EP0033262A1 - Electrolysis diaphragm and method for its manufacture - Google Patents
Electrolysis diaphragm and method for its manufacture Download PDFInfo
- Publication number
- EP0033262A1 EP0033262A1 EP81400058A EP81400058A EP0033262A1 EP 0033262 A1 EP0033262 A1 EP 0033262A1 EP 81400058 A EP81400058 A EP 81400058A EP 81400058 A EP81400058 A EP 81400058A EP 0033262 A1 EP0033262 A1 EP 0033262A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- diaphragm according
- microporous
- parts
- carboxylic acid
- divinylbenzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- 239000003085 diluting agent Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 229920002313 fluoropolymer Polymers 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 5
- 229910001514 alkali metal chloride Inorganic materials 0.000 abstract 1
- 239000002585 base Substances 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000010425 asbestos Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229910052895 riebeckite Inorganic materials 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 235000010216 calcium carbonate Nutrition 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 230000002706 hydrostatic effect Effects 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- SFRUVBWDAJNXSB-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C SFRUVBWDAJNXSB-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical class C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical class OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910002835 Pt–Ir Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000005172 methylbenzenes Chemical class 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical group O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
Definitions
- the present invention relates to a diaphragm for electrolysis, based on fluorinated resins, having a marked hydrophilic character, as well as the process for preparing this diaphragm.
- hydrophilic diaphragms ie diaphragms which are easily wetted with an electrolyte, can be obtained by a simple process which gives them properties favorable for electrolysis, particularly in contact with concentrated detergents.
- One of the objects of the invention is a microporous diaphragm based on fluorinated resin, intended in particular for the electrolysis of alkali metal halide, coated on at least part of the internal surface of the pores with a carboxylic acid copolymer unsaturated and non-ionic unsaturated monomer.
- Another object of the invention is the process for obtaining this diaphragm comprising the formation of a porous sheet based on fluorinated resin, the impregnation of this sheet by a mixture containing at least one unsaturated carboxylic acid, at least one nonionic monomer and at least one polymerization initiator, this mixture having a low viscosity, the copolymerization of this mixture, the draining of the sheet after impregnation and copolymerization of the comonomers in said sheet .
- microporous sheet can be prepared by a wide variety of methods, many of these methods being well known today.
- the fluorinated resins which may be used are in particular polytetrafluoroethylene, polytrifluoroethylene, polyhexafluoropropylene, polyvinyl fluoride, polyvinylidene fluoride,. polyperfluoroalkoxyethylene, polyhaloethylenes comprising one or two chlorine atoms and three or two fluorine atoms on each ethylene unit and in particular polychlorotrlfluoroethylene, the corresponding polyhalopropylenes, copolymers of ethylene and / or propylene and unsaturated hydrocarbons halogens, at least partially fluorinated having 2 or 3 carbon atoms.
- These resins can be reinforced with various fibers, either mineral, such as asbestos, glass, zirconia or carbon quartz, or organic, such as polypropylene or optionally halogenated, and especially fluorinated, polyhalovinylidene, etc. fibers. ...
- the proportion of reinforcing fibers can be from 0 to 200% of the weight of the resin. As already mentioned above when a relatively high proportion of asbestos is present, greater than 30% of the weight of resin, the diaphragm generally has satisfactory wettability without additional treatment.
- the overall porosity should preferably be 50 to 95% and the equivalent average pore diameter is between 0.1 and 12 micrometers and preferably between 0.2 and 6 micrometers, this equivalent diameter being the diameter of a cylindrical pore theoretical which allows the same speed of passage of a liquid weakly viscous, under a determined pressure, than the real pore.
- the carboxylic acid monomers used carry one or two carboxylic groups. It can be acrylic, methacrylic acids and their halogenated, phenylacrylic, ethylacrylic, maleic, itaconic, butyl acrylic, vinyl benzoic acids, etc. Acrylic and methacrylic acids are preferred.
- the nonionic monomers can carry a single ethylenic bond, such as styrene, methylstyrene, ethylvinylbenzene, chloro- or fluorostyrenes, or-methylstyrenes, as well as vinylpyridine or pyrrolidone. They can have several unsaturations and also promote crosslinking of the polymer layer formed.
- divinylbenzenes and in particular the para isomer which is preferred, trivinylbenzene, divinylnaphthalenes, divinylethyl or methylbenzenes, trivinyl 1-3-4 cyclohexane, etc.
- At least one non-ionic monounsaturated monomer and one pluri-unsaturated monomer is then between 0.1 and 10 and preferably between 0.4 and 2.5.
- the commercially available divinylbenzene ethylvinylbenzene mixture is advantageously used.
- the proportion by weight of unsaturated acid on all of the carboxylic and nonionic comonomers is between 40 and 98% by weight and preferably between 70 and 95% and it is important that this mixture of monomers optionally and preferably added with diluent, present a low viscosity preferably less than 2 cp so as to be able to penetrate under a slight depression (from 1 to 100 mmHg below atmospheric pressure) in the pores of the microporous substrate.
- an inert diluent is added to the mixture of monomers, in particular methanol, ethanol, isopropanol, butanols, acetone, methyl isobutyl ketone, dioxane , chloro or dibromomethane, optionally halogenated aliphatic hydrocarbons having from 2 to 10 carbon atoms, dimethylformamide, dimethylacetamide, dimethylsulfoxide etc ...
- Ethanol is the preferred diluent; in general the diluents must have a tension relatively low values at room temperature and be miscible with comonomers and possibly with water.
- comonomers preferably 1600 to 30 parts of diluent are used.
- the copolymer formed from the diluted aln ⁇ comonomers will be present in an at least monolecular layer on at least part of the internal surface of the pores.
- a radical polymerization initiator is added to the mixture of comonomers; it must not cause significant polymerization at room temperature in the absence of activating radiation (ultraviolet), but cause polymerization of the comonomers in a time preferably less than 12 h, at a temperature below that of softening of the fluorinated polymer put in use, and preferably less than 100 ° C. Mention may be made, among the polymerization initiators, of benzoyl, lauroyl, t-butyl, cumyl peroxides, t-butyl peracetate or perbenzoate and also azobisisobutyronitrile.
- the polymerization temperature conditions can be adapted to the choice of diluent so as to prevent it from leaving too quickly during the in situ polymerization.
- Activators can be used for this, for example dimethylaniline which, combined with benzoyl peroxide, makes it possible to obtain a polymerization around 40 ° C.
- the process for preparing these wettable microporous diaphragms therefore comprises in its first phase the preparation of a microporous sheet.
- a porophore filler into a latex of fluorinated resin and in particular of polytetrafluoroethylene containing a plasticizing agent, 900 to 1200 and preferably 400 to 900 parts by weight of porophores, 0.5 to 2 parts of plasticizing agent and 1 to 20 parts of water being added to 100 parts of resin of a latex containing 40 to 60% by weight of dry matter, to mix the whole in a kneader moderately agitated, that is to say of which the rotor turns unless at 100 revolutions / min, to preform by rolling a sheet using the paste obtained, to dry it and then to sinter it at a temperature of the order of the melting point of the polymer used.
