SU1165239A3 - Electrolytic cell for chloralkali electrolysis - Google Patents

Electrolytic cell for chloralkali electrolysis Download PDF

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Publication number
SU1165239A3
SU1165239A3 SU782605603A SU2605603A SU1165239A3 SU 1165239 A3 SU1165239 A3 SU 1165239A3 SU 782605603 A SU782605603 A SU 782605603A SU 2605603 A SU2605603 A SU 2605603A SU 1165239 A3 SU1165239 A3 SU 1165239A3
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SU
USSR - Soviet Union
Prior art keywords
electrolytic cell
copolymer
perfluorinated
methyl
layer
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Application number
SU782605603A
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Russian (ru)
Inventor
Чарльз Инглэнд Дэвид
Рафаэль Резник Пол
Original Assignee
Е.И.Дюпон Де Немур Энд Компани (Фирма)
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/14—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Abstract

ЭЛЕКТРОЛИТИЧЕСКАЯ ЯЧЕЙКА ДЛЯ ХЛОРЩЕЛОЧНОГО ЭЛЕКТРОЛИЗА, содержаща  корпус, именмций анодный и катодный участки, разделенные диафрагмой , выполненной из многослойной мембраны, в которой по меньшей мере один слой образован перфторированным ионообменным сополимером с боковыми группами CFjCF-jSOjM, где М - Na или К, и один слой на поверхности - перфторированным карбоксилсодержащим сополимером , отличающа с  тем, что, с целью увеличени  долговечности электролитической  чейки, перфторированный карбоксилсодержащий сополимер представл ет собой гйдролизо- ванный сополимер метил-перфтор-ELECTROLYTIC CELL FOR CHLORESHINE ELECTROLYSIS a layer on the surface is a perfluorinated carboxyl-containing copolymer, characterized in that, in order to increase the durability of the electrolytic cell, the perfluorinated carboxyl-containing copolymer is oh gydrolizo- vanny copolymer of perfluoro-methyl

