Document rp6498EVaNNRVndkek02NjkMq

Date Division/Dept. Author 02.06.2023 EL-SC-QRG EL Product Compliance EU Use of fluoropolymers in chemical manufacturing plants Table of content 1. Executive Summary 2 2. Demonstration of the need of fluoropolymers in chemical production 3 2.1. Solvents required for the manufacturing/processing in plant 1 5 2.1.1. Production of OLED 1: Presentation of compatible materials for the production equipment and implementation in the production 6 2.1.2. Production of OLED 2: Presentation of compatible materials for the production equipment and implementation in the production 10 2.1.3. Production of OLED 3: Presentation of compatible materials for the production equipment and implementation in the production 13 2.1.4. Production of intermediate for API: Presentation of compatible materials for the production equipment and implementation in the production 16 2.1.5. Purification of a polymer for patterning process in semiconductor manufacturing: Presentation of compatible materials for the production/processing equipment and implementation in the production/processing 19 2.1.6. Typical examples of equipment with PFAS components in plant 1 22 2.2. Solvents required for the manufacturing/processing in plant 2 and in plant 3 27 2.2.1. Presentation of compatible materials for the production equipment in plant 2 and plant 3 28 2.2.2. Typical examples of equipment with PFAS components in plant 2 31 2.2.3. Further examples of fluoropolymer equipment/components 35 2.3. Summary and conclusion on the use of fluoropolymer-components in production equipment 40 2.4. Investigation of alternatives and (in)compatibilities 40 2.5. Conclusion 64 3. Exposition 65 4. Waste management and recycling 65 5. Impact 66 6. Summary and conclusion 66 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 1 1. Executive Summary As indicated in Table A.1. of Annex A of the restriction proposal, the PFAS applications in the chemical industry were not researched in detail during the preparation of the proposal. As a result, the use of fluoropolymers in chemical industry was not considered as a derogation. In order to support the authorities with their evaluation, we provide substantial data on - the indispensable need of fluoropolymers in chemical production (for details, see chapters 2.1 - 2.3), - the chemical resistance and leaching behavior of PTFE (for details, see chapter 2.4) - the incompatibility/lack of non-PFAS alternatives (for details, see chapter 2.4), - the enormous impact of a potential ban, due to the ubiquitous presence of fluoropolymer components in production equipment (for details, see chapter 2.1), - the range of PFAS emissions resulting from the use of fluoropolymers in production, namely: o information on the very low turnover and disposal volumes of fluoropolymers (for details, see chapter 3), o information on the disposal of our fluoropolymer components at a hazardous waste incineration plant (for details, see chapter 4), - the immense potential impact on our company (for details, see chapter 5). Considering the evidence provided, we ask for a time-unlimited derogation for the use of fluoropolymer materials in chemical manufacturing. This derogation must include all upstream processes to manufacture these fluoropolymers and articles to ensure resilience of the chemical industry in the EU market. The restriction proposal contains a list of applications for which temporary exemptions are considered, but the use of fluoropolymers in chemical industry production has not been taken into account. Industrial chemical manufacturing is highly integrated, often including multiple process steps, and using multipurpose facilities/plants. Fluoropolymers and other PFAS-containing articles are uniquely suited for use in these production steps. Use of these materials is critical due to their unparalleled chemical and permeation resistance, chemical durability, temperature stability and low leaching potential. The restriction proposal in its current form would inevitably jeopardize the functioning of the European chemical industry, and critically impact downstream use sectors, such as the semiconductor and pharmaceutical industries. Taken together, the use of PFAS in manufacturing plants is understood as essential to the chemical industry. The proposed ban will negatively affect its current innovative strength and the desired resilience of European industry. Fluoropolymer components are used in chemical manufacturing facility equipment and infrastructure numbering in the many thousands. In order to bring clarity, we provide concrete examples of production usage in chapters 2.1 and 2.2.. USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 2 Non-PFAS alternatives cannot fulfil the specific application requirements and thorough testing of alternatives has so far not resulted in viable alternatives (see chapter 2.4) - which is based on the unique properties of the C-F-bond in PFAS materials. The lack of alternatives exists for many of the industry's uses of fluorocarbon-containing articles and products and potential alternatives must be evaluated on a case-by-case basis. With adequate risk management measures related to use and disposal of articles (including fluoropolymers), exposure to the environment or populations across all our product life cycle phases (service life, end-of-life, disposal) can be strongly limited. The enormous impact of an implementation of the current draft restriction proposal on worker employment as well as on business figures of our company is described in a separate confidential document. With the information provided we hope to contribute to an appropriate regulation of PFAS including fluoropolymers while avoiding critical impacts on EU industry. Given the broad range and complexity of PFAS uses in this area, we are open to a direct exchange allowing us to give more detailed insights - which also includes the option to visit our site in Darmstadt. Additional comments will be submitted separately by Merck to provide also regarding other PFAS uses a better basis for an adequate regulation of PFAS materials. Merck is additionally actively contributing to industry association comments as e.g. from VCI, Cefic, SEMI, SIA and EFPIA - some comments are already submitted, others will be submitted later in course of the consultation phase. 2. Demonstration of the need of fluoropolymers in chemical production In the organization of Merck Electronics there are several plants on the company's site in Darmstadt, Germany. We consider these plants as representative to show current fluoropolymer use in chemical plants using batch production and a broad set of organic solvents as well as strong acids or bases. These cases are representative to demonstrate why fluoropolymers materials are needed in such equipment. By providing data on the (in)compatibility of different solvents with production materials we demonstrate that fluoropolymer materials are the only ones fulfilling the extreme needs in chemical manufacturing. In addition to the manufacturing plants, fluoropolymers are also required in the packaging of some chemicals for a safe transportation. To exemplify the practical relevance of fluoropolymers we selected one typical week of production/processing in three of our plants in our organization. In Table 1 the substance classes manufactured/processed are displayed including the respective solvents required. The substances USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 3 manufactured/processed are for use in Electronic industry (OLED, liquid crystals, liquid crystal intermediate, chemical for semiconductor manufacturing), Pharmaceutical industry (intermediate for API, excipient for vaccine) and Cosmetic industry (cosmetic raw material). Plant 1 is used for process developments and process optimizations. On average, plant 1 has a yearly turnover of about 1000 t of solvents. Plant 2 and plant 3 are larger scale production plants (for "fine chemical production dimensions"). Based on the solvents/starting materials/processing aids required for the production, the use of fluoropolymers is essential to provide the required chemical resistance and avoid product contamination. It should be noted that fluoropolymers are much more expensive than non-PFAScomponents [see chapter 2.4]. Nevertheless, safety of workers and the environment as well as product quality, most of the times, require the use of fluoropolymers. Fluorine-free components are used, e.g., for packaging of (dry) starting materials/processing aids/products where no contact to, e.g., solvents is possible. Table 1 Examples of productions/processing during one week in three plants each, in the organization of Merck Electronics Plant 1 2 3 Substance class OLED 1 OLED 2 OLED 3 Intermediate for API Purification of a polymer for patterning process in semiconductor manufacturing OLED 4 Liquid crystal Intermediate for liquid crystal Excipient for vaccine Purification excipient 1 Purification of excipient 2 Cosmetic raw material Downstream use Electronic industry Electronic industry Electronic industry Pharmaceutical industry Semiconductor industry Electronic industry Electronic industry Electronic industry Pharmaceutical industry Pharmaceutical industry Pharmaceutical industry Cosmetic industry Number of batches 1 1 1 1 3 1 1 1 1 3 6 2 In the following sections the manufacturing of each of these products is looked at in more detail regarding solvents used, processing temperatures and the respective compatibility to different materials - and information is given where respective components are used in the production equipment. In the following chapters the compatibility of different materials is shown in "compatibility tables" as colored circles and a figure: a green circle with "1" means fully compatible, fully resistant, whereas yellow and red circles represent a partially or no resistance towards the solvent. The materials with USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 4 other than green circles should not be used for a proper and safe handling of the equipment and product. Blue colored materials in the compatibility table headers are different fluoropolymers; the green colored materials are "fluorine free materials". Basis for the conclusion on compatibility are information from DECHEMA Werkstofftabellen [https://dechema.de/dwt.html], information from material suppliers as well as internal data - which are also exemplarily shown in the following sections. 