- the porophore agent which is preferably calcium carbonate is then removed by immersion in acid which is preferably acetic acid in aqueous solution at 15-20% by weight.
- porous sheets in particular in the case where the fluoropolymer used is a copolymer of ethylene and chlorotrifluoroethylene, or a PTFE latex, associated with mineral or organic fibers (asbestos, zirconia, fibrillated polyolefins) by dispersing the copolymer in an amount of 5 to 50% of the weight of fibers in the electrolyte, that is to say containing about 15% of sodium hydroxide and 15% of sodium chloride to which a surfactant is added.
- the fluoropolymer used is a copolymer of ethylene and chlorotrifluoroethylene, or a PTFE latex, associated with mineral or organic fibers (asbestos, zirconia, fibrillated polyolefins) by dispersing the copolymer in an amount of 5 to 50% of the weight of fibers in the electrolyte, that is to say containing about 15% of sodium hydroxide and 15% of sodium chloride to which a surfactant
- This suspension is deposited on a surface allowing filtration; this surface can in particular be a perforated cathode. After spinning and drying, the sheet formed during filtration is heated to 260 ° C temperature which is maintained from 30 min to 1 hour.
- the porous sheet thus formed is then impregnated with a mixture of comonomers and of polymerization initiator and, in general of inert diluent.
- the proportion of diluent mentioned above must be chosen according to various other parameters and in particular, the proportion of the crosslinking agent comonomer, in particular divinylbenzene, relative to the unsaturated carboxylic acids and the proportion of polymerization initiator in particular. benzoyl peroxide.
- the overall condition which must be respected, and which leads to a choice in the combination of the various other parameters, is that 0.1 to 6% of the total pore volume, before the in situ copolymerization, of the microporous support sheet, are occupied by of the carboxylic copolymer.
- the proportion by weight of divinylbenzene can be between 2.5 and 25 parts per 100 parts of unsaturated carboxylic acid. It is also good to use only small amounts of polymerization initiator, for example, less than 5 parts by weight of benzoyl peroxide per 100 parts of comonomers and little or no accelerator of copolymerization such as dimethylaniline (less than 2 parts).
- This impregnation can be done for example by immersion in a tank containing this liquid mixture and filtration under vacuum from 10 to 100 mmHg.
- the sheet optionally on its support, and in particular on a cathode, is then introduced into an enclosure where the temperature, or actinic rays, in particular ultraviolet rays, allow the action of the polymerization initiators. It can be immersed in a liquid, water for example. It is important that the temperature is not too high, generally less than 150 ° C. and does not substantially modify the structure of the microporous sheet by too rapid departure of the diluent or destruction of the deposited copolymer.
- the polymerization time (which corresponds approximately to the half-life of the initiator used) is preferably less than 12 hours.
- a preferred means of polymerization is immersion in water between 40 ° C and 100 ° C.
- Table I given with the examples below clearly illustrates the influence of various factors such as the porosity of the diaphragm or, which is directly the cause, the proportion of porophore agent, the weight ratio between the carboxylic acids and the non-ionic monomers and the amount of diluent added on the pressure drop of the electrolyte through the diaphragm or in other words on the hydrostatic pressure, due to the anolyte, necessary to ensure satisfactory percolation and on the electrical voltage in the cell.
- the factors mentioned can be chosen to achieve a specific goal.
- the mixture is homogenized for 5 minutes in a mixer WERNER type whose Z-shaped rotors rotate at a speed of 45 rpm.
- the dough obtained is put into sheets using a LESCUYER type roller mixer.
- the thickness is reduced to 1.2 mm.
- the initial speed of rotation of the cylinders by 15 rpm is gradually reduced to 5 rpm in 2 to 4 minutes.
- the sheet thus formed is dried for 15 hours at 90 ° C then 2 hours at 120 ° C and then sintered in a hot air circulation oven whose temperature has risen, at a rate of 100 ° C / h, to 360 ° C where it is kept for 15 minutes.
- the calcium carbonate is eliminated by immersion for 72 hours in an aqueous solution of acetic acid at 25% by weight added with 2 g / 1 of fluorinated surfactant brand "ZONYL FSN from EI Du Pont De Nemours Co . "
- the diaphragm is then rinsed with water and then immersed for 12 hours in ethanol.
- divinylbenzene contains 45% by weight of ethylvinylbenzene and 55% of divinylbenzene.
- the copolymerization is brought about by immersion for 2 hours in water at 80 ° C.
- This diaphragm which has been given remarkable wettability, is kept in water until it is used. It is then placed, in contact with a cathode, in braided laminated iron from the company "GANTOIS", an electrolysis cell.
- the anode is made of expanded titanium coated with Pt-Ir alloy.
- the distance between the electrodes is 5.5 mm; it is held in place by a rubber seal.
- the electrolyte introduced into the anode compartment is a brine containing 300 g / l of sodium chloride.
- the temperature is 85 ° C.
- the current density is 25 A / dm 2
- the electric voltage is 3.35 V
- the electrolyte charge is 40 cm.
- the sodium hydroxide of the catholyte has a concentration of 123 g / l
- the faradaic yield (OH ion) is 94%.
- Example 1 The test of Example 1 is repeated by varying the quantity of calcium carbonate and the proportion of the diluent and peroxide comonomers of the impregnation mixture.
- test 235 The first two control tests (1 and 2) had to be stopped after 25 hours, which is the time when the load h and voltage U measurements were made. The same is true of test 235.
- the electrolyte charge R is the hydrostatic pressure on the diaphragm expressed in cm or the electrolyte height of density 1.2 approximately, multiplied by this last figure.
- the amount of NaOH is expressed in grams / liter.
- the yield R (OH)% is a faradaic yield calculated from the sodium hydroxide formed.
- T% is the percentage of the pore volume occupied by the dry polymer.
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Abstract
Description
La présente invention concerne un diaphragme pour électrolyse, à base de résines fluorées, présentant un caractère hydrophile marqué, ainsi que le procédé de préparation de ce diaphragme.The present invention relates to a diaphragm for electrolysis, based on fluorinated resins, having a marked hydrophilic character, as well as the process for preparing this diaphragm.
