed by pilot scale testing which usually takes around five years to demonstrate that the materials have the necessary lifespan. After this, these materials are tested in operational installations (approximately 5-10 years). Upon completion of this phase the application of the alternative starts. Based on experience, a minimum of 20 years (excluding the time for the R&D work) is normal. It should also be noted that having multiple different parts increases the risk of mistake should (chemically) incompatible parts be accidentally placed in the wrong location during maintenance (e.g. titanium containing parts can be used in wet but not dry chlorine areas due to chlorine-titanium fire risk). Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org A sector group of Cefic ' European Chemical Industry Council - Cefic aisbl EUTransparency Register e 61879112323-90 Page 14 of 19 0 chide 17. 5 Waste management In the majority of cases PFAS containing materials are collected at the end of their life and treated via waste incineration or in a chemical waste incineration plant (see Figure 8). Interestingly, incineration could be used to recover fluorine (as calcium fluoride) for later reuse. Incineration is currently employed because, as confirmed in the restriction dossier, recycling of such fluoropolymer materials is "hardly possible/ cost effective". Pilot scale recycling programmes (e.g. in Germany) have found that metal salt impurities tend to accumulate in the material during electrolysis making chlor-alkali membrane recycling even more difficult. We are aware of investigations into new recycling options outside Europe (e.g. South Korea) but are not aware of their technological readiness, feasibility or applicability to chloralkali materials. The recycling situation is however further complicated by the layered structure of the membrane/ diaphragm materials where it is very difficult to separate the fluorinated components from the rest of the material (e.g. metal impurities/ multi-fluoropolymer layers). We are informed that membrane/ diaphragm suppliers are currently recovering spent equipment to see how such impurities could be addressed as part of a developing recycling scheme, but more work is needed. On emissions, there remain uncertainties as to the levels of PFAS that are entering the plant in the raw materials (water/ salt). Unfortunately, due to limitations with the analysis of complex chlor-alkali products and effluents, it remains challenging to determine where any trace levels of PFAS might be coming from or where (if any) they could be released. To assist here, we will continue developing the analytics as part of our ongoing monitoring programme and to work to further minimise emissions by investigating optimal emission control measures. However, Euro Chlor members feel that addressing PFAS emissions and end-of-life is of such high importance that we want to continue to improve waste management of these materials. Therefore Euro Chlor's membership are seeking to: a) Replace materials where possible with non-PFAS alternatives at the earliest opportunity; b) Increase the share of PFAS containing waste that goes to the best possible waste handling and treatment methods and; c) Recycle PFAS-containing wastes as sustainable options for this become readily available (with the understanding that this is currently limited for membranes/ diaphragms). Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium cefic.be www.eurochlor.org A sector group of Cefic ID European Chemical Industry Council - Cefic aisbl EUTransparency Register r 61879112323-90 Page 15 of 19 0 chide 17. Figure 8: Waste solutions for PFAS materials used in chlor-alkali production based on a survey of Euro Chlor members 6 Summary In chlor-alkali production fluorinated materials (mostly fluoropolymers) are used (see Appendix 1). At present though there are currently no alternatives available or in research and development for the membranes and diaphragms in the electrolysis cells. This seems to be confirmed in preliminary assessments by NGOs4 and in independent research 5,6. Alternatives were available in the past (mercuryand asbestos-based) but they have been phased out via EU regulation due to environmental and health problems and remain highly undesirable for Europe's chlor-alkali sector. Figure 9 shows where replacement could be possible in our process but note that many carry significant safety and performance risks that should be considered. Based on the variety of chlor-alkali products that are needed for the healthy and safe functioning of society, we support Cefic's request for an exemption for the use of PFAS in the chemical industry's industrial settings to enable the continued use of PFAS-containing materials for the combined production of chlorine, sodium/potassium hydroxide and hydrogen. Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org ee, A sector group of Cefic European Chemical Industry Council - Cefic aisbl EUTransparency Register rt. 61879112323-90 Page 16 of 19 0 chili' water Demin water preparation residue Salt Chemicals HCI NaOH Catholyte circulation & cooling Catholyte concentration & cooling Caustic storage and transport Brine saturation i Precipitation i Brine filtration i Ion-exchange Electrolysis purge sludge/waste Sulfate removal waste Brine dechlorination Chlorate destruction a2SO4 Hydrogen cooling Chlorine cooling Hydrogen compression Chlorine drying H25O4 Chlorine compression Hydrogen storage and transport Chlorine liquefaction Chlorine storage and transport 1 Hydrochloric acid production v L Sodium hypochlorite production Hydrochloric acid storage and transport sodium hypochlorite storage and Alternatives exist and can be applied today Alternatives exist but carry safety performance risks No alternatives exist/ in development Figure 9: Overview of options for PFAS alternatives in the chlor-alkali process. Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org A sector group of Cefic 44 European Chemical Industry Council - Cefic aisbl EU Transparency Register e 61879112323-90 Page 17 of 19 0 chloir 17. APPENDIX 1. PFAS materials used by chlor-alkali PFAS material Perfluoro sulfonic acid (PFSA) with Polytetrafluoroethylene (PTFE) Perfluoro sulfonic acid (PFSA) with perfluoro carboxylic acids (PFCA) and Polytetrafluoroethylene (PTFE) Polytetrafluoroethylene (PTFE) PTFE-M TFM copolymerized PTFE introducing an oxygen molecule Polyvinylidene fluoride (PVDF) Ethylene chlorotrifluoroethylene (ECTFE) Fluorinated ethylene propylene (FEP) Perfluoralkoxy (PFA) VITFEP (FEP-FKM) FKM FFKM PFPE or PFAE or PFPAE or PCTFE Main application Membrane for HCI-ODC technology Membrane for Chlor-Alkali-Technology (incl. NaCI-ODC) Electrolyser: Hoses/tubes/pipes, gaskets, sealing, constituent of ODC for NaCI-ODC, HCI-ODC, percolator for NaCI-ODC; diaphragm Liner, gasket, sealing, valves etc for piping, valves, instruments, static and rotating equipment Material for brine filters Liner for equipment, piping and valves, gaskets, hoses Electrolyser insulating frame Liner for instruments, static and rotating equipment, piping Filter material for brine filters Liner for Equipment, Piping, Instruments Liner for Equipment, Piping, Valves Liner, hoses, fittings for piping, valves, instruments, static and rotating equipment Gaskets Gaskets/O-rings in Electrolysers, Piping, Rotating equipment 0-rings in valves, pumps Grease e.g. for electrolysers, piping, valves, instruments Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium @cefic.be www.eurochlor.org A sector group of Cefic * European Chemical Industry Council - Cefic aisbl EUTransparency Register e 61879112323-90 Page 18 of 19 0 chLai 17. APPENDIX 2. Key references 1 2023 Cefic input to EU PFAS REACH restriction consultation. 2 Best Available Techniques (BAT) Reference Document for the Production of Chlor-alkali. Industrial Emissions Directive 2010/75/EU (Integrated Pollution Prevention and Control). European Commission (2014). https://publications.jrc.ec.europa.eu/repository/bitstream/JRC91156/cak_bref_102014.pdf (checked 09/2023) 3 https://www.eurochlor.org/uses/ (checked 09/2023) 4 https://pfas.chemsec.org/ (checked 09/2023) 5 An overview of the uses of per- and polyfluoroalkyl substances (PFAS). J. Gluege et al. (2020), Environ. Sci. Process Impacts, 22: 2345-2373. 6 The concept of essential use for determining when uses of PFASs can be phased out. I.T. Cousins et al. (2019), Environ. Sci. Process Impacts, 21(11): 1803-1815. About Euro Chlor Euro Chlor represents 38 full member companies producing chlorine and caustic soda at 58 manufacturing locations in 19 EU countries. We represent 97% of European chlor-alkali producers. Euro Chlor is a sector group of Cefic, the association representing the European Chemical Industry. For more information please contact: Ton Manders Euro Chlor Technical and Safety Director @cefic.be. Disclaimer: This paper represents the views of the Euro Chlor Sector Group, not necessarily of Cefic as a whole Euro Chlor Rue Belliard 40 B-1040 Brussels Belgium cefic.be www.eurochlor.org A sector group of Cefic European Chemical Industry Council - Cefic aisbl EUTransparency Register e 64879142323-90 Page 19 of 19