2.1. Solvents required for the manufacturing/processing in plant 1 As it can be seen in Table 2, almost exclusively organic solvents are required for the production/processing steps of the mentioned five products, e.g., anisole, ethanol, n-heptane, dichloro methane, tetrahydrofurane. Table 2 Solvents used in the production/processing in plant 1 Acetone Acetnonitrile Anisole 1-Butanole t-Butyl methyl ether (1050C) Cyclohexane Dichloro methane Ethanol Ethyl acetate n-Heptane (10-60 C) Methanol 2-Propanole (20-95 C) PGMEA Sodium hydroxide solution (21-32 %, 50 C) Sodium hydrogen carbonate solution (20 C) Tetrahydrofuran e Toluene (0-110C) Water (20-50 C) Water/HCl (30 %; -10 50C) OLED 1 x OLED 2 OLED 3 x Intermediate x for API Polymer for patterning process in x semiconductor manufacturing x x x x x x x x x x x x x x x x x x x x x USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 5 2.1.1. Production of OLED 1: Presentation of compatible materials for the production equipment and implementation in the production Based on the solvents required, the materials in the production equipment have to be chosen. Table 3 shows the compatibility of different materials towards the solvents required in the production of OLED 1. When looking on the green circles in the table below, it is evident that a use of PTFE/FEP/PFA or FKM is required. Table 3 Compatibility of equipment materials towards solvents used for the production of OLED 1 Compatibility list of plastics/elastomers towards typical solvent and reagents PTFE 0 no data FEP 1 resistant PFA 2 partially resistant ECTFE 3 conditionally resistant PVDF 4 not resistant Polytetrafluorethylene Fluorinated ethylene propylene Perfluoroalkoxyl polymer ethylene chloro trifluoro ethylene Polyvinylidene fluoride FKM FFKM Fluorocarbon-based Fluoroelastomer Materials Perfluorelastomers EPDM NBR VMQ CSM Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Vinyl Methyl Silicone Chlorosulfonated polyethylene synthetic rubber Compatibility list based on own testing, DECHEMA Werkstoffliste, and information from material supplier Solvent Spalte16 Anisole Ethanol Water PTFE/FEP/PFA 20C 50C Spalte2 Spalte3 1 0 1 1 1 1 Fluorine containing material ECTFE (Halar) PVDF FKM ("Viton") 20C 50C 20C 50C 20C 50C Auswahl2 Auswahl22 Auswahl23 Auswahl24 Auswahl25 Auswahl26 0 0 0 0 4 4 1 2 1 1 2 3 1 1 1 1 1 1 FFKM ("Kalrez") 20C 50C Auswahl27 Auswahl28 1 0 1 1 1 1 Fluorine free material EPDM NBR VMQ ("Silikon") CSM ("Hypalon") 20C 50C 20C 50C 20C 50C 20C 50C Auswahl29 Auswahl210 Auswahl211 Auswahl212 Auswahl213 Auswahl214 Auswahl215 Auswahl216 4 4 4 4 4 4 2 0 1 1 2 3 1 3 1 1 1 1 1 1 1 2 1 1 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 6 Table 4 shows the production equipment and the components that are not made of steel or glass and the type of materials including the number of those pieces. The equipment is as follows: pendulum centrifuge, three sizes of reactors, a large filter, 3 stirrable tank pallets, equipment for sampling, vacuum drying oven, compressed air diaphragm pump, dry vacuum compressor, vacuum line. Each equipment contains numerous "small components". These components are essential parts of the equipment, are/maybe re-used for some time and batches, cleaned in between, and disposed of after a certain time of usage. The time of usage depends on the components: whereas a filter is only used once; o-rings/seals are replaced when damaged; also, valves are used for a long time. When we speak of "components" in the following all of abovementioned variants are meant. The number of components relevant for production of OLED 1 is immense. Ca 1100 pieces require materials made of fluoropolymers whereas about 20 pieces are made of other materials. Table 4 Production equipment and materials used for the production of OLED 1 Equipment 100 L pendulum centrifuge, gummed 2500 L reactor, VA-steel 1600 L reactor, glass-lined Component/Element filter cloth material ball valve lid bearing housing pump, submersion, pipe lining seal seal material material vessel lid seals ball valve bottom valve lining seal seat + seal glass construction Protego seals entry system bag butterfly valve seal tube camlock coupling tri-clamp filter body gasket candle vessel lid discharge tube seals ball valve bottom valve lining seal seat + seal glass construction Protego seals Material PE-fiber PFA PTFE PTFE PTFE PTFE FEP/Silikon PFTE PFA PTFE PTFE PFTE PTFE PE PTFE PTFE/Viton PTFE PTFE/Viton FEP/Silikon PFTE FEP/Silikon PTFE PFTE PFA PTFE PTFE PTFE PTFE Numb er 1 2 4 1 1 17 2 4 5 10 2 1 200 5 1 2 4 2 6 1 2 1 4 5 10 2 1 300 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 7 Equipment 2500 L reactor, glass-lined 125 L single-layer filter 800 L heated, stirrable tank pallet 500 L heated, stirrable tank pallet 800 L heated, stirrable tank pallet sampling vacuum drying oven compressed air diaphragm pump SIHI dry vacuum compressor Component/Element entry system bag butterfly valve seal tube camlock coupling tri-clamp filter body gasket candle vessel lid seals ball valve bottom valve lining seal seat + seal glass construction Protego seal entry system bag butterfly valve seals tube camlock coupling tri-clamp filter body gasket seals sterile screw connection candle material material ball valve material seals lining seal filter plate connection ball valve seals lining seal connection ball valve seals lining seal connection ball valve vials lining seal lid + seal seals hordes tube seals membrane seals door O-rings foils camlock coupling material material condenser Material PE PTFE PTFE/Viton PTFE PTFE/Viton FEP/Silikon PFTE FEP/Silikon PFTE PFA PTFE PTFE PTFE PTFE PE PTFE PTFE/Viton PTFE PTFE/Viton FEP/Silikon PFTE PFTE FEP/Silikon PFA PTFE Cellulose-Kieselguhr PTFE PFA PTFE PTFE PFA PTFE PTFE PFA PTFE PP/PTFE FEP/Silikon PTFE/Silikon PTFE PTFE PTFE PFTE PTFE USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS Numb er 5 1 2 4 2 6 1 2 4 5 10 2 1 300 5 1 2 6 2 6 1 10 4 4 8 1 4 2 4 4 2 4 4 2 4 4 1 20 6 4 2 2 5 8 Equipment vacuum line Component/Element butterfly valve valve body lining gas- and liquid rinsing seals material Material FEP/Viton PFA/PTFE PTFE PTFE Numb er 1 2 2 50 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 9 2.1.2. Production of OLED 2: Presentation of compatible materials for the production equipment and implementation in the production Based on the solvents required, the materials in the production equipment have to be chosen. Table 5 shows the compatibility of different materials towards the solvents required in the production of OLED 2. When looking on the green circles in the table below, it is evident that a use of PTFE/FEP/PFA or FKM is required. Table 5 Compatibility of equipment materials towards solvents used for the production of OLED 2 Compatibility list of plastics/elastomers towards typical solvent and reagents PTFE 0 no data FEP 1 resistant PFA 2 partially resistant ECTFE 3 conditionally resistant PVDF 4 not resistant Polytetrafluorethylene Fluorinated ethylene propylene Perfluoroalkoxyl polymer ethylene chloro trifluoro ethylene Polyvinylidene fluoride FKM FFKM Fluorocarbon-based Fluoroelastomer Materials Perfluorelastomers EPDM NBR VMQ CSM Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Vinyl Methyl Silicone Chlorosulfonated polyethylene synthetic rubber Compatibility list based on own testing, DECHEMA Werkstoffliste, and information from material supplier Solvent Spalte16 Ethanol Ethyl acetate n-Heptane Toluene Water PTFE/FEP/PFA 20C 50C Spalte2 Spalte3 1 1 1 1 1 1 1 0 1 1 Fluorine containing material ECTFE (Halar) PVDF FKM ("Viton") 20C 50C 20C 50C 20C 50C Auswahl2 Auswahl22 Auswahl23 Auswahl24 Auswahl25 Auswahl26 1 2 1 1 2 3 1 2 3 3 4 4 1 1 1 1 1 1 1 2 1 1 3 3 1 1 1 1 1 1 FFKM ("Kalrez") 20C 50C Auswahl27 Auswahl28 1 1 1 1 1 1 1 0 1 1 Fluorine free material EPDM NBR VMQ ("Silikon") CSM ("Hypalon") 20C 50C 20C 50C 20C 50C 20C 50C Auswahl29 Auswahl210 Auswahl211 Auswahl212 Auswahl213 Auswahl214 Auswahl215 Auswahl216 1 1 2 3 1 3 1 1 3 0 4 4 4 4 3 3 4 4 1 1 4 4 4 4 4 4 4 4 4 4 4 4 1 1 1 1 1 2 1 1 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 10 Table 6 shows the production equipment and the components that are not made of steel or glass and the type of materials including the number of those pieces. The equipment is as follows: pendulum centrifuge, peeler centrifuge, three sizes of reactors, a large filter, equipment for sampling, vacuum drying oven, compressed air diaphragm pump, dry vacuum compressor, vacuum line. Each of these equipment contains numerous "small components". The number of components is immense: ca 1100 pieces require materials made of fluoropolymers whereas about 20 pieces can be made of other materials. Table 6 Production equipment and materials used for the production of OLED 2 Equipment 100 L pendulum centrifuge, gummed 40 L peeler centrifuge 630 L reactor, glass-lined 100 L reactor, glass-lined Component/Element filter cloth material ball valve lid bearing housing pump, submersion, pipe tri-clamp seals lining seal seal material material material door pump, submersion, pipe O-rings material vessel lid seals ball valve bottom valve lining seal seat + seal glass construction Protego seals entry system