Depuis un certain nombre d'années, les diaphragmes conventionnels en amiante, pour électrolyse, déposés sur les cathodes des cellules destinées notamment à l'obtention de chlore et de soude, sont progressivement remplacés par des diaphragmes à base de résines fluorées contenant éventuellement des fibres de renforcement. De tels diaphragmes présentent de nombreux avantages dûs en particulier aux propriétés chimiques des résines fluorées mais aussi un inconvénient notable, également inhérent à ces résines, qui tient à leur faible mouillabilité. Ce défaut est atténué lorsque des fibres telles que l'amiante sont incorporées en proportions importantes dans les diaphragmes, mais l'on sait le danger que présente cette matière pour ses utilisateurs. De nombreuses solutions ont été proposées pour pallier cet inconvénient ; outre l'emploi de charges particulières telles que les oxydes ou hydroxydes de titane, zirconium ou aluminium ou l'amiante, on a aussi suggéré l'introduction de groupes contenant du soufre, des groupes sulfoniques en particulier, soit par traitement in situ de la résine mise en oeuvre, comme le décrit le brevet US 4.153.520, soit par addition de résine préalablement sulfonée, décrite notamment dans le brevet français publié sous le n° 2.152.988.For a number of years, conventional asbestos diaphragms, for electrolysis, deposited on the cathodes of cells intended in particular for obtaining chlorine and sodium hydroxide, have been gradually replaced by diaphragms based on fluorinated resins possibly containing fibers. reinforcement. Such diaphragms have numerous advantages due in particular to the chemical properties of fluorinated resins but also a notable drawback, also inherent in these resins, which is due to their low wettability. This defect is mitigated when fibers such as asbestos are incorporated in large proportions in the diaphragms, but we know the danger that this material presents for its users. Many solutions have been proposed to overcome this drawback; in addition to the use of particular fillers such as oxides or hydroxides of titanium, zirconium or aluminum or asbestos, it has also been suggested the introduction of groups containing sulfur, sulfonic groups in particular, either by in situ treatment of the resin used, as described in US Pat. No. 4,153,520, or by addition of previously sulfonated resin, described in particular in the French patent published under No. 2,152,988.
On a maintenant trouvé que des diaphragmes hydrophiles, c'est-à-dire facilement- mouillés par un électrolyte, pouvaient être obtenus par un procédé simple qui leur confère des propriétés favorables pour l'électrolyse, particulièrement au contact de lessives concentrées.It has now been found that hydrophilic diaphragms, ie diaphragms which are easily wetted with an electrolyte, can be obtained by a simple process which gives them properties favorable for electrolysis, particularly in contact with concentrated detergents.
Un des objets de l'invention est un diaphragme microporeux à base de résine fluorée, destiné notamment à l'électrolyse d'halogénure de métaux alcalins, revêtu sur au moins une partie de la surface interne des pores d'un copolymère d'acide carboxylique insaturé et de monomère insaturé non ionique.One of the objects of the invention is a microporous diaphragm based on fluorinated resin, intended in particular for the electrolysis of alkali metal halide, coated on at least part of the internal surface of the pores with a carboxylic acid copolymer unsaturated and non-ionic unsaturated monomer.
Un autre objet de l'invention est le procédé d'obtention de ce diaphragme comprenant la formation d'une feuille poreuse à base de résine fluorée, l'imprégnation de cette feuille par un mélange contenant au moins un acide carboxylique insaturé, au moins un monomère non ionique et au moins un initiateur de polymérisation, ce mélange présentant une faible viscosité, la copolymérisation de ce mélange, l'égouttage de la feuille après imprégnation et copolymérisation des comonomères dans ladite feuille.Another object of the invention is the process for obtaining this diaphragm comprising the formation of a porous sheet based on fluorinated resin, the impregnation of this sheet by a mixture containing at least one unsaturated carboxylic acid, at least one nonionic monomer and at least one polymerization initiator, this mixture having a low viscosity, the copolymerization of this mixture, the draining of the sheet after impregnation and copolymerization of the comonomers in said sheet .
La feuille microporeuse peut être préparée par des procédés très divers, beaucoup de ces procédés étant aujourd'hui bien connus.The microporous sheet can be prepared by a wide variety of methods, many of these methods being well known today.
Les résines fluorées susceptibles d'être utilisées sont notamment le polytétrafluoroéthylène, le polytrifluoroéthylène, le poly- hexafluoropropylène, le polyfluorure de vinyle, le polyfluorure de vinylidène, le . polyperfluoroalcoxyéthylène, les polyhalogéno- éthylènes comprenant un ou deux atomes de chlore et trois ou deux atomes de fluor sur chaque motif éthylène et notamment le poly- chlorotrlfluoroéthylène, les polyhalogénopropylènes correspondants, les copolymères d'éthylène et/ou de propylène et d'hydrocarbones insaturés halogènes, au moins partiellement fluorés ayant 2 ou 3 atomes de carbone. Parmi ces composés, on peut citer notamment les produits connus sous les marques "TEFLON" de Du Pont de Nemours, "SOREFLON" de la Société Produits Chimiques Ugine Kuhlmann, "HALAR" de Allied Chemicals Co.The fluorinated resins which may be used are in particular polytetrafluoroethylene, polytrifluoroethylene, polyhexafluoropropylene, polyvinyl fluoride, polyvinylidene fluoride,. polyperfluoroalkoxyethylene, polyhaloethylenes comprising one or two chlorine atoms and three or two fluorine atoms on each ethylene unit and in particular polychlorotrlfluoroethylene, the corresponding polyhalopropylenes, copolymers of ethylene and / or propylene and unsaturated hydrocarbons halogens, at least partially fluorinated having 2 or 3 carbon atoms. Among these compounds, mention may be made in particular of the products known under the brands "TEFLON" from Du Pont de Nemours, "SOREFLON" from the company Produits Chimiques Ugine Kuhlmann, "HALAR" from Allied Chemicals Co.
Ces résines peuvent être renforcées par différentes fibres soit minérales telles que les fibres d'amiante, de verre, de quartz de zircone ou de carbone, soit organiques telles que les fibres de polypropylène ou de polyéthylène éventuellement halogéné et notamment fluorés, de polyhalogénovinylidène etc....These resins can be reinforced with various fibers, either mineral, such as asbestos, glass, zirconia or carbon quartz, or organic, such as polypropylene or optionally halogenated, and especially fluorinated, polyhalovinylidene, etc. fibers. ...
La proportion des fibres de renforcement peut être de 0 à 200 % du poids de la résine. Comme cela a déjà été signalé ci-dessus lorsqu'une proportion d'amiante relativement élevée est présente, supérieure à 30 % du poids de résine, le diaphragme a généralement une mouillabilité satisfaisante sans traitement additionnel.The proportion of reinforcing fibers can be from 0 to 200% of the weight of the resin. As already mentioned above when a relatively high proportion of asbestos is present, greater than 30% of the weight of resin, the diaphragm generally has satisfactory wettability without additional treatment.