Description

Изобретение относитс  к технологии получени  ионообменных мембран и может быть использовано в электрохимической промышленности, в частности в электролитических процессах получени  щелочи и хлора. Широкое распространение в качестве материала дл  диафрагм электролитических  чеек, предназначенных дл  хлорщелочного электролиза, получили перфторированные ионообменные полимеры . Достоинством этих полимеров  вл етс  высока  химическа  устойчивость к агрессивным средам. Известна электролитическа   чейка дл  хлорщелочного электролиза, в которой материалом дл  диафрагмы служит перфтррированный сополимер с сульфонамидными или сульфонатными группами ij . Использование указанной мембраны в процессе электролиза позвол ет достичь КПД по току 93-96%. Однако в процессе работы свойства мембраны быстро ухудшаютс , в результате чего резко снижаетс  эффективность до ток Наиболее близкой к предлагаемой  вл етс  электролитическа   чейка дл  хлорщелочного электролиза, соде жаща  корпус с анодными и катодными участками, разделенными диафрагмой, вьшолненной из многослойной мембраHisi , в которой по меньшей мере один слой образован перфторированным ион обменным сополимером с боковыми группами -CFjCFjSO M,где М представ л ет собой атом натри  или кали , и один слой на поверхности - перфторн ррванным сополимером с группами OCFjCOOM При использовании известной  чей ки в пр0цессе получени  галогена КПД по току составл ет 93-97%, при концентрации щелочи в катодном пространстве до 40%. Недостатком известной электролитической  чейки  вл етс  ее недолговечность из-за невысокой механической прочности мембраны. Цель изобретени  - увеличение долговечности электролитической  чейки. Дл  достижени  цели в электролитическдй  чейке дл  хлорщелочного электролиза, содержащей корпус, имеющий анодный и катодный участки, разделенные диафрагмой, вьтолненной из многослойной мембраны, в которой 92 по меньшей мере один слой образован перфторированным ионообменным сополиметром с боковыми группами -СРгСР ЗОдМ, где М -Na или К, и один слой на поверхности - перфторированньп«1 карбоксилсодержащим сополимером , перфторированный карбоксилсодержащий сополимер представл ет собой гидролизованный сополимер метил-перфтор-(4,7-диокса-5-метил-8-ноненоата ) и тетрафторэтилена, содержащий группы OCFjCFgCOOM, где М - Na или К, с эквивалентной массой 900-1100. Сополимеры согласно изобретению могут быть получены сополимеризацией смеси соответствующих мономеров, конкретно сополимеризацией метилового эфира перфтор-4,7-диоксана-5-метил-8-ноненовой кислоты и тетрафторэтилена с образованием карбоксилсодержащего сополимера и сополимеризующей перфтор-3,6-диокса-4-метил-7- октан-сульфонилфторида и тетрафторэтилена с образованием сульфополимера . При использовании пленок сополимеров согласно изобретению в качестве диафрагм электролитической  чейки необходимо, чтобы эквивалентный вес (ЭВ) карбоксильного сополимера не превьппал 1500. Увеличение ЭВ ведет к возрастанию сопротивлени  мембраны и ухудшению эксплуатационных свойств  чейки. Сополим(ры согласно изобретению могут быть получены известными методами полимеризации, в частности радикальной полимеризацией в присутствии инициаторов свободно-радикаль-д ного типа в среде фторированного растворител  или воды. Мембраны на основе указанных сополимеров представл ют собой многослойные пленочные структуры с толщиной 0,050 ,5 мм. Пример t. Пленку сополимера тетрафторэтилена и перфтор-3,6-диокса-4-метил-7-октенсульфонилфторида , имеющего ЭВ 1100, толщиной 0,127 мм помещают в пресс и покрывают одну поверхность 1 г порошка сополимера тетрафторэтилена и метилового эфира перфтор-4,7-диокса-5-метил-8-ноненовой кислоты с ЭВ 900. Материал выдерживают в течение 4 мин при без давлени  и 2 мин при при давлении 2120 кгс/см. Полученную мембрану обрабатываютThe invention relates to the technology of obtaining ion-exchange membranes and can be used in the electrochemical industry, in particular in electrolytic processes for the preparation of alkali and chlorine. Perfluorinated ion-exchange polymers are widely used as material for diaphragms of electrolytic cells for chlor-alkali electrolysis. The advantage of these polymers is their high chemical resistance to aggressive media. A known electrolytic cell for chlor-alkali electrolysis, in which the perforated polymer with sulfonamide or sulfonate groups ij serves as the material for the diaphragm. The use of this membrane in the electrolysis process allows an efficiency of 93-96% to be achieved. However, during operation, the properties of the membrane deteriorate rapidly, resulting in a sharp decrease in efficiency until the current. The electrolytic cell for chlor-alkali electrolysis is closest to the proposed one, containing a housing with anodic and cathodic regions separated by a diaphragm made from a hisi multilayer membrane. At least one layer is formed by a perfluorinated ion exchange copolymer with side groups -CFjCFjSO M, where M is a sodium or potassium atom, and one layer on the surface is perfluoro-dispersed copolymer with OCFjCOOM groups When using known ki in the process of producing halogen, the current efficiency is 93-97%, with an alkali concentration in the cathode space of up to 40%. A disadvantage of the known electrolytic cell is its fragility due to the low mechanical strength of the membrane. The purpose of the invention is to increase the durability of the electrolytic cell. To achieve the goal in an electrolytic cell for chlor-alkali electrolysis, there is a body having an anode and cathode areas separated by a diaphragm filled from a multi-layer membrane, in which 92 at least one layer is formed by a perfluorinated ion-exchange copolymeter with side groups -SRGSR ZODM, where M is M-SRCPR ZODM, where M is M-X-ray. or K, and one layer on the surface - perfluorinated " 1 carboxyl-containing copolymer, the perfluorinated carboxyl-containing copolymer is a hydrolyzed methyl perfluoro- (4,7-dioxa-5-me) copolymer yl-8-nonenoata) and tetrafluoroethylene containing OCFjCFgCOOM groups, where M - Na or K having an equivalent weight of 900-1100. The copolymers according to the invention can be obtained by copolymerizing a mixture of the corresponding monomers, specifically by copolymerizing perfluoro-4,7-dioxane-5-methyl-8-nonenoic acid methyl ester and tetrafluoroethylene to form a carboxyl-containing copolymer and copolymerizing perfluoro-3,6-dioxa-4-methyl -7- octane-sulfonyl fluoride and tetrafluoroethylene to form a sulfopolymer. When using the copolymer films of the invention as diaphragms of an electrolytic cell, it is necessary that the equivalent weight (EV) of the carboxyl copolymer does not exceed 1500. An increase in EV leads to an increase in membrane resistance and a deterioration in the performance properties of the cell. Copolyme (ry according to the invention can be obtained by known methods of polymerization, in particular radical polymerization in the presence of free radical initiators of the type in a fluorinated solvent or water. Membranes based on these copolymers are multilayer film structures with a thickness of 0.050, 5 mm Example t. A film of a copolymer of tetrafluoroethylene and perfluoro-3,6-diox-4-methyl-7-octenesulfonyl fluoride, having an EV of 1100, is 0.127 mm thick, placed in a press and coated with one surface 1 g of powder copolymer and tetrafluoroethylene and methyl perfluoro-4,7-dioxa-5-methyl-8-nonenoic acid with EV 900. The material is kept for 4 minutes at no pressure and 2 minutes at a pressure of 2120 kgf / cm. The resulting membrane is treated