bag butterfly valve seals tube camlock coupling tri-clamp filter body gasket candle vessel lid seals ball valve bottom valve lining seal seat + seal glass construction entry system Protego seals bag Material PE-fiber PFA PTFE PTFE PTFE PTFE PTFE/Viton FEP/Silikon FEP/Silikon PTFE FEP/Silikon PFTE PFA PTFE PTFE PTFE PTFE PE PTFE PTFE/Viton PTFE PTFE/Viton FEP/Silikon PFTE FEP/Silikon PFTE PFA PTFE PTFE PTFE PTFE PE USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS Numb er 1 1 2 1 1 17 4 2 15 17 2 4 5 10 2 1 300 5 1 2 4 2 6 1 2 4 5 10 2 1 200 5 11 Equipment 1600 L reactor, glass-lined 125 L single-layer filter vacuum drying oven sampling compressed air diaphragm pump SIHI dry vacuum compressor vacuum line Component/Element butterfly valve seals tube camlock coupling tri-clamp filter body gasket candle vessel lid discharge tube seals ball valve bottom valve lining seal seat + seal glass construction Protego seals bag entry system seals butterfly valve tube camlock coupling tri-clamp filter body gasket seals sterile screw connection candle material material ball valve material lining seal filter plate seals hordes vials tube seals membrane door O-rings foils lid + seal camlock coupling material material seals butterfly valve valves condenser body lining gas- and liquid rinsing seals material Material PTFE PTFE/Viton PTFE PTFE/Viton FEP/Silikon PFTE FEP/Silikon PTFE PFTE PFA PTFE PTFE PTFE PTFE PE PTFE/Viton PTFE PTFE PTFE/Viton FEP/Silikon PFTE PFTE FEP/Silikon PFA PTFE Cellulose-Kieselguhr FEP/Silikon PTFE/Silikon PTFE PP/PTFE PTFE PTFE PFTE PTFE FEP/Viton PFA/PTFE PTFE PTFE Numb er 1 2 4 2 6 1 2 1 4 5 10 2 1 300 5 2 1 4 2 6 1 10 4 4 8 1 1 20 6 4 4 2 2 5 1 2 2 50 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 12 2.1.3. Production of OLED 3: Presentation of compatible materials for the production equipment and implementation in the production Based on the solvents required, the materials in the production equipment have to be chosen. Table 7 shows the compatibility of different materials towards the solvents required in the production of OLED 3. When looking on the green circles in the table below, it is evident that a use of PTFE/FEP/PFA or FKM is required. Table 7 Compatibility of equipment materials towards solvents used for the production of OLED 3 Compatibility list of plastics/elastomers towards typical solvent and reagents PTFE 0 no data FEP 1 resistant PFA 2 partially resistant ECTFE 3 conditionally resistant PVDF 4 not resistant Polytetrafluorethylene Fluorinated ethylene propylene Perfluoroalkoxyl polymer ethylene chloro trifluoro ethylene Polyvinylidene fluoride FKM FFKM Fluorocarbon-based Fluoroelastomer Materials Perfluorelastomers EPDM NBR VMQ CSM Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Vinyl Methyl Silicone Chlorosulfonated polyethylene synthetic rubber Compatibility list based on own testing, DECHEMA Werkstoffliste, and information from material supplier PTFE/FEP/PFA Solvent 20C 50C Spalte16 Spalte2 Spalte3 2-Propanole 1 1 Anisole 1 0 2-Methyl-2-butanole 1 1 Sodium hydroxide soluton (501%) 1 Tetrahydrofurane 1 0 Water 1 1 Fluorine containing material ECTFE (Halar) PVDF FKM ("Viton") 20C 50C 20C 50C 20C 50C Auswahl2 Auswahl22 Auswahl23 Auswahl24 Auswahl25 Auswahl26 1 2 1 1 1 1 0 0 0 0 4 4 1 2 1 0 1 4 1 1 3 3 3 4 4 4 3 3 4 4 1 1 1 1 1 1 FFKM ("Kalrez") 20C 50C Auswahl27 Auswahl28 1 1 1 0 1 1 1 1 1 1 1 1 Fluorine free material EPDM NBR VMQ ("Silikon") CSM ("Hypalon") 20C 50C 20C 50C 20C 50C 20C 50C Auswahl29 Auswahl210 Auswahl211 Auswahl212 Auswahl213 Auswahl214 Auswahl215 Auswahl216 1 1 3 3 1 1 1 1 4 4 4 4 4 4 2 0 3 3 1 1 0 0 1 3 1 0 3 3 4 4 1 1 4 4 4 4 4 4 4 4 1 1 1 1 1 2 1 1 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 13 Table 8 shows the production equipment and the components that are not made of steel or glass and the type of materials including the number of those pieces. The equipment is as follows: two sizes of reactors, two large filters, equipment for sampling, packaging material, compressed air diaphragm pump, dry vacuum compressor, vacuum line. Each of these equipment contains numerous "small components". The number of components is immense: ca 600 pieces require materials made of fluoropolymers whereas about 10 pieces are made of other materials. Table 8 Production equipment and materials used for the production of OLED 3 Equipment 100 L reactor, glass-lined 160 L reactor, glass-lined 125 L single-layer filter Component/Element vessel lid seals ball valve lining seal bottom valve seat + seal glass construction Protego seals bag entry system butterfly valve seals tube camlock coupling tri-clamp filter body gasket candle vessel lid seals ball valve lining seal bottom valve seat + seal glass construction Protego seals bag entry system butterfly valve seals tube camlock coupling tri-clamp filter body gasket candle seals sterile screw connection material material ball valve lining seal Material FEP/Silikon PFTE PFA PTFE PTFE PTFE PTFE PE PTFE PTFE/Viton PTFE PTFE/Viton FEP/Silikon PFTE FEP/Silikon PFTE PFA PTFE PTFE PTFE PTFE PE PTFE PTFE/Viton PTFE PTFE/Viton FEP/Silikon PFTE PFTE FEP/Silikon PFA PTFE USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 14 Equipment 35 L single-layer filter packaging material sampling compressed air diaphragm pump SIHI dry vacuum compressor vacuum line material Component/Element material plate + cloth seals sterile screw connection material material ball valve material lining seal material plate + cloth container seal vials lid + seal tube camlock coupling seals material membrane material seals condenser body butterfly valve valves lining gas- and liquid rinsing seals material Material Cellulose-Kieselguhr + PE-fiber PFTE FEP/Silikon PFA PTFE Cellulose-Kieselguhr + PE-fiber FEP/Silikon PP/PTFE PTFE PTFE PFTE PTFE FEP/Viton PFA/PTFE PTFE PTFE USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 15 2.1.4. Production of intermediate for API: Presentation of compatible materials for the production equipment and implementation in the production Based on the solvents required, the materials in the production equipment have to be chosen. Table 9 shows the compatibility of different materials towards the solvents required in the production of an intermediate for API. When looking on the green circles in the table below, it is evident that a use of PTFE/FEP/PFA or FKM is required. Table 9 Compatibility of equipment materials towards solvents used for the production of intermediate for API Compatibility list of plastics/elastomers towards typical solvent and reagents PTFE 0 no data FEP 1 resistant PFA 2 partially resistant ECTFE 3 conditionally resistant PVDF 4 not resistant Polytetrafluorethylene Fluorinated ethylene propylene Perfluoroalkoxyl polymer ethylene chloro trifluoro ethylene Polyvinylidene fluoride FKM FFKM Fluorocarbon-based Fluoroelastomer Materials Perfluorelastomers EPDM NBR VMQ CSM Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Vinyl Methyl Silicone Chlorosulfonated polyethylene synthetic rubber Compatibility list based on own testing, DECHEMA Werkstoffliste, and information from material supplier Fluorine containing material Fluorine free material P PTFE/FEP/PFA ECTFE (Halar) PVDF FKM ("Viton") FFKM ("Kalrez") EPDM NBR VMQ ("Silikon") CSM ("Hypalon") Solvent 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C Spalte16 Spalte2 Spalte3 Auswahl2 Auswahl22 Auswahl23 Auswahl24 Auswahl25 Auswahl26 Auswahl27 Auswahl28 Auswahl29 Auswahl210 Auswahl211 Auswahl212 Auswahl213 Auswahl214 Auswahl215 Auswahl216 Acetone 1 1 1 2 3 4 4 4 1 1 1 0 4 4 3 3 2 2 Dichloro methane 1 1 2 4 1 3 3 3 1 1 4 4 4 4 4 4 4 4 Methanol 1 1 1 1 1 1 3 4 1 1 1 0 3 3 2 2 1 1 Sodium hydroxide soluton (501%) 1 1 1 3 3 3 4 1 1 1 0 3 3 4 4 1 1 Tetrahydrofurane 1 0 4 4 3 3 4 4 1 1 4 4 4 4 4 4 4 4 Water 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 1 1 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 16 Table 10 shows the production equipment and the components that are not made of steel or glass and the type of materials including the number of those pieces. The equipment is as follows: two sizes of reactors, a large filter, vacuum drying oven, scrubber, equipment for sampling, compressed air diaphragm pump, dry vacuum compressor, vacuum line. Each of these equipment contains numerous "small components". The number of components is immense. Ca 600 pieces require materials made of fluoropolymers whereas about 20 pieces are made of other materials. Table 10 Production equipment and materials used for the production of an intermediate for API Equipment 630 L reactor, glass-lined 400 L reactor, glass-lined 125 L single-layer filter vacuum drying oven Component/Element vessel lid seals ball valve bottom valve lining seal seat + seal glass construction Protego seals entry system bag butterfly valve seals tube camlock coupling tri-clamp filter body gasket candle vessel lid seals ball valve bottom valve lining seal seat + seal glass construction Protego seals entry system bag butterfly valve seals tube camlock coupling tri-clamp filter body gasket seals sterile screw connection candle material material ball valve material seals lining seal material plate + cloth door Material FEP/Silikon PFTE PFA PTFE PTFE PTFE PTFE PE PTFE PTFE/Viton PTFE PTFE/Viton FEP/Silikon PFTE FEP/Silikon PFTE PFA PTFE PTFE PTFE PTFE PE PTFE PTFE/Viton PTFE PTFE/Viton FEP/Silikon PFTE PFTE FEP/Silikon PFA PTFE Cellulose-Kieselguhr + PEfiber FEP/Silikon Numb er 2 4 5 10 2 1 200 5 1 2 8 2 6 1 2 4 5 10 2 1 200 5 1 2 6 2 6 1 10 4 4 8 1 1 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 17 Equipment scrubber P002, ADA-107 ML400L auf DN200 ETFE P002, ADA-110 ML630L auf DN200 Hast sampling compressed air diaphragm pump SIHI dry vacuum compressor vacuum line Component/Element hordes heating system + vacuum system tri-clamp container seals pump O-rings foils