La porosité globale doit être de 50 à 95 % de préférence et le diamètre moyen équivalent des pores est compris entre 0,1 et 12 micromètres et de préférence entre 0,2 et 6 micromètres, ce diamètre équivalent étant le diamètre d'un pore cylindrique théorique qui permet la même vitesse de passage d'un liquide faiblement visqueux, sous une pression déterminée, que le pore réel.The overall porosity should preferably be 50 to 95% and the equivalent average pore diameter is between 0.1 and 12 micrometers and preferably between 0.2 and 6 micrometers, this equivalent diameter being the diameter of a cylindrical pore theoretical which allows the same speed of passage of a liquid weakly viscous, under a determined pressure, than the real pore.
Les monomères acides carboxyliques mis en oeuvre sont porteurs d'un ou deux groupes carboxyliques. Ce peut être les acides acrylique, méthacrylique et leurs dérivés halogénés, phénylacrylique, êthylacrylique, maléique, itaconique, butyl-acrylique, vinylben- zoique etc.....Les acides acrylique et méthacrylique sont préférés.The carboxylic acid monomers used carry one or two carboxylic groups. It can be acrylic, methacrylic acids and their halogenated, phenylacrylic, ethylacrylic, maleic, itaconic, butyl acrylic, vinyl benzoic acids, etc. Acrylic and methacrylic acids are preferred.
Les monomères non ioniques peuvent être porteurs d'une seule liaison éthylénique, tels que le styrène, le méthylstyrène, l'éthylvinylbenzène, les chloro- ou fluorostyrènes, ou-méthylstyrènes, ainsi que la vinylpyridine ou pyrrolidone. Ils peuvent présenter plusieurs insaturations et favoriser aussi une réticulation de la couche de polymère formée. On peut citer à titre d'exemples, les divinylbenzènes et notamment l'isomère para qui est préféré, le trivinylbenzène, les divinylnaphtalènes, les divinyléthyl ou mé- thylbenzènes, le trivinyl 1-3-4 cyclohexane etc...The nonionic monomers can carry a single ethylenic bond, such as styrene, methylstyrene, ethylvinylbenzene, chloro- or fluorostyrenes, or-methylstyrenes, as well as vinylpyridine or pyrrolidone. They can have several unsaturations and also promote crosslinking of the polymer layer formed. By way of example, mention may be made of divinylbenzenes and in particular the para isomer which is preferred, trivinylbenzene, divinylnaphthalenes, divinylethyl or methylbenzenes, trivinyl 1-3-4 cyclohexane, etc.
On peut et préfère utiliser à la fois au moins un monomère non ionique mono-insaturé et un monomère pluri-insaturé. La proportion numérique des molécules ou motifs de ces deux types de monomères est alors comprise entre 0,1 et 10 et de préférence entre 0,4 et 2,5. Le mélange divinylbenzène éthylvinylbenzène disponible dans le commerce est employé avantageusement.It is possible and preferred to use at least one non-ionic monounsaturated monomer and one pluri-unsaturated monomer. The numerical proportion of the molecules or units of these two types of monomers is then between 0.1 and 10 and preferably between 0.4 and 2.5. The commercially available divinylbenzene ethylvinylbenzene mixture is advantageously used.
La proportion pondérale d'acide insaturé sur l'ensemble des comonomères carboxyliques et non ioniques est comprise entre 40 et 98 % en poids et de préférence entre 70 et 95 % et il importe que ce mélange de monomères additionné éventuellement et préférentiellement de diluant, présente une faible viscosité de préférence inférieure à 2 cp de façon à pouvoir pénétrer sous une légère dépression (de 1 à 100 mmHg en-dessous de la pression atmosphérique) dans les pores du substrat microporeux. De façon à contrôler la quantité de monomères introduite et la dispersion dans la porosité, un diluant inerte est additionné au mélange de monomères, notamment le méthanol, l'éthanol, l'isopropanol, les butanols, l'acétone, la méthylisobutylcétone, le dioxane, les chloro ou dibromométhane, les hydrocarbures aliphatiques éventuellement halogénés ayant de 2 à 10 atomes de carbone, le diméthylformamide, le diméthylacétamide, le diméthylsulfoxyde etc.....L'êthanol est le diluant préféré ; en général les diluants doivent avoir une tension de valeurs relativement faible à la température ambiante et être miscibles avec les comonomères et éventuellement avec l'eau. Pour 100 parties en poids de comonomères, on met en oeuvre de préférence de 1600 à 30 parties, de diluant. Le copolymère formé à partir des comonomères alnε dilués sera présent en une couche au moins mono- moléculaire sur au moins une partie de la surface interne des pores.The proportion by weight of unsaturated acid on all of the carboxylic and nonionic comonomers is between 40 and 98% by weight and preferably between 70 and 95% and it is important that this mixture of monomers optionally and preferably added with diluent, present a low viscosity preferably less than 2 cp so as to be able to penetrate under a slight depression (from 1 to 100 mmHg below atmospheric pressure) in the pores of the microporous substrate. In order to control the amount of monomers introduced and the dispersion in the porosity, an inert diluent is added to the mixture of monomers, in particular methanol, ethanol, isopropanol, butanols, acetone, methyl isobutyl ketone, dioxane , chloro or dibromomethane, optionally halogenated aliphatic hydrocarbons having from 2 to 10 carbon atoms, dimethylformamide, dimethylacetamide, dimethylsulfoxide etc ... Ethanol is the preferred diluent; in general the diluents must have a tension relatively low values at room temperature and be miscible with comonomers and possibly with water. Per 100 parts by weight of comonomers, preferably 1600 to 30 parts of diluent are used. The copolymer formed from the diluted alnε comonomers will be present in an at least monolecular layer on at least part of the internal surface of the pores.
Un initiateur de polymérisation radicalaire est ajouté dans le mélange de comonomères ; il ne doit pas causer de polymérisation sensible à température ambiante en l'absence de radiation activante (ultraviolet), mais causer une polymérisation des comonomères en un temps de préférence inférieur à 12 H, à une température inférieure à celle de ramollissement du polymère fluoré mis en oeuvre, et de préférence inférieure à 100 °C. On peut citer parmi les initiateurs de polymérisation les peroxydes de benzoyle, de lauroyle, de t-butyle, de cumyle, les peracétate ou perbenzoate de t-butyle ainsi que l'azobisisobutyronitrile.A radical polymerization initiator is added to the mixture of comonomers; it must not cause significant polymerization at room temperature in the absence of activating radiation (ultraviolet), but cause polymerization of the comonomers in a time preferably less than 12 h, at a temperature below that of softening of the fluorinated polymer put in use, and preferably less than 100 ° C. Mention may be made, among the polymerization initiators, of benzoyl, lauroyl, t-butyl, cumyl peroxides, t-butyl peracetate or perbenzoate and also azobisisobutyronitrile.
