CN103540951A - Ion exchange membrane for electrolysis of oxygen cathode and preparation method thereof - Google Patents
Ion exchange membrane for electrolysis of oxygen cathode and preparation method thereof Download PDFInfo
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- CN103540951A CN103540951A CN201310537577.1A CN201310537577A CN103540951A CN 103540951 A CN103540951 A CN 103540951A CN 201310537577 A CN201310537577 A CN 201310537577A CN 103540951 A CN103540951 A CN 103540951A
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- exchange membrane
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- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000001301 oxygen Substances 0.000 title claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 38
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000012528 membrane Substances 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 21
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 11
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 11
- 239000004744 fabric Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 210000004379 membrane Anatomy 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 16
- 230000007704 transition Effects 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 230000002708 enhancing effect Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 8
- 210000002469 basement membrane Anatomy 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 150000003460 sulfonic acids Chemical class 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 32
- 239000003513 alkali Substances 0.000 description 20
- 239000012266 salt solution Substances 0.000 description 16
- 239000011780 sodium chloride Substances 0.000 description 16
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003843 chloralkali process Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- XBGRTQUFSZKHJS-UHFFFAOYSA-N methyl 2-methylnon-8-enoate Chemical class COC(=O)C(C)CCCCCC=C XBGRTQUFSZKHJS-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 1
- TUFKHKZLBZWCAW-UHFFFAOYSA-N 2-(1-ethenoxypropan-2-yloxy)ethanesulfonyl fluoride Chemical compound C=COCC(C)OCCS(F)(=O)=O TUFKHKZLBZWCAW-UHFFFAOYSA-N 0.000 description 1
- HYWVMDJRPASBJK-UHFFFAOYSA-N COC(CCOC(COC=C)C)=O Chemical class COC(CCOC(COC=C)C)=O HYWVMDJRPASBJK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- PGXWDLGWMQIXDT-UHFFFAOYSA-N methylsulfinylmethane;hydrate Chemical compound O.CS(C)=O PGXWDLGWMQIXDT-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 perfluoroethylene-propylene Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention belongs to the technical field of polymer materials and specifically relates to an ion exchange membrane for electrolysis of an oxygen cathode and a preparation method thereof. The ion exchange membrane for electrolysis of the oxygen cathode is a multi-layer composite membrane comprising a perfluorosulfonic acid ion exchange resin layer, a perfluorocarboxylic acid ion exchange resin layer, a reinforcing mesh fabric, a hydrophilic coating and a multifunctional coating, wherein the thickness of the perfluorosulfonic acid resin layer is 80-150 mu m, the thickness of the perfluorocarboxylic acid resin layer is 8-15 mu m, the hydrophilic coating with the thickness of 3-12 mu m is coated on the surface on the anode side of the membrane, and the multifunctional coating with the thickness of 3-12 mu m is coated on the surface on the cathode side of the membrane. The preparation method comprises the following steps: spraying the carboxylic acid side of the ion membrane after transformation by using a dispersion solution containing perfluorosulfonic acid resin, a catalyst and a lower alcohol and drying to form the multifunctional coating. According to the preparation method provided by the invention, the surface of the ion membrane is endowed with a catalytic structure and the function, oxygen is in full contact with the surface of the ion membrane, and reaction is performed on the surface, so that the cell voltage is reduced and the catalytic efficiency is simultaneously improved.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of ion-exchange membrane for oxygen cathode electrolysis and preparation method thereof.
Background technology
Chlorine industry is produced caustic soda and chlorine by electrolysis brackish water, produces by product hydrogen simultaneously, is the basic chemical industry primary industry that occupies critical role in national economy.Current domestic soda processes is mainly ionic membrane method, and in production cost, power consumption cost accounts for 60%, therefore reduces power consumption and has very important significance for improving chlor-alkali industry economic benefit tool.Fundamentally, the huge current consumption of chlorine industry is to be determined by its chemical reaction itself.Therefore, fundamentally change the electrochemical reaction of electrolysis brackish water, thereby reduce theoretical decomposition voltage, can effectively realize the reduction of power consumption.
Electrode reaction and the electromotive force of the electrolysis of conventional ion film:
Anode: 2Cl
--2e → Cl
2↑
Negative electrode: 2H
2o+2e → H
2↑+2OH
- 
So traditional electrical solution theoretical decomposition voltage is poor is 1.36V-(0.83V)=2.19V.