tube material seal material material seals material seals vials tube membrane seals material lid + seal camlock coupling material material seals butterfly valve valve seals condenser body lining gas- and liquid rinsing material Material PTFE/Silikon PTFE PTFE PTFE/Viton FEP/Silikon EPDM PTFE PP/PTFE PTFE PFTE PTFE PTFE FEP/Viton PFA/PTFE PTFE PTFE Numb er 10 6 10 4 2 15 2 4 4 4 4 2 2 5 1 2 2 50 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 18 2.1.5. Purification of a polymer for patterning process in semiconductor manufacturing: Presentation of compatible materials for the production/processing equipment and implementation in the production/processing Based on the solvents required, the materials in the production/processing equipment have to be chosen. Table 11 shows the compatibility of different materials towards the solvents required in the processing of polymer purification. When looking on the green circles in the table below, it is evident that a use of PTFE/FEP/PFA or FKM is required. Table 11 Compatibility of equipment materials towards solvents used for the purification of a polymer for patterning process in semiconductor manufacturing Compatibility list of plastics/elastomers towards typical solvent and reagents PTFE 0 no data FEP 1 resistant PFA 2 partially resistant ECTFE 3 conditionally resistant PVDF 4 not resistant Polytetrafluorethylene Fluorinated ethylene propylene Perfluoroalkoxyl polymer ethylene chloro trifluoro ethylene Polyvinylidene fluoride FKM FFKM Fluorocarbon-based Fluoroelastomer Materials Perfluorelastomers EPDM NBR VMQ CSM Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Vinyl Methyl Silicone Chlorosulfonated polyethylene synthetic rubber Compatibility list based on own testing, DECHEMA Werkstoffliste, and information from material supplier Fluorine containing material Fluorine free material Pro PTFE/FEP/PFA ECTFE (Halar) PVDF FKM ("Viton") FFKM ("Kalrez") EPDM NBR VMQ ("Silikon") CSM ("Hypalon") Solvent 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C Spalte16 Spalte2 Spalte3 Auswahl2 Auswahl22 Auswahl23 Auswahl24 Auswahl25 Auswahl26 Auswahl27 Auswahl28 Auswahl29 Auswahl210 Auswahl211 Auswahl212 Auswahl213 Auswahl214 Auswahl215 Auswahl216 2-Propanole 1 1 1 2 1 1 1 1 1 1 1 1 3 3 1 1 1 1 Acetonitrile 1 1 1 1 1 1 3 4 1 1 3 0 4 4 0 0 0 0 Cyclohexane 1 1 1 2 1 1 1 1 1 1 4 4 1 0 4 4 4 4 Ethyl acetate 1 1 1 2 3 3 4 4 1 1 3 0 4 4 4 4 3 3 t-Butyl methyl ether 1 1 2 2 1 0 4 4 0 0 4 4 4 4 0 0 0 0 PGMEA 1 0 0 0 0 0 4 4 1 0 1 0 4 4 0 0 0 0 Tetrahydrofurane 1 0 4 4 3 3 4 4 1 1 4 4 4 4 4 4 4 4 Water 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 1 1 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 19 Table 12 shows the production equipment and the components that are not made of steel or glass and the type of materials including the number of those pieces. The equipment is as follows: three different reactors, three agitated pressure filters, three vacuum drying ovens, equipment for sampling, compressed air diaphragm pump, dry vacuum compressor, vacuum line. Each of these equipment contains numerous "small components". The number of components/elements that can be classified as consumables is immense: ca 1200 pieces require materials made of fluoropolymers whereas about 30 pieces are made of other materials. Table 12 Production equipment and materials used for the purification of a polymer for patterning process in semiconductor manufacturing Equipment 100 L reactor, glass 100 L reactor, glass-lined 160 L reactor, glass-lined Component/Element vessel lid seal ball valve bottom valve lining seal seat + seal glass construction Protego seals entry system bag butterfly valve seals tube camlock coupling tri-clamp filter body gasket candle vessel lid seals ball valve bottom valve lining seal seat + seal glass construction Protego seals entry system bag butterfly valve seals tube camlock coupling tri-clamp filter body gasket candle vessel lid seals ball valve bottom valve glass construction lining seal seat + seal Protego Material FEP/Silikon PFTE PFA PTFE PTFE PTFE PTFE PE PTFE PTFE/Viton PFTE PTFE/Viton FEP/Silikon PFTE FEP/Silikon PFTE PFA PTFE PTFE PTFE PTFE PE PTFE PTFE/Viton PFTE PTFE/Viton FEP/Silikon PFTE FEP/Silikon PFTE PFA PTFE PTFE PTFE Number 2 4 2 4 2 1 450 5 1 2 4 2 6 1 2 4 5 10 2 1 200 5 1 2 4 2 6 1 2 4 5 10 2 1 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 20 Equipment agitated pressure filter agitated pressure filter agitated pressure filter vacuum drying oven vacuum drying oven vacuum drying oven Component/Element seals entry system bag butterfly valve seals tube camlock coupling tri-clamp filter body gasket filter support fabric filter layer 1 filter layer 2 seals candle material material material material stirrer stopcock filter support fabric filter layer 1 filter layer 2 seals coating material material material material material stirrer stopcock filter support fabric filter layer 1 filter layer 2 seals lining material material material material material stirrer stopcock coating material seals hordes ball valve glass construction shovel container door O-rings foils lining seals material seal seals hordes ball valve glass construction shovel container door O-rings foils lining seals material seal seals door O-rings Material PTFE PE PTFE PTFE/Viton PFTE PTFE/Viton FEP/Silikon PFTE ETFE ECTFE PTFE PTFE Polyetheretherketon (PEEK) PTFE ETFE ECTFE PTFE PTFE Polyetheretherketon (PEEK) PTFE ETFE ECTFE PTFE PTFE Polyetheretherketon (PEEK) PTFE PTFE/Silikon PTFE/Silikon PTFE PTFE PTFE PE/PS/PP FEP/Silikon PTFE/Silikon PTFE/Silikon PTFE PTFE PTFE PE/PS/PP FEP/Silikon PTFE/Silikon PTFE/Silikon Number 200 5 1 2 4 2 6 1 1 1 1 20 1 5 1 1 1 20 1 5 1 1 1 20 1 5 1 20 6 3 40 1 2 1 20 6 3 40 1 2 1 20 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 21 Equipment sampling compressed air diaphragm pump SIHI dry vacuum compressor vacuum line Component/Element hordes foils ball valve lining glass construction seals shovel material container seal vials material tube camlock coupling seals material membrane material seals butterfly valve valves condenser body lining gas- and liquid rinsing seals material Material PTFE PTFE PTFE PE/PS/PP FEP/Silikon PTFE PTFE PFTE PTFE FEP/Viton PFA/PTFE PTFE PTFE Number 6 3 40 1 2 9 10 2 4 5 1 2 2 50 2.1.6. Typical examples of equipment with PFAS components in plant 1 On the following pages some exemplary pictures are shown taken from different equipment and components in plant 1. This visualizes the variety of uses and applications of fluoropolymers in a chemical plant. Of course, this is only a very small part of the large number of components mentioned in the tables above. USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 22 Picture 1 Typical equipment with PFAS components - 100 L reactor USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 23 Picture 2 Typical equipment with PFAS components - centrifuge USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 24 Picture 3 Typical equipment with PFAS components - vacuum drying oven USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 25 Picture 4 Typical equipment with PFAS components - 1000L reactor USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 26 2.2. Solvents required for the manufacturing/processing in plant 2 and in plant 3 As it can be seen in Table 13, in plant 2 almost exclusively organic solvents are required for the production of the mentioned three products, e.g., ethanol, n-heptane, toluene, sodium hydroxide solution. Table 13 Solvents used in the production in plant 2 Acetone Acetnonitrile Anisole 1-Butanole t-Butyl methyl ether (1050C) Cyclohexane Dichloro methane Ethanol Ethyl acetate n-Heptane (10-60 C) Methanol 2-Propanole (20-95 C) PGMEA Sodium hydroxide solution (21-32 %, 50 C) Sodium hydrogen carbonate solution (20 C) Tetrahydrofuran e Toluene (0-110C) Water (20-50 C) Water/HCl (30 %; -10 50C) OLED 4 x Liquid crystal Intermediate for liquid crystal x x x x x x x x x x As it can be seen in Table 14, in plant 3 almost exclusively organic solvents are required for the production/processing steps of the four mentioned products, e.g., ethanol, toluene, 2-propanole. Table 14 Solvents used in the production/processing in plant 3 Acetone Acetnonitrile Anisole 1-Butanole t-Butyl methyl ether (1050C) Cyclohexane Dichloro methane Ethanol Ethyl acetate n-Heptane (10-60 C) Methanol 2-Propanole (20-95 C) PGMEA Sodium hydroxide solution (21-32 %, 50 C) Sodium hydrogen carbonate solution (20 C) Tetrahydrofuran e Toluene (0-110C) Water (20-50 C) Water/HCl (30 %; -10 - 50C) Excipient for vaccine Purification of excipient 1 Purification of excipient 2 Cosmetic raw material x x x x x x x x USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 27 2.2.1. Presentation of compatible materials for the production equipment in plant 2 and plant 3 Based on the solvents required, the materials in the production equipment have to be chosen. Table 15 to Table 21 show the compatibility of different materials towards the solvents required in the production/processing of products in the plants 2 and 3 in the respective selected week. When looking on the green circles in the table below, it is evident that a use of PTFE/FEP/PFA or FKM is required. Table 15 Compatibility of equipment materials towards solvents used for the production of OLED 4 Compatibility list of plastics/elastomers towards typical solvent and reagents PTFE 0 no data FEP 1 resistant PFA 2 partially resistant ECTFE 3 conditionally resistant PVDF 4 not resistant Polytetrafluorethylene Fluorinated ethylene propylene Perfluoroalkoxyl polymer ethylene chloro trifluoro ethylene Polyvinylidene fluoride FKM FFKM Fluorocarbon-based Fluoroelastomer Materials Perfluorelastomers EPDM NBR VMQ CSM Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Vinyl Methyl Silicone Chlorosulfonated polyethylene