Les conditions de température de la polymérisation peuvent être adaptées au choix du diluant de façon à éviter son départ trop rapide au moment de la polymérisation in situ. On peut utiliser pour cela des activateurs, par exemple la diméthylaniline qui, associée au peroxyde de benzoyle, permet d'obtenir une polymérisation vers 40°C.The polymerization temperature conditions can be adapted to the choice of diluent so as to prevent it from leaving too quickly during the in situ polymerization. Activators can be used for this, for example dimethylaniline which, combined with benzoyl peroxide, makes it possible to obtain a polymerization around 40 ° C.
Le procédé de préparation de ces diaphragmes microporeux mouillables comprend donc dans sa première phase la préparation d'une feuille microporeuse. Parmi les procédés préférés pour ce faire, on peut citer ceux mettant en oeuvre des charges porophores tels que décrits dans les brevets français publiés sous les numéros 2.229.739 ; 2.280.435 ; 2.280.609 et 2.280.435 dont les descriptions sont incorporées ici par référence. Il est également possible d'introduire une charge porophore dans un latex de résine fluorée et notamment de polytétrafluoroéthylène contenant un agent plastifiant, 900 à 1200 et de préférence 400 à 900 parties en poids de porophores, 0,5 à 2 parties d'agent plastifiant et 1 à 20 parties d'eau étant ajouté dans 100 parties de résine d'un latex contenant 40 à 60 % en poids de matière sèche, de mélanger l'ensemble dans un malaxeur agité modérément c'est-à-dire dont le rotor tourne à moins de 100 tours/mn, de préformer par laminage une feuille à l'aide de la pâte obtenue, de la sécher puis de la fritter à une température de l'ordre du point de fusion du polymère mis en oeuvre. L'agent porophore qui est de préférence du carbonate de calcium est ensuite éliminé par immersion dans de l'acide qui est de préférence de l'acide acétique en solution aqueuse à 15-20 % en poids.The process for preparing these wettable microporous diaphragms therefore comprises in its first phase the preparation of a microporous sheet. Among the preferred methods for this, mention may be made of those employing porophoric fillers as described in the French patents published under the numbers 2.229.739; 2,280,435; 2,280,609 and 2,280,435, the descriptions of which are incorporated here by reference. It is also possible to introduce a porophore filler into a latex of fluorinated resin and in particular of polytetrafluoroethylene containing a plasticizing agent, 900 to 1200 and preferably 400 to 900 parts by weight of porophores, 0.5 to 2 parts of plasticizing agent and 1 to 20 parts of water being added to 100 parts of resin of a latex containing 40 to 60% by weight of dry matter, to mix the whole in a kneader moderately agitated, that is to say of which the rotor turns unless at 100 revolutions / min, to preform by rolling a sheet using the paste obtained, to dry it and then to sinter it at a temperature of the order of the melting point of the polymer used. The porophore agent which is preferably calcium carbonate is then removed by immersion in acid which is preferably acetic acid in aqueous solution at 15-20% by weight.
On peut aussi obtenir des feuilles poreuses, notamment dans le cas où le polymère fluoré mis en oeuvre est un copolymère d'éthylène et de chlorotrifluoroéthylène, ou un latex de PTFE, associé à des fibres minérales ou organiques (amiante, zircone, polyoléfines fibrillés) en dispersant le copolymère à raison de 5 à 50 % du poids de fibres dans de l'électrolyte, c'est-à-dire contenant environ 15 % de soude et 15 % de chlorure de sodium auquel on ajoute un agent tensio-actif.One can also obtain porous sheets, in particular in the case where the fluoropolymer used is a copolymer of ethylene and chlorotrifluoroethylene, or a PTFE latex, associated with mineral or organic fibers (asbestos, zirconia, fibrillated polyolefins) by dispersing the copolymer in an amount of 5 to 50% of the weight of fibers in the electrolyte, that is to say containing about 15% of sodium hydroxide and 15% of sodium chloride to which a surfactant is added.
Cette suspension est déposée sur une surface permettant la filtration ; cette surface peut être notamment une cathode perforée. Après essorage et séchage, la feuille formée lors de la filtration est chauffée jusqu'à 260°C température qui est maintenue de 30 mn à 1 heure.This suspension is deposited on a surface allowing filtration; this surface can in particular be a perforated cathode. After spinning and drying, the sheet formed during filtration is heated to 260 ° C temperature which is maintained from 30 min to 1 hour.
La feuille poreuse ainsi formée est ensuite imprégnée d'un mélange de comonomères et d'initiateur de polymérisation et, en général de diluant inerte. La proportion de diluant mentionnée plus haut doit être choisie en fonction de différents autres paramètres et en particulier, de la proportion du comonomère agent de la réticulation, notamment le divinylbenzène, par rapport aux acides carboxyliques insaturés et de la proportion d'initiateur de polymérisation notamment de peroxyde de benzoyle. La condition globale qui doit être respectée, et qui entraîne un choix dans la combinaison des divers autres paramètres, est que 0,1 à 6 % du volume poreux total, avant la copolymérisation in situ, de la feuille microporeuse-support, soient occupés par du copolymère carboxylique. La proportion pondérale divinylbenzène peut être comprise entre 2,5 et 25 parties pour 100 parties d'acide carboxylique insaturé. Il est bon également de ne mettre en oeuvre que de faibles quantités d'initiateur de polymérisation, par exemple, moins de 5 parties en poids de peroxyde de benzoyle pour 100 parties de comonomères et pas ou peu d'accélérateur de copolymérisation telle que la diméthylaniline (moins de 2 parties).The porous sheet thus formed is then impregnated with a mixture of comonomers and of polymerization initiator and, in general of inert diluent. The proportion of diluent mentioned above must be chosen according to various other parameters and in particular, the proportion of the crosslinking agent comonomer, in particular divinylbenzene, relative to the unsaturated carboxylic acids and the proportion of polymerization initiator in particular. benzoyl peroxide. The overall condition which must be respected, and which leads to a choice in the combination of the various other parameters, is that 0.1 to 6% of the total pore volume, before the in situ copolymerization, of the microporous support sheet, are occupied by of the carboxylic copolymer. The proportion by weight of divinylbenzene can be between 2.5 and 25 parts per 100 parts of unsaturated carboxylic acid. It is also good to use only small amounts of polymerization initiator, for example, less than 5 parts by weight of benzoyl peroxide per 100 parts of comonomers and little or no accelerator of copolymerization such as dimethylaniline (less than 2 parts).
Cette imprégnation peut se faire par exemple par immersion dans un bac contenant ce mélange liquide et filtration sous dépression de 10 à 100 mmHg.This impregnation can be done for example by immersion in a tank containing this liquid mixture and filtration under vacuum from 10 to 100 mmHg.