As far back as the eighties in 20th century, U.S. EletechSystems company starts to utilize the principle of fuel cell gas diffusion electrode to prepare oxygen cathode type ion-exchange membrane electrolyzer.Its cathodic reaction is:
Negative electrode:
Therefore the theoretical decomposition voltage of oxygen cathode technique is poor, be 1.36V-0.40V=0.96V.
Theoretical decomposition voltage is poor: 2.19V-0.96V=1.23V, oxygen cathode technique can be energy-conservation more than 30% in theory, and (oxygen cathode technology has consumed oxygen certainly, and output H not
2).Ion film caustic soda film pole span technology ton alkali energy consumption is 2100kwh, and new oxygen cathode technology ton alkali energy consumption, lower than 1500kwh, receives the concern of chlor-alkali industry with the advantage of ton alkali economize on electricity 600kwh.Take that to produce 300000 tons of caustic soda projects per year be example, if all change oxygen cathode technology into, 1.8kwh every year can economize on electricity.World's chlor-alkali aggregated capacity has reached approximately 8,000 ten thousand tons, Chinese chlor-alkali aggregated capacity account for world's aggregated capacity near half, by this energy-saving effect, calculate, once this technology large-scale industrialization on market is promoted ，Jiang Dui world chlor-alkali general layout, produce great effect.
Current business-like for chlorine industry perfluorinated ion-exchange membrane (Membrane Used In Chlor-alkali Cell) be perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane, the anode side of film is that perfluorinated sulfonic acid layer, cathode side are perfluorocarboxylic acid layer.Sulphonic layer has higher ion and sees through ability, and is in 20%～30%, to have lower bath voltage at alkali concn, thereby can save significantly power consumption; And carboxylic layer can stop OH
-the infiltration migration of ion anode, guarantees higher current efficiency.
Yet, traditional Membrane Used In Chlor-alkali Cell is when for oxygen cathode chloralkali process, the defect that exists some to be difficult to overcome: oxygen can only react at catalysis electrode surface and the annex of electric groove, has increased to a certain extent reaction resistance, has improved bath voltage and has reduced catalytic efficiency simultaneously.
Summary of the invention
For solving the problems of the technologies described above, the present invention proposes a kind of have better catalytic performance and physical strength simultaneously, be applicable to perfluorinated ion-exchange membrane of oxygen cathode electrolysis process and preparation method thereof.
Technical scheme of the present invention is: for the ion-exchange membrane of oxygen cathode electrolysis, and the multilayer complex films that it is comprised of perfluorinated sulfonic acid resinbed, perfluorinated carboxylic acid ion-exchange resin's layer, enhancing screen cloth, hydrophilic coating and multi-functional coatings; Perfluorinated sulfonic resin bed thickness 80-150 micron wherein, perfluorinated carboxylic acid resin's layer is thick 8-15 micron, the hydrophilic coating of film anode side (sulfonic acid side) surface-coated 3-12 micron thick, the multi-functional coatings of film cathode side (carboxylic acid side) surface-coated 3-12 micron thick.
The basement membrane total thickness of described perfluorinated ion-exchange membrane between 90-189 micron, preferred 100-135 micron.
Described perfluorinated sulfonic acid resinbed, adopts current disclosed perfluorinated sulfonic resin material, preferably tetrafluoroethylene and perfluor sulfonyl base vinyl ether (as perfluor 3,6-dioxa-4-methyl-7-octene sulfonic acid fluoride, structural formula is: CF
2=CFOCF
2cF (CF
3) OCF
2cF
2sO
2f) perfluorinated sulfonic resin that copolymerization obtains, exchange capacity is 0.9-1.20mmo1/g.
Described perfluorinated carboxylic acid ion-exchange resin's layer, adopts current disclosed perfluorinated carboxylic acid resin's material, preferably tetrafluoroethylene and a small amount of perfluorocarboxylic acid ester vinyl ether (as perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters, structural formula is: CF
2=CFOCF
2cF (CF
3) OCF
2cF
2cOOCH
3) polymkeric substance that copolymerization forms, loading capacity is 0.9-1.05mmol/g.