synthetic rubber Compatibility list based on own testing, DECHEMA Werkstoffliste, and information from material supplier Fluorine containing material Fluorine free material P PTFE/FEP/PFA ECTFE (Halar) PVDF FKM ("Viton") FFKM ("Kalrez") EPDM NBR VMQ ("Silikon") CSM ("Hypalon") Solvent 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C Spalte16 Spalte2 Spalte3 Auswahl2 Auswahl22 Auswahl23 Auswahl24 Auswahl25 Auswahl26 Auswahl27 Auswahl28 Auswahl29 Auswahl210 Auswahl211 Auswahl212 Auswahl213 Auswahl214 Auswahl215 Auswahl216 2-Propanole 1 1 1 2 1 1 1 1 1 1 1 1 3 3 1 1 1 1 Ethanol 1 1 1 2 1 1 2 3 1 1 1 1 2 3 1 3 1 1 Sodium hydroxide soluton (501%) 1 1 1 3 3 3 4 1 1 1 0 3 3 4 4 1 1 Toluene 1 0 1 2 1 1 3 3 1 0 4 4 4 4 4 4 4 4 Water 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 1 1 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 28 Table 16 Compatibility of equipment materials towards solvents used for the production of Liquid Crystal Compatibility list of plastics/elastomers towards typical solvent and reagents PTFE 0 no data FEP 1 resistant PFA 2 partially resistant ECTFE 3 conditionally resistant PVDF 4 not resistant Polytetrafluorethylene Fluorinated ethylene propylene Perfluoroalkoxyl polymer ethylene chloro trifluoro ethylene Polyvinylidene fluoride FKM FFKM Fluorocarbon-based Fluoroelastomer Materials Perfluorelastomers EPDM NBR VMQ CSM Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Vinyl Methyl Silicone Chlorosulfonated polyethylene synthetic rubber Compatibility list based on own testing, DECHEMA Werkstoffliste, and information from material supplier Fluorine containing material Fluorine free material P PTFE/FEP/PFA ECTFE (Halar) PVDF FKM ("Viton") FFKM ("Kalrez") EPDM NBR VMQ ("Silikon") CSM ("Hypalon") Solvent 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C Spalte16 Spalte2 Spalte3 Auswahl2 Auswahl22 Auswahl23 Auswahl24 Auswahl25 Auswahl26 Auswahl27 Auswahl28 Auswahl29 Auswahl210 Auswahl211 Auswahl212 Auswahl213 Auswahl214 Auswahl215 Auswahl216 Ethanol 1 1 1 2 1 1 2 3 1 1 1 1 2 3 1 3 1 1 n-Heptane 1 1 1 1 1 1 1 1 1 1 4 4 1 1 4 4 4 4 Toluene 1 0 1 2 1 1 3 3 1 0 4 4 4 4 4 4 4 4 Table 17 Compatibility of equipment materials towards solvents used for the production of an intermediate for liquid crystal Compatibility list of plastics/elastomers towards typical solvent and reagents PTFE 0 no data FEP 1 resistant PFA 2 partially resistant ECTFE 3 conditionally resistant PVDF 4 not resistant Polytetrafluorethylene Fluorinated ethylene propylene Perfluoroalkoxyl polymer ethylene chloro trifluoro ethylene Polyvinylidene fluoride FKM FFKM Fluorocarbon-based Fluoroelastomer Materials Perfluorelastomers EPDM NBR VMQ CSM Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Vinyl Methyl Silicone Chlorosulfonated polyethylene synthetic rubber Compatibility list based on own testing, DECHEMA Werkstoffliste, and information from material supplier Fluorine containing material Fluorine free material P PTFE/FEP/PFA ECTFE (Halar) PVDF FKM ("Viton") FFKM ("Kalrez") EPDM NBR VMQ ("Silikon") CSM ("Hypalon") Solvent 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C Spalte16 Spalte2 Spalte3 Auswahl2 Auswahl22 Auswahl23 Auswahl24 Auswahl25 Auswahl26 Auswahl27 Auswahl28 Auswahl29 Auswahl210 Auswahl211 Auswahl212 Auswahl213 Auswahl214 Auswahl215 Auswahl216 n-Heptane 1 1 1 1 1 1 1 1 1 1 4 4 1 1 4 4 4 4 Toluene 1 0 1 2 1 1 3 3 1 0 4 4 4 4 4 4 4 4 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 29 Table 18 Compatibility of equipment materials towards solvents used for the production/processing of Excipient for vaccine Compatibility list of plastics/elastomers towards typical solvent and reagents PTFE 0 no data FEP 1 resistant PFA 2 partially resistant ECTFE 3 conditionally resistant PVDF 4 not resistant Polytetrafluorethylene Fluorinated ethylene propylene Perfluoroalkoxyl polymer ethylene chloro trifluoro ethylene Polyvinylidene fluoride FKM FFKM Fluorocarbon-based Fluoroelastomer Materials Perfluorelastomers EPDM NBR VMQ CSM Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Vinyl Methyl Silicone Chlorosulfonated polyethylene synthetic rubber Compatibility list based on own testing, DECHEMA Werkstoffliste, and information from material supplier Fluorine containing material Fluorine free material P PTFE/FEP/PFA ECTFE (Halar) PVDF FKM ("Viton") FFKM ("Kalrez") EPDM NBR VMQ ("Silikon") CSM ("Hypalon") Solvent 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C Spalte16 Spalte2 Spalte3 Auswahl2 Auswahl22 Auswahl23 Auswahl24 Auswahl25 Auswahl26 Auswahl27 Auswahl28 Auswahl29 Auswahl210 Auswahl211 Auswahl212 Auswahl213 Auswahl214 Auswahl215 Auswahl216 2-Propanole 1 1 1 2 1 1 1 1 1 1 1 1 3 3 1 1 1 1 Toluene 1 0 1 2 1 1 3 3 1 0 4 4 4 4 4 4 4 4 Water 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 1 1 Table 19 Compatibility of equipment materials towards solvents used for the processing of Purification of excipient 1 No solvent required during processing of this material Table 20 Compatibility of equipment materials towards solvents used for the processing of Purification of excipient 2 Compatibility list of plastics/elastomers towards typical solvent and reagents PTFE 0 no data FEP 1 resistant PFA 2 partially resistant ECTFE 3 conditionally resistant PVDF 4 not resistant Polytetrafluorethylene Fluorinated ethylene propylene Perfluoroalkoxyl polymer ethylene chloro trifluoro ethylene Polyvinylidene fluoride FKM FFKM Fluorocarbon-based Fluoroelastomer Materials Perfluorelastomers EPDM NBR VMQ CSM Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Vinyl Methyl Silicone Chlorosulfonated polyethylene synthetic rubber Compatibility list based on own testing, DECHEMA Werkstoffliste, and information from material supplier Fluorine containing material Fluorine free material Pr PTFE/FEP/PFA ECTFE (Halar) PVDF FKM ("Viton") FFKM ("Kalrez") EPDM NBR VMQ ("Silikon") CSM ("Hypalon") Solvent 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C 20C 50C Spalte16 Spalte2 Spalte3 Auswahl2 Auswahl22 Auswahl23 Auswahl24 Auswahl25 Auswahl26 Auswahl27 Auswahl28 Auswahl29 Auswahl210 Auswahl211 Auswahl212 Auswahl213 Auswahl214 Auswahl215 Auswahl216 Hydrochloric acid (35 %) 1 1 1 1 1 1 1 2 1 1 3 0 4 4 3 4 1 2 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 30 Table 21 Compatibility of equipment materials towards solvents used for the production/processing of Cosmetic raw material Compatibility list of plastics/elastomers towards typical solvent and reagents PTFE 0 no data FEP 1 resistant PFA 2 partially resistant ECTFE 3 conditionally resistant PVDF 4 not resistant Polytetrafluorethylene Fluorinated ethylene propylene Perfluoroalkoxyl polymer ethylene chloro trifluoro ethylene Polyvinylidene fluoride FKM FFKM Fluorocarbon-based Fluoroelastomer Materials Perfluorelastomers EPDM NBR VMQ CSM Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Vinyl Methyl Silicone Chlorosulfonated polyethylene synthetic rubber Compatibility list based on own testing, DECHEMA Werkstoffliste, and information from material supplier PTFE/FEP/PFA Solvent 20C 50C Spalte16 Spalte2 Spalte3 Ethanol 1 1 t-Butyl methyl ether 1 1 Sodium hydroxide soluton (501%) 1 Fluorine containing material ECTFE (Halar) PVDF FKM ("Viton") 20C 50C 20C 50C 20C 50C Auswahl2 Auswahl22 Auswahl23 Auswahl24 Auswahl25 Auswahl26 1 2 1 1 2 3 2 2 1 0 4 4 1 1 3 3 3 4 FFKM ("Kalrez") 20C 50C Auswahl27 Auswahl28 1 1 0 0 1 1 Fluorine free material EPDM NBR VMQ ("Silikon") CSM ("Hypalon") 20C 50C 20C 50C 20C 50C 20C 50C Auswahl29 Auswahl210 Auswahl211 Auswahl212 Auswahl213 Auswahl214 Auswahl215 Auswahl216 1 1 2 3 1 3 1 1 4 4 4 4 0 0 0 0 1 0 3 3 4 4 1 1 2.2.2. Typical examples of equipment with PFAS components in plant 2 On the following pages three examples are displayed for larger equipment. In the tables the components with fluoropolymers are shown, in the pictures some selected (!) indications are given where fluoropolymers are used in the equipment. The high number of fluoropolymers is visible in Picture 5 to Picture 7 of the equipment, indicated with arrows. USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 31 Example 1: agitated nutsche filter Table 22 Overview of components with fluoropolymers (highlighted in pink) in an agitated nutsche filter Picture 5 Agitated nutsche filter with selected indications of fluoropolymers USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 32 Example 2: reactor Table 23 Overview of components with fluoropolymers (highlighted in pink) in a reactor Picture 6 reactor with selected indications of fluoropolymers USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 33 Example 3: centrifuge Table 24 Overview of components with fluoropolymers (highlighted in pink) in centrifuge Picture 7 centrifuge with selected indications of fluoropolymers USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 34 2.2.3. Further examples of fluoropolymer equipment/components Below some further examples of fluoropolymer-equipment/-components are shown. This type of equipment/components is used when required by the solvents/reaction solution: Picture 8 Product distributor with PTFE lined hoses and several sealings USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 35 Picture 9 Mobile pump with body, hose, and sealings made of PTFE USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 36 Picture 10 Further fluoropolymer-(containing) components USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 37 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 38 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 39 2.3. Summary and conclusion on the use of fluoropolymercomponents in production equipment Representative examples for production processes show that the required solvents are mainly organic solvents. Based on the compatibility information obtained from material suppliers and experiments conducted in our testing lab, the use of fluoropolymers is indispensable to run the equipment and processes in line with occupational health & safety requirements and environmental requirements. For consequences of the use of fluorine-free components, please refer to chapter 2.4. For each production process, a large number of equipment is used. In each equipment, a huge number of fluoropolymer parts are installed: ~600-1200 fluoropolymer materials in total in equipment for the exemplary production processes. The number of fluorine-free components is very low and in the range 10-20 (where, e.g., contact to solvent is excluded). The manifold use of the fluoropolymers is evident from the tables and pictures. In addition to the manufacturing plants, fluoropolymers are also required in the packaging of some chemicals for a safe transportation. 