Claims (1)

ЭЛЕКТРОЛИТИЧЕСКАЯ ЯЧЕЙКА ДЛЯ ХЛОРЩЕЛОЧНОГО ЭЛЕКТРОЛИЗА, содержащая корпус, имеющий анодный и ка- тодный участки, разделенные диафрагмой, выполненной из многослойной мембраны, в которой по меньшей мере один слой образован перфторированным ионообменным сополимером с боковыми группами CF2CF2S03M, где М - Na или К, и один слой на поверхности - перфторированным карбоксилеодержащим сополимером, отличающаяся тем, что, с целью увеличения долговечности электролитической ячейки, перфторированный карбоксилсодержащий сополимер представляет собой гидролизованный сополимер метил-перфтор-(4,7-диокса-5-метил-8-ноненоата) и тетрафторэтилена, содержащий группы &ELECTROLYTIC CELL FOR CHLOROCHALIC ELECTROLYSIS, comprising a housing having anode and cathode sections separated by a diaphragm made of a multilayer membrane in which at least one layer is formed by a perfluorinated ion-exchange copolymer with side groups CF 2 CF 2 S0 3 M, where M is Na or K, and one layer on the surface of a perfluorinated carboxy-containing copolymer, characterized in that, in order to increase the durability of the electrolytic cell, the perfluorinated carboxy-containing copolymer is g drolizovanny copolymer of methyl perfluoro (4,7-dioxa-5-methyl-8-nonenoata) and tetrafluoroethylene containing Group & OCF2CF2COOM, где М - Na или К, с эквивалентной массой 900-1100.OCF 2 CF 2 COOM, where M is Na or K, with an equivalent weight of 900-1100. 1 1652391 165239
SU782605603A 1977-04-20 1978-04-19 Electrolytic cell for chloralkali electrolysis SU1165239A3 (en)

Applications Claiming Priority (1)

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US78972577A 1977-04-20 1977-04-20

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SU1165239A3 true SU1165239A3 (en) 1985-06-30

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JP (2) JPS53132089A (en)
AU (2) AU525335B2 (en)
BE (1) BE866121A (en)
BR (1) BR7802433A (en)
CA (1) CA1133425A (en)
DE (1) DE2817344A1 (en)
FR (1) FR2388012A1 (en)
GB (1) GB1604102A (en)
IL (1) IL54540A (en)
IT (1) IT1094102B (en)
MX (1) MX151031A (en)
NL (1) NL7804221A (en)
NZ (1) NZ187023A (en)
SU (1) SU1165239A3 (en)
ZA (1) ZA782225B (en)

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JPS5792028A (en) * 1980-11-29 1982-06-08 Asahi Chem Ind Co Ltd Fluorocarbon cation exchange membrane
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US7071271B2 (en) * 2003-10-30 2006-07-04 3M Innovative Properties Company Aqueous emulsion polymerization of functionalized fluoromonomers
WO2010066823A1 (en) * 2008-12-11 2010-06-17 Solvay Solexis S.P.A. Purification of fluoroionomer compositions
JP5799926B2 (en) * 2012-09-27 2015-10-28 旭硝子株式会社 Method for producing fluorine-containing copolymer

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IL54540A0 (en) 1978-07-31
BR7802433A (en) 1979-01-16
CA1133425A (en) 1982-10-12
ZA782225B (en) 1979-04-25
NL7804221A (en) 1978-10-24
BE866121A (en) 1978-10-19
MX151031A (en) 1984-09-12
AU3516478A (en) 1979-10-25
DE2817344A1 (en) 1978-10-26
IL54540A (en) 1981-09-13
AU525335B2 (en) 1982-11-04
NZ187023A (en) 1980-11-28
GB1604102A (en) 1981-12-02
DE2817344C2 (en) 1990-11-15
FR2388012A1 (en) 1978-11-17
JPS53132089A (en) 1978-11-17
JPS59211583A (en) 1984-11-30
IT7822494A0 (en) 1978-04-19
JPS6356257B2 (en) 1988-11-07
IT1094102B (en) 1985-07-26
AU1304888A (en) 1988-06-16

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