Described enhancing screen cloth comprises fortifying fibre, fortifying fibre is selected from: tetrafluoroethylene (PTFE) fiber, perfluoroethylene-propylene fiber, Ion Exchange Fiber (CN101003588), one or more in poly-perfluoro propyl vinyl ether fiber, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fibre fluorocarbon polymer fiber.
Described hydrophilic coating is by be coated in dry forming after ion exchange resin membrane surface containing nano inorganic oxide-lower alcohol dispersion liquid of perfluorinated sulfonic resin, preferably ethanol or propyl alcohol of lower alcohol wherein, and nano inorganic oxide is ZrO preferably
2.
Described multi-functional coatings is by be coated in dry forming after ion exchange resin membrane surface containing nano inorganic oxide-catalyzer-lower alcohol dispersion liquid of perfluorinated sulfonic resin, wherein catalyzer is redox catalyst, preferably the nano-silver powder of particle diameter 10-60nm or silver-colored line; Lower alcohol is ethanol or propyl alcohol preferably, and nano inorganic oxide is ZrO preferably
2.The effect of multi-functional coatings is: hydrophilic, air release and catalysis.
Ion-exchange membrane for oxygen cathode electrolysis of the present invention, its preparation methods steps is as follows:
A, described perfluorinated carboxylic acid resin, the perfluorinated sulfonic resin of employing, prepare perfluorinated ion exchange resin basement membrane by melting co-extrusion or the compound technique of multi hot press;
Enhancing screen cloth is inserted to ion exchange fluoro resin membrane surface for b, employing continous vacuum recombining process or inner formation strengthens ionic membrane;
C, the enhancing ionic membrane of step b gained is hydrolyzed to 6-12 hour in the KOH of the massfraction 25% of 90 ℃ (or NaOH) water-organic solvent solution makes the transition;
D, with containing massfraction 3-10% perfluorinated sulfonic resin, 5-15% nano inorganic oxide-lower alcohol dispersion liquid, the ionic membrane sulfonic acid side after to transition sprays, form hydrophilic coating after dry;
E, with containing nano inorganic oxide-catalyzer-lower alcohol dispersion liquid (mass ratio (3-12): (1-10): (88-96)) of perfluorinated sulfonic resin, the ionic membrane carboxylic acid side after to transition sprays, form multi-functional coatings after dry;
F, spray complete film and be immersed in massfraction 0.2%-2% aqueous sodium hydroxide solution, after standing aging 2-24 hour, obtain oxygen cathode electrolysis ion-exchange membrane of the present invention.
In above-mentioned steps c, organic solvent is a kind of in ethanol, Virahol or DMSO.
In above-mentioned steps d and e, the preferred ZrO of nano inorganic oxide
2, a kind of in lower alcohol preferred alcohol, propyl alcohol and Virahol.
In above-mentioned steps e, catalyzer is redox catalyst, and the nano-silver powder of preferable particle size 10-60nm or diameter are 15～300nm, length 10～200 μ m silver lines.
Ion-exchange membrane for oxygen cathode electrolysis prepared by the present invention, can the Membrane Used In Chlor-alkali Cell electrolyzer for oxygen cathode electrolysis process on.
Beneficial effect of the present invention is: by catalytic structure and function endowing ionic membrane surface, keep ion film strength and thickness simultaneously.Like this, both can keep film strength and conductivity, can give again ionic membrane surface with catalytic performance, fully adapt to oxygen cathode chloralkali process.Oxygen and ionic membrane surface fully contacts and in its surface reaction, has reduced bath voltage and has improved catalytic efficiency simultaneously.
Embodiment
Below in conjunction with embodiment, illustrate the present invention.
Embodiment 1:
(1) preparation of resin granular material
Perfluorinated sulfonic resin is tetrafluoroethylene and perfluor 3, and 6-dioxa-4-methyl-7-octene sulfonic acid fluoride carries out the powder that in-situ polymerization obtains, and loading capacity is 0.95mmol/g.Tetrafluoroethylene and perfluor 4, the powder that the methyl-8-nonenoic acid methyl esters copolymerization of 7-dioxa-5 obtains, loading capacity is 0.95mmol/g.Perfluorinated sulfonic resin powder and perfluorinated carboxylic