2.4. Investigation of alternatives and (in)compatibilities There are at least the following requirements on the materials used in the production equipment: - Chemical resistance towards solvents (and towards the mixture of chemicals in a reaction process, including organic solvents of different types a well as strong acids and bases) - No leaching of component material into product - Chemical durability - Temperature stability For our multipurpose plants with changing chemical conditions from production process to production process, the chemical resistance (to protect worker and the environment) and the linked stability towards leaching (to protect the product) are the main reasons for the use of fluoropolymer in our equipment. The use of fluoropolymers enables us to run a multipurpose plant with flexible production processes for different kind of products and solvents and to continuously comply with the obligations to minimize any exposures of chemicals towards the worker and the environment, as e.g., laid down in the Chemical Agents Directive (98/24/EC) and, e.g., the German Gefahrstoffverordnung (GefVO, 7 (4)). USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 40 It should be noted that the costs of fluoropolymer exceed the costs of fluorine-free components by far: as an example, the costs for a (simple) O-ring (ca 10.1 cm x 0.5 cm) are shown as used to tighten lines and hoses: Material of O-ring NBR Silicon EPDM FKM* Silicon mantled with FEP* PTFE* FFKM* * PFAS Ca costs for O-ring [Euro/piece] 0.60 1.50 2.30 4.30 17 19 230 Fluoropolymers are chemically resistant and do not leach. They do not change their form, durability, behavior during the use, e.g., in contact with solvents. Data for the resistance of fluoropolymers are shown below. Our company has a testing lab and experience which material can be used in which components of a production plant. This is usually checked by multiple tests. (In)Compatibility data with fluorine-free components Respective information from external sources is complemented by tests in our laboratory regarding the (in)compatibility of fluorine-free towards common solvents. In the following plenty of evidence is provided concerning the incompatibility of the fluorine-free polymers EPDM (Ethylene Propylene Diene (Monomer) Rubber), Silicon, NBR (Nitrile Butadiene Rubber). These materials were exposed to dichloro methane, heptane, tetrahydrofurane, or toluene, respectively, for 4 days at 40C. These solvents are commonly used in chemical production as it can be seen in Table 2, Table 13, and Table 14. The size, mass and volume of the components are measured before exposure, after 4 days of exposure and after drying. Pictures of the components are taken at the same time. Pictures of the "exposure vessel with component including solvent" are taken at start, after 24 h, at the end of the exposure (96 h). The results of the measurements are shown in Table 25. Pictures of the components and component with solvent exposure are displayed in USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 41 Picture 11 to Picture 27. Please note that the pictures shown are not necessarily in the same scale. Therefore, the scale paper in the background should be used as reference. The exposure of solvent at 40C for 4 days results for all material-solvent combinations to a distinct increase in volume (except for NBR in heptane). The relative volume increase ranges from about 50 % to > 200 %. For EPDM in heptane a curving of the component is observed (Picture 12), whereas a rupture of the component was noted for EPDM in THF (Picture 13), and EPDM in toluene (Picture 14). Furthermore, there is a mass change of the component after exposure to solvent with subsequent drying. This mass change is in the range of 2-5 % and similar for all components; for the flat seal made of EPDM and the NBR components, a discoloration was observed (yellowish), whereas for the EPDM round seal and for the silicon component, the solvents remain transparent. The discoloration of the solvents and, even more, the (relative) mass change are indicators for leaching of "polymer ingredients" into the product. This contamination of the product is not acceptable for our fine chemical industry customers, e.g., coming from pharmaceutical industry, semiconductor industry or display industry. Compatibility data with the fluoropolymer PTFE In our test lab, a test was performed to check the compatibility of a black and a white PTFE sealing for IBCs; samples of these components were stored in closed bottles with dichloro methane, ethylacetate, xylene and tetrahydrofurane (THF) for 40 days at 80C. These conditions are extreme when comparing to the conditions used for the exemplary experiment with the fluorine-free components. Before and after exposure, the sizes of the samples were measured, and the weight was determined. A second measurement of the weight of the samples was done after drying for 12 hours at 80C. GC-FID analyses of the solvents after the exposure were conducted and compared with chromatograms of blank solvents without PTFE exposure. A volume change was not observed for the PTFE-components. The relative mass change is shown in Table 26. A very slight increase of mass of the samples was observed with all solvents: directly after exposure the increase was in the range 0.1-1.1 %; after 12 h drying at 80C, the relative mass change was lower and in the range 0-0.7 %. A discoloration of solvent during exposure was not observed (see Picture 28). A chromatogram of the dichloro methane used for exposure to white PTFE showed only some small additional peaks (Picture 30) compared to blank dichloro methane (Picture 29). A chromatogram with dichloro methane used for exposure of black PTFE (Picture 31) was almost identical to the blank and less peaks were found than with white PTFE. The amount of leaching components was estimated to be very low and in the ppm-range. USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 42 Table 25 Overview on compatibility experiments conducted with 4 fluorine-free components in 4 different solvents including information on relative volume change, relative mass change and color change of solvent Sample declaration material Material Sample declaration Solvent Solvent temperature C Calculation of rel. volume change according to DIN ISO 1817 using density balance rel. volume change in % after 4d in solvent after ~72h drying rel. mass change in % after 4d in solvent after ~72h drying Colour of solvent after 24h in solvent after 96h in solvent A EPDM (flat seal) 1 DCM 40 A EPDM (flat seal) 2 heptane 40 A EPDM (flat seal) 3 THF 40 A EPDM (flat seal) 4 toluene 40 58.74 91.54 99.72 126.56 -8.19 -9.19 -6.71 -7.85 36.86 30.93 43.11 51.09 -4.38 distinctly yellow distinctly yellow -4.27 slightly yellow bright yellow -4.49 distinctly yellow distinctly yellow -4.76 bright yellow distinctly yellow B EPDM (round seal) 1 DCM 40 B EPDM (round seal) 2 heptane 40 B EPDM (round seal) 3 THF 40 B EPDM (round seal) 4 toluene 40 72.21 132.11 125.11 116.77 -3.15 -3.76 -3.89 -3.51 88.53 86.33 102.76 105.4 -2.61 no discoloration no discoloration -3.1 no discoloration no discoloration -3.21 no discoloration no discoloration -2.91 no discoloration no discoloration C Silicon 1 DCM 40 89,00 -3.52 C Silicon 2 heptane 40 111.24 -3.5 C Silicon 3 THF 40 117.02 -0.81 C Silicon 4 toluene 40 100.43 -6.79 78.52 52,00 71.04 59.11 -2.23 no discoloration no discoloration -2.21 no discoloration no discoloration 0.63 no discoloration no discoloration -5.39 no discoloration no discoloration D NBR 1 DCM 40 217.73 -4.76 234.62 -3.91 slightly yellow bright yellow D NBR 2 heptane 40 2.54 -3.81 2.92 -3.44 no discoloration slightly yellow D NBR 3 THF 40 187.22 -5.1 140.72 -4.5 slightly yellow bright yellow D NBR 4 toluene 40 135.01 -5.04 98.56 -4.34 slightly yellow bright yellow For use of elastomers, a relative volume change of 0-10% 10-20% 20-30% >30% or <-2% means resistant partially resistant conditionally resistant not resistant EPDM NBR Ethylene Propylene Diene (Monomer) Rubber Nitrile Butadiene Rubber Table 26 Relative mass change of two PTFE samples after 40 days of exposure to different solvents and subsequent drying Material Relative mass change [%] * Dichloro methane Ethylacetate Tetrahydrofurane PTFE white 0.5/0.2 0.2/0.1 0.1/.01 PTFE black 1.1/0.7 0.4/0.2 0.5/0.3 * first figure represents the change directly after removal of sample from solvent; the second figure was obtained after 12 h drying at 80C Xylene 0.1/0 0.5/0.3 USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 43 Picture 11 Experiment with EPDM component and dichloro methane: before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 44 Picture 12 Experiment with EPDM component and heptane: before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 45 Picture 13 Experiment with EPDM component and tetrahydrofurane (THF): before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 46 Picture 14 Experiment with EPDM component and toluene