La feuille éventuellement sur son support, et notamment sur une cathode, est alors introduite dans une enceinte où la température, ou des rayons actiniques, notamment ultraviolets, permettent l'action des initiateurs de polymérisation. Elle peut être immergée dans un liquide, l'eau par exemple. Il importe que la température ne soit pas trop élevée, généralement inférieure à 150°C et ne modifie pas sensiblement la structure de la feuille microporeuse par départ trop rapide du diluant ou destruction du copolymère déposé. La durée de polymérisation (qui correspond environ à la durée de demi-vie de l'intiateur mis en oeuvre) est de préférence inférieure à 12 heures.The sheet optionally on its support, and in particular on a cathode, is then introduced into an enclosure where the temperature, or actinic rays, in particular ultraviolet rays, allow the action of the polymerization initiators. It can be immersed in a liquid, water for example. It is important that the temperature is not too high, generally less than 150 ° C. and does not substantially modify the structure of the microporous sheet by too rapid departure of the diluent or destruction of the deposited copolymer. The polymerization time (which corresponds approximately to the half-life of the initiator used) is preferably less than 12 hours.
Un moyen préféré de polymérisation est l'immersion dans de l'eau entre 40°C et 100°C.A preferred means of polymerization is immersion in water between 40 ° C and 100 ° C.
Le tableau I donné avec les exemples ci-après illustre clairement l'influence de divers facteurs tels que le porosité du diaphragme ou, ce qui en est directement la cause, la proportion d'agent porophore, le rapport pondéral entre les acides carboxyliques et les monomères non ioniques et la quantité de diluant ajouté sur la perte de charge de l'électrolyte à travers le diaphragme ou en d'autres termes sur la pression hydrostatique, dûe à l'anolyte, nécessaire pour assurer une percolation satisfaisante et sur la tension électrique dans la cellule. On verra aussi que les facteurs évoqués peuvent être choisis pour atteindre un but déterminé.Table I given with the examples below clearly illustrates the influence of various factors such as the porosity of the diaphragm or, which is directly the cause, the proportion of porophore agent, the weight ratio between the carboxylic acids and the non-ionic monomers and the amount of diluent added on the pressure drop of the electrolyte through the diaphragm or in other words on the hydrostatic pressure, due to the anolyte, necessary to ensure satisfactory percolation and on the electrical voltage in the cell. We will also see that the factors mentioned can be chosen to achieve a specific goal.
Des exemples de mise en oeuvre de l'invention sont donnés ci-après aux seules fins d'illustration de celle-ci.Examples of implementation of the invention are given below for the sole purpose of illustrating the latter.
On introduit dans 167 g de latex de polytétrafluoroéthylène à 60 % d'extrait sec, marque "SOREFLON", de la Société "Produits Chimiques Ugine Kuhlmann", 700 g de carbonate de calcium pulvérulent, appellation commerciale "CALIBRITE 1400" de la Société OMYA et 42 g de PEROLENE (PEROLENE S P Z) en solution aqueuse à 62 g/1.Is introduced into 167 g of polytetrafluoroethylene latex with 60% dry extract, brand "SOREFLON", from the company "Produits Chimiques Ugine Kuhlmann", 700 g of powdered calcium carbonate, trade name "CALIBRITE 1400" from the company OMYA and 42 g of PEROLENE (PEROLENE SPZ) in aqueous solution at 62 g / 1.
Le mélange est homogénéisé pendant 5 minutes dans un malaxeur de type WERNER dont les rotors en forme de Z tournent à une vitesse de 45 tours/mn.The mixture is homogenized for 5 minutes in a mixer WERNER type whose Z-shaped rotors rotate at a speed of 45 rpm.
La pâte obtenue est mise en feuille au moyen d'un mélangeur à cylindres de type LESCUYER. L'épaisseur est réduite à 1,2 mm La vitesse intiale de rotation des cylindres de 15 tours/mn est réduite progressivement à 5 tours/mn en 2 à 4 minutes.The dough obtained is put into sheets using a LESCUYER type roller mixer. The thickness is reduced to 1.2 mm. The initial speed of rotation of the cylinders by 15 rpm is gradually reduced to 5 rpm in 2 to 4 minutes.
La feuille ainsi formée est séchée 15 heures à 90°C puis 2 heures à 120°C et ensuite frittée dans un four à circulation d'air chaud dont la température est montée, à raison de 100°C/h, à 360°C où elle est maintenue 15 minutes.The sheet thus formed is dried for 15 hours at 90 ° C then 2 hours at 120 ° C and then sintered in a hot air circulation oven whose temperature has risen, at a rate of 100 ° C / h, to 360 ° C where it is kept for 15 minutes.
Le carbonate de calcium est éliminé par immersion pendant 72 heures dans une solution aqueuse d'acide acétique à 25 % en poids additionné de 2 g/1 d'agent .tensio-actif fluoré de marque "ZONYL F.S.N. de E-I Du Pont De Nemours Co."The calcium carbonate is eliminated by immersion for 72 hours in an aqueous solution of acetic acid at 25% by weight added with 2 g / 1 of fluorinated surfactant brand "ZONYL FSN from EI Du Pont De Nemours Co . "
Le diaphragme est alors rincé à l'eau puis immergé pendant 12 heures dans de l'éthanol.The diaphragm is then rinsed with water and then immersed for 12 hours in ethanol.
0n filtre ensuite à travers le diaphragme microporeux formé la solution ci-dessous, sous une dépression de 50 mm de mercure :
- - éthanol 330 parties
- - acide méthacrylique 100 parties
- - divinylbenzène commercial 10 parties
- - peroxyde de benzoyle 2 parties
- - ethanol 330 parts
- - 100 parts methacrylic acid
- - commercial divinylbenzene 10 parts
- - benzoyl peroxide 2 parts
Les parties mentionnées sont exprimées en poids.The parts mentioned are expressed by weight.
Le divinylbenzène commercial contient 45 % en poids d'éthylvinylbenzène et 55 % de divinylbenzène.Commercial divinylbenzene contains 45% by weight of ethylvinylbenzene and 55% of divinylbenzene.
On provoque la copolymérisation par immersion pendant 2 heures dans de l'eau à 80°C.The copolymerization is brought about by immersion for 2 hours in water at 80 ° C.
Ce diaphragme auquel a été conférée une mouillabilité remarquable, est conservé dans de l'eau jusqu'à son utilisation. Il est alors disposé, au contact d'une cathode, en fer tressé laminé de la Société "GANTOIS", d'une cellule d'électrolyse.This diaphragm, which has been given remarkable wettability, is kept in water until it is used. It is then placed, in contact with a cathode, in braided laminated iron from the company "GANTOIS", an electrolysis cell.
L'anode est en titane déployé revêtu d'alliage Pt-Ir.The anode is made of expanded titanium coated with Pt-Ir alloy.
La distance entre électrode est 5,5 mm ; elle est maintenue par un joint de caoutchouc.The distance between the electrodes is 5.5 mm; it is held in place by a rubber seal.
L'électrolyte introduit dans le compartiment anodique est une saumure à 300 g/1 de chlorure de sodium.The electrolyte introduced into the anode compartment is a brine containing 300 g / l of sodium chloride.