before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 47 Picture 15 Experiment with EPDM component and dichloro methane (DCM) before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 48 Picture 16 Experiment with EPDM component and heptane before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 49 Picture 17 Experiment with EPDM component and tetrahydrofurane (THF) before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 50 Picture 18 Experiment with EPDM component and toluene before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 51 Picture 19 Experiment with silicon component and dichloro methane (DCM) before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 52 Picture 20 Experiment with silicon component and heptane before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 53 Picture 21 Experiment with silicon component and tetrahydrofurane (THF) before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 54 Picture 22 Experiment with silicon component and toluene before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 55 Picture 23 Experiment with NBR component and dichloro methane (DCM) before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 56 Picture 24 Experiment with NBR component and heptane before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 57 Picture 25 Coloration of paper towel used for drying of NBR component after 96h exposure to heptane USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 58 Picture 26 Experiment with NBR component and tetrahydrofurane (THF) before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 59 Picture 27 Experiment with NBR component and toluene before start, after 96h of exposure and after drying and within the solvent during the time of the experiment USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 60 Picture 28 Sample bottle with black PTFE and different solvents after 40 d exposure at 80C Picture 29 Chromatogram GC-FID, dichloro methane, blank USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 61 Picture 30 Chromatogram GC-FID, dichloro methane, after 40 d exposure to PTFE, white Picture 31 Chromatogram GC-FID, dichloro methane, after 40 d exposure to PTFE, black Additional data on compatibility testing The additional example below shows the difficulty and complexity of the compatibility topic: Although silicon is considered as resistant against methanol according to state-of-the-art compatibility tables, a silicon hose was completely deteriorated when exposing to an alkaline solution of methanol at 40C for 330 h (Picture 32). It should be noted that the solution contained fluorides. USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 62 Picture 32 Silicon hose before and after exposure to an alkaline solution of methanol (fluorides containing) Furthermore, there are additional fluorine-free plastics (e.g., PEEK) and elastomers. Although some of those materials are resistant to (some) organic solvents, all properties of the material have to be considered as well as the explicit area of application: PEEK is a quite hard plastic and could be used for some applications requiring a strong durability (e.g., plastic screws), but PEEK is less suitable for use in flexible sealings, fittings. Assessment of results of the presented compatibility experiments The exposure of components made of the fluorine-free materials EPDM, Silicon, and NBR to common organic solvents like dichloro methane, heptane, tetrahydrofurane or toluene resulted in almost all cases in distinct increase in volume; in some cases, a rupture of the component was observed. When these fluorine-free materials are installed into production equipment and exposed to these solvents the increases of volume can lead to leaky connections, fittings, blocked valves.... Leaking production equipment leads to high danger for workers, and the environment and this is contradictory to the minimization rule of the Chemicals Agents Directive and national laws. In addition, in these experiments a significant mass loss was observed (2-5 % range). This can be interpreted as leaching of "fluorine-free polymer substances" into the solvent (and subsequently potentially the product). Overall, it can be concluded that the use of these fluorine-free materials is not suitable to fulfill the requirements mentioned at the beginning of this chapter and to fulfill occupational health and safety, environmental, quality and regulatory requirements set to a production facility. USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 63 The exposure of components made of PTFE to the common solvents like dichloro methane, ethylacetate, xylene, and tetrahydrofurane under much harsher conditions showed no volume change, a very minor mass increase and a very minor leaching of substances into the solvents (ppm-range). Overall, it can be concluded that the use of the fluoropolymer PTFE is suitable to fulfill the requirements mentioned at the beginning of this chapter and the occupational health and safety, environmental, quality and regulatory requirements set to a production facility. When looking into literature and comments from suppliers of such production equipment, there are some statements about the good compatibility of fluorine-free polymers towards the organic solvents. However, as the experiment with the silicon sample with methanol (and fluoride) shows, an in-depth testing and evaluation of a sample of a production equipment is mandatory to ensure safety of workers, the environment, and the product. The use of fluorine-free alternatives is always preferred due to the significant costs of the fluoropolymers, so alternatives are always carefully assessed. 2.5. Conclusion The use of fluoropolymers in the chemical production is always carefully evaluated due to the high costs for these materials; however, a huge number of different fluoropolymer components is required to run a production that is safe to the worker, the environment and to protect the product. The safety of the production is linked, at least, to the following properties of the materials used: - Chemical resistance towards solvents (and towards the mixture of chemicals in a reaction process) - No leaching of component material into product - Chemical durability - Temperature stability Based on the compatibility information obtained from material suppliers and experiments conducted in our testing lab, the use of fluoropolymers is indispensable to run the equipment and processes in line with occupational health & safety requirements and environmental requirements. No fluorine-free alternative is able to meet these requirements. Consequently, a (chemical) production with organic solvents is only possible with the use of fluoropolymers; referring to the nature of the C-F bond, an alternative to fluoropolymers cannot be developed. USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 64 3. Exposition Merck Electronics is a downstream user of fluoropolymers. From a life cycle perspective, our use is in the service life stage. There is no evidence that the use of fluoropolymers in components (such as hoses or PTFE-lined pipelines) leads to significant emissions of PFAS into air or water. Even in case of damage or use of very corrosive substances, emissions of PFAS are considered to be strongly limited. The amount of fluoropolymers annually disposed of is estimated to be in the range of 30 kg to 100 kg/plant. During inspections, services and maintenance, all parts are checked and replaced, if required. These figures are considered as very low, especially when comparing to the yearly average use of 1000 t of solvents in plant 1. Additional information regarding the end of life/waste stage is found in the following chapter. 4. Waste management and recycling In Merck Electronics an EHS Waste Management Standard provides a consistent framework for waste management across all sites. As waste producer, Merck is responsible for the ultimate disposal of all waste and therefore chooses the service providers with the utmost care, contractually stipulating disposal requirements, especially when it comes to hazardous waste. The generation of waste is prevented and minimized by, for instance, developing new production processes or optimizing existing ones. Articles are reused and recycled when possible. When prevention or recycling is not feasible, the best is done to recover materials from the waste created. This, of course also applies to production equipment containing PFAS polymers. At the end of life, articles and production equipment containing PFAS polymers, are considered as hazardous waste (contaminated with chemicals), are segregated, and collected, to be treated at a regulated waste disposal facility. One indispensable pillar of this waste management is the thermal treatment to ensure the proper disposal of our chemical waste. In a hazardous waste incineration plant, waste is treated by hightemperature incineration according to the Federal Immission Control Act and the 17th Ordinance to this Act (17th BImSchV) and the ordinances issued pursuant to it. Requirements for the design of the furnace, the minimum temperatures and specific limit values for emissions of inorganic and organic pollutants are clearly regulated. According to these ordinances, for hazardous waste incineration plants a minimum incineration temperature of 1,100C is required for waste with a halogen content in the waste greater than 1%. As example, information on the hazardous waste incineration plant in Biebesheim, Germany is given here: Two independent incineration lines are used. Each incineration line consists of a rotary kiln with an afterburner chamber and a downstream flue gas cleaning system. The waste is broken down into its atomic and molecular components at a temperature of around 1,200 C with an open flame. In the downstream post-combustion chamber, the resulting combustion gases are mixed with air to promote optimal burnout. The combustion gases are purified in a multi-stage exhaust gas treatment system USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 65 (including for example scrubber, fabric filter, activated carbon filter and catalyst, and mercury retention)i. Emissions are continuously monitored, and the measurement results transmitted to the competent authorities. According to Regulation (EU) 2019/1021 and other publicationsii iii iv v high-temperature incineration is correlated to temperatures > 1,100 C and 2 seconds contact time. Under these conditions, fluoropolymers are considered to be destroyed (RAC also proposes similar conditions in case of PFAS incineration in the opinion on the PFAS firefighting foam restriction Annex XV dossier [vi]: "If PFAS containing waste is incinerated or co-incinerated, the temperature shall be at least 1 100 C"). These conditions are achieved in the hazardous waste incinerators used and furthermore the abovedescribed downstream waste gas purification system filters resulting combustion gases in several stages. As all of the hazardous waste (including fluoropolymers) is disposed of in such incineration plants we conclude that the use of fluoropolymers in our chemical production does not lead to a relevant environmental/human exposure at/after the waste stage. 5. Impact From the data above, it is evident that a chemical production/processing with organic solvents (and some acids/bases) is only possible with the use of fluoropolymers as only fluoropolymers fulfill the requirements set on a chemical production/processing regarding worker safety, environmental safety and product quality. Due to the unique nature of the C-F bond and the resulting unique properties of the fluoropolymers, it is considered to be impossible to identify adequate alternatives. Thus, the whole chemical industry in EU would be largely jeopardized with critical impact also on downstream industries as e.g. semiconductor or pharmaceutical industry. Information on the economic impact on Merck Electronics is given in a confidential attachment to the Merck Electronics submission related to PFAS use in chemical manufacturing. 6. Summary and conclusion Three Merck Electronics plants in Darmstadt, Germany were selected to exemplify the practical importance of PFAS fluoropolymers based on typical productions. These plants are considered as representative to show current PFAS fluoropolymers use in chemical plants using batch production processes and utilizing a broad set of organic solvents as well as strong acids or bases. In the production processes considered, solvents such as anisole, ethanol, n-heptane, dichloromethane, tetrahydrofuran, and toluene were used. USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 66 Final products of the considered examples are for use in the Electronic industry (OLEDs, liquid crystals, process chemicals for semiconductor manufacturing), Pharmaceutical industry (APIs, excipients for vaccine) and Cosmetic industry (cosmetic raw materials). Due to economic considerations, fluoropolymers are only used in chemical production where absolutely necessary. Accepting the high costs, a huge number of different fluoropolymer components are required to run a production that is safe for the worker, the environment, and ensures product quality. The safety of the production can be directly linked to, at least, the following properties of the materials used: - Chemical resistance towards solvents (and towards the mixture of chemicals in a reaction process) - No leaching of component material into product - Chemical durability - Temperature stability Based on the compatibility information obtained from material suppliers and experiments conducted in our testing lab, the use of fluoropolymers is necessary to meet the requirements above and to run the equipment and processes in line with occupational health & safety requirements and environmental requirements. In addition to manufacturing plants, fluoropolymers are also required in the packaging of some chemicals for safe transportation. No fluorine-free alternative is able to meet these requirements with the solvents used. In some literature examples, as well as in some equipment-supplier information, statements can be found about general compatibility of fluorine-free polymers towards some organic solvents. However, practical testing and evaluation of a sample of a production equipment is mandatory to ensure safety of workers, the environment, and the product. Such testing is standard in our operations. Information on potential alternatives given in the set of documents accompanying the published restriction draft is not validated in such a way. Thus, general statements are not necessarily valid for a specific use of these materials. Fluoropolymer components have turned out to be the only material being able to withstand the various challenging conditions in the manufacturing plants. Due to the unique nature of the C-F bond and the resulting unique properties of the fluoropolymers, it is considered to be impossible to identify adequate alternatives. Merck Electronics is a downstream user of fluoropolymers. From a life cycle perspective, the use is in the service life stage. The use of fluoropolymers in components (such as hoses or PTFE-lined pipelines) does not lead to significant emissions of PFAS into air or water - even in case of damage or use of very corrosive substances. The amount of fluoropolymers disposed of annually is estimated to be in the range from 30 to 100 kg per plant. These figures are considered as very low, especially when compared to the yearly average use of 1000 t of solvents in plant 1. In the organization of Merck Electronics, an EHS Waste Management Standard provides a consistent framework for waste management across all sites. As a waste producer, Merck is responsible for the USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 67 ultimate disposal of this waste and therefore chooses the service providers in this regard with the utmost care, contractually stipulating disposal requirements, especially when it comes to hazardous waste. At the end of life, articles and production equipment containing PFAS polymers are considered contaminated articles, segregated, and collected, to be treated at a hazardous waste incineration plant - conditions under which PFAS are destroyed. Consequently, we conclude that the use of fluoropolymers in our chemical production does not lead to a significant environmental/human exposure at or after the waste stage. Chemical production with organic solvents and strong acids/bases is only possible with the use of fluoropolymers as only fluoropolymers fulfill the requirements regarding worker safety, environmental safety, and product quality. Based on the current broad PFAS restriction proposal, fluoropolymers will not be available anymore for use in chemical production 18 months after entry into force of the restriction. Thus, the entire chemical industry in the EU would be largely jeopardized by implementation of the current restriction proposal with critical impact also on downstream industries as e.g., semiconductor or pharmaceutical industry. With the information and facts delivered in the previous chapters, we provided substantial evidence on the indispensable need of fluoropolymers in chemical production plants. There are approximately a thousand fluoropolymer components in a chemical plant to provide the required safety for workers, the environment, and the product. The total amount of fluoropolymers disposed of per year is very low compared with the amount of chemicals used/handled. No fluorine-free alternative is known to meet the requirements with the solvents used and each and every potential alternative needs adequate, in-depth testing with real production chemicals. Considering the resistance and durability profile needed, suitable alternative substances would likely have comparable persistence properties to PFAS. With adequate risk management measures related to chemicals as well as to contaminated articles, (including fluoropolymers) exposure to the environment or population during service life and at/after end-of life/waste stage can be strongly limited. The potential impact of the current restriction proposal on our company is described in the confidential attachment to this submission. We request a thorough adaptation of the restriction proposal reflecting a time-unlimited derogation for the use of fluoropolymers in the chemical industry and the upstream processes to manufacture respective fluoropolymer articles. USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 68 [i] HIM- Infos: https://www.indaver.de/entsorgen/anlagen/biebesheim/sonderabfallverbrennungsanlage/ [ii] Yamada, T., Taylor, P. Buck, R. Kaiser, M. Giraud, R. (2005): Thermal Degradation of Fluorotelemer Treated Articles and Related Materials. Chemosphere 61, 974-984. [iii] UNEP-POPs (2021): UNEP/POPS/COP10/INF20: Guidance on best available techniques and best environmental practices for the use of perfluorooctane sulfonic acid, perfluorooctanoic acid, and their related compounds listed under the Stockholm Convention, p. 29-30, Meeting Documents(brsmeas.org) [iv] Umweltbundesamt (2020), Texte 137/2022, Sanierungsmanagement fr lokale und flchenhafte PFAS Kontaminationen Anhang C: Sanierungsverfahreniv)) on persistent organic pollutants, thermal treatment processes in particular are suitable for recycling or disposing of waste containing PFAS [v] UBA; Das Magazin des Umweltbundesamtes, Schwerpunkt; 01, 2020. PFAS -gekommen um zu bleiben [vi] RAC OPINION ON AN ANNEX XV DOSSIER PROPOSING RESTRICTIONS ON PFAS IN FIREFIGHTING FOAMS (ECHA/RAC/RES-O-0000007226-75-01/F) USE OF FLUOROPOLYMERS IN CHEMICAL MANUFACTURING PLANTS - MERCK ELECTRONICS 69