Après 200 heures de fonctionnement, les conditions de marche étant alors stables, la température est 85°C, la densite de courant est 25 A/dm2, la tension électrique est 3,35 V, la charge d'électrolyte est 40 cm. La soude du catholyte a une concentration de 123 g/l, le rendement faradique (ion OH) est 94 %.After 200 hours of operation, the operating conditions then being stable, the temperature is 85 ° C., the current density is 25 A / dm 2 , the electric voltage is 3.35 V, the electrolyte charge is 40 cm. The sodium hydroxide of the catholyte has a concentration of 123 g / l, the faradaic yield (OH ion) is 94%.
Un diaphragme microporeux préparé comme ci-dessus à l'exception du traitement par les comonomères acide carboxylique, monomères non ioniques qui ne lui est pas appliqué, est utilisé dans les mêmes conditions que celles de l'exemple 1.A microporous diaphragm prepared as above with the exception of the treatment with the carboxylic acid comonomers, nonionic monomers which is not applied to it, is used under the same conditions as those of Example 1.
Après 15 heures de fonctionnement, la tension monte à 4,0 V et la charge s'élève à 60 cm. Elle augmente ensuite très rapidement et l'électrolyse doit être arrêtée.After 15 hours of operation, the voltage rises to 4.0 V and the charge rises to 60 cm. It then increases very quickly and electrolysis must be stopped.
On reproduit l'essai de l'exemple 1 en faisant varier la quantité de carbonate de calcium et la proportion des comonomères de diluant et de peroxyde du mélange d'imprégnation.The test of Example 1 is repeated by varying the quantity of calcium carbonate and the proportion of the diluent and peroxide comonomers of the impregnation mixture.
Les diverses données sont mentionnées dans le tableau I dans lequel :
- - A.M = acide méthacrylique
- - DVB = mélange commercial à 55 % en poids de divinylbenzène et 45 % d'éthylvinylbenzène
- - PB = peroxyde de benzoyle.
- - AM = methacrylic acid
- - DVB = commercial mixture at 55% by weight of divinylbenzene and 45% of ethylvinylbenzene
- - PB = benzoyl peroxide.
Les résultats indiqués sont relevés après 200 heures de marche, sauf indication contraire.The results indicated are recorded after 200 hours of walking, unless otherwise indicated.
Les deux premiers essais témoins (1 et 2) ont dû être arrêtés après 25 heures qui est le temps où ont été effectuées les mesures de charge h et de tension U. Il en est de même de l'essai 235.The first two control tests (1 and 2) had to be stopped after 25 hours, which is the time when the load h and voltage U measurements were made. The same is true of test 235.
Les chiffres concernant les matières mises en oeuvre sont des parties en poids, celles de carbonates de calcium sont rapportées à 100 parties de polymère fluoré (sec).The figures concerning the materials used are parts by weight, those of calcium carbonates are related to 100 parts of fluoropolymer (dry).
La charge d'électrolyte R est la pression hydrostatique sur le diaphragme exprimée en cm ou la hauteur d'électrolyte de densité 1,2 environ, multipliée par ce dernier chiffre.The electrolyte charge R is the hydrostatic pressure on the diaphragm expressed in cm or the electrolyte height of density 1.2 approximately, multiplied by this last figure.
La quantité de NaOH est exprimée en gramme/litre.The amount of NaOH is expressed in grams / liter.
Le rendement R(OH)% est un rendement faradique calculé d'après la soude formée.The yield R (OH)% is a faradaic yield calculated from the sodium hydroxide formed.
T % est le pourcentage du volume poreux occupé par le polymère sec.
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT81400058T ATE24550T1 (en) | 1980-01-29 | 1981-01-19 | DIAPHRAGM FOR ELECTROLYSIS AND PROCESS FOR ITS MANUFACTURE. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8001843 | 1980-01-29 | ||
FR8001843 | 1980-01-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0033262A1 true EP0033262A1 (en) | 1981-08-05 |
EP0033262B1 EP0033262B1 (en) | 1986-12-30 |
Family
ID=9237978
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81400058A Expired EP0033262B1 (en) | 1980-01-29 | 1981-01-19 | Electrolysis diaphragm and method for its manufacture |
Country Status (6)
Country | Link |
---|---|
US (2) | US4341615A (en) |
EP (1) | EP0033262B1 (en) |
JP (1) | JPS5932550B2 (en) |
AT (1) | ATE24550T1 (en) |
CA (1) | CA1165276A (en) |
DE (1) | DE3175761D1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2505879A1 (en) * | 1981-05-15 | 1982-11-19 | Chloe Chemie | DIAPHRAGM, PROCESS FOR PREPARING THE SAME, AND ELECTROLYSIS METHOD FOR CARRYING OUT THE SAME |
US4647360A (en) * | 1985-10-04 | 1987-03-03 | The Dow Chemical Company | Inert carbon fiber diaphragm |
GB2181158A (en) * | 1985-10-08 | 1987-04-15 | Electricity Council | Electrolytic process for the manufacture of salts |
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US4505797A (en) * | 1983-03-24 | 1985-03-19 | Ionics, Incorporated | Ion-exchange membranes reinforced with non-woven carbon fibers |
JPS61130347A (en) * | 1984-11-30 | 1986-06-18 | Asahi Glass Co Ltd | Novel double-layered diaphragm for electrolysis |
US4689134A (en) * | 1985-04-18 | 1987-08-25 | Dorr-Oliver Inc. | Non ion selective membrane in an EAVF system |
US4879316A (en) * | 1987-02-26 | 1989-11-07 | The University Of Tennessee Research Corporation | Interpenetrating polymer network ion exchange membranes and method for preparing same |
US5152898A (en) * | 1989-10-23 | 1992-10-06 | Texaco Inc. | Separation of organic oxygenates |
US5196508A (en) * | 1991-04-11 | 1993-03-23 | Pall Corporation | Method for making uniform polyvinylidene difluoride membranes |
US5198505A (en) * | 1991-04-11 | 1993-03-30 | Pall Corporation | Uniform polyvinylidene difluoride membranes |
US5458719A (en) * | 1993-03-24 | 1995-10-17 | Pall Corporation | Method for bonding a porous medium to a substrate |
JP2999365B2 (en) * | 1994-05-10 | 2000-01-17 | 倉敷紡績株式会社 | Method for hydrophilizing porous body made of fluororesin |
USRE37307E1 (en) | 1994-11-14 | 2001-08-07 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
US5547551A (en) * | 1995-03-15 | 1996-08-20 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
US6254978B1 (en) | 1994-11-14 | 2001-07-03 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
USRE37701E1 (en) * | 1994-11-14 | 2002-05-14 | W. L. Gore & Associates, Inc. | Integral composite membrane |
US5599614A (en) * | 1995-03-15 | 1997-02-04 | W. L. Gore & Associates, Inc. | Integral composite membrane |
US6054230A (en) * | 1994-12-07 | 2000-04-25 | Japan Gore-Tex, Inc. | Ion exchange and electrode assembly for an electrochemical cell |
US6635384B2 (en) * | 1998-03-06 | 2003-10-21 | Gore Enterprise Holdings, Inc. | Solid electrolyte composite for electrochemical reaction apparatus |
US6689501B2 (en) | 2001-05-25 | 2004-02-10 | Ballard Power Systems Inc. | Composite ion exchange membrane for use in a fuel cell |
US6613203B1 (en) | 2001-09-10 | 2003-09-02 | Gore Enterprise Holdings | Ion conducting membrane having high hardness and dimensional stability |
GB2464014B (en) * | 2007-07-07 | 2012-07-04 | Itm Power Research Ltd | Electrolysis of salt water |
WO2011028998A1 (en) | 2009-09-03 | 2011-03-10 | E. I. Du Pont De Nemours And Company | Improved catalyst coated membranes having composite, thin membranes and thin cathodes for use in direct methanol fuel cells |
CN109415827B (en) * | 2016-06-27 | 2021-07-02 | 西门子股份公司 | Inorganic fiber reinforced gas separator for electrochemical conversion processes |
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US3694281A (en) * | 1969-04-28 | 1972-09-26 | Pullman Inc | Process for forming a diaphragm for use in an electrolytic cell |
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FR1371843A (en) * | 1963-06-25 | 1964-09-11 | Centre Nat Rech Scient | Improvements to semi-permeable membranes |
US3291632A (en) * | 1963-09-16 | 1966-12-13 | Pittsburgh Plate Glass Co | Method of preparing a membrane of divinyl benzene, styrene and maleic anhydride |
CA845032A (en) * | 1966-12-03 | 1970-06-23 | Hacker Heinz | Gas-tight diaphragms for electrochemical cells |
DE1959147C3 (en) | 1968-11-26 | 1979-12-06 | E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) | Fluorocarbon polymer surfactant article |
US3887499A (en) * | 1971-12-06 | 1975-06-03 | Ionics | Cation exchange membranes having carboxylic and sulfonic acid functionality |
US4007138A (en) * | 1972-05-25 | 1977-02-08 | Badische Anilin- & Soda-Fabrik Aktiengesellschaft | Manufacture of ion-exchanging shaped articles |
FR2250793B1 (en) * | 1973-11-09 | 1978-12-29 | Commissariat Energie Atomique | |
US4178218A (en) * | 1974-03-07 | 1979-12-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Cation exchange membrane and use thereof in the electrolysis of sodium chloride |
US4056447A (en) * | 1975-03-06 | 1977-11-01 | Oronzio De Nora Impianti Elettrochimici S.P.A. | Electrolyzing alkali metal chlorides using resin bonded asbestos diaphragm |
US4153520A (en) * | 1975-05-20 | 1979-05-08 | E. I. Du Pont De Nemours And Company | Method for the electrolytic production of chlorine from brine |
US4057481A (en) * | 1976-05-24 | 1977-11-08 | Allied Chemical Corporation | High performance, quality controlled bipolar membrane |
GB1538810A (en) * | 1976-08-10 | 1979-01-24 | Sumitomo Electric Industries | Hydrophilic porous fluorocarbon structures and process for their production |
JPS5329290A (en) * | 1976-08-31 | 1978-03-18 | Toyo Soda Mfg Co Ltd | Production of cation exchange membrane |
JPS5336643A (en) * | 1976-09-17 | 1978-04-05 | Fujikura Ltd | Method of producing battery separator |
US4262041A (en) * | 1978-02-02 | 1981-04-14 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Process for preparing a composite amphoteric ion exchange membrane |
IT1110461B (en) * | 1978-03-01 | 1985-12-23 | Oronzio De Nora Impianti | ANIONIC MEMBRANES CONSTITUTING COPOLYMERS OF (2) OR (4) -VINYLPYRIDINE WITH DIVINYLBENZENE OR WITH HALOGENATED VINYL MONOMERS |
EP0004237A1 (en) * | 1978-03-14 | 1979-09-19 | Elf Atochem S.A. | Ion exchange membranes; their preparation and their use in the electrolysis of sodium chloride |
US4243508A (en) * | 1979-04-26 | 1981-01-06 | Dankese Joseph P | Electrochemical apparatus |
US4255240A (en) * | 1979-06-04 | 1981-03-10 | E. I. Du Pont De Nemours And Company | Ion-exchange structures of copolymer blends |
US4292146A (en) * | 1979-08-07 | 1981-09-29 | Hooker Chemicals & Plastics Corp. | Porous polyfluoroalkylene sheet useful for separating anolyte from catholyte in electrolytic cells |
NZ195570A (en) * | 1979-12-28 | 1983-05-31 | Ici Australia Ltd | Cation exchange resin based on perhalogenated fluorine-containing polymer |
-
1981
- 1981-01-19 DE DE8181400058T patent/DE3175761D1/en not_active Expired
- 1981-01-19 AT AT81400058T patent/ATE24550T1/en not_active IP Right Cessation
- 1981-01-19 EP EP81400058A patent/EP0033262B1/en not_active Expired
- 1981-01-21 US US06/226,693 patent/US4341615A/en not_active Expired - Lifetime
- 1981-01-28 CA CA000369507A patent/CA1165276A/en not_active Expired
- 1981-01-29 JP JP56010906A patent/JPS5932550B2/en not_active Expired
-
1982
- 1982-05-14 US US06/378,075 patent/US4410638A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3694281A (en) * | 1969-04-28 | 1972-09-26 | Pullman Inc | Process for forming a diaphragm for use in an electrolytic cell |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2505879A1 (en) * | 1981-05-15 | 1982-11-19 | Chloe Chemie | DIAPHRAGM, PROCESS FOR PREPARING THE SAME, AND ELECTROLYSIS METHOD FOR CARRYING OUT THE SAME |
US4647360A (en) * | 1985-10-04 | 1987-03-03 | The Dow Chemical Company | Inert carbon fiber diaphragm |
GB2181158A (en) * | 1985-10-08 | 1987-04-15 | Electricity Council | Electrolytic process for the manufacture of salts |
GB2181158B (en) * | 1985-10-08 | 1989-11-15 | Electricity Council | Electrolytic process for the manufacture of salts |
Also Published As
Publication number | Publication date |
---|---|
JPS56152985A (en) | 1981-11-26 |
ATE24550T1 (en) | 1987-01-15 |
EP0033262B1 (en) | 1986-12-30 |
JPS5932550B2 (en) | 1984-08-09 |
CA1165276A (en) | 1984-04-10 |
DE3175761D1 (en) | 1987-02-05 |
US4410638A (en) | 1983-10-18 |
US4341615A (en) | 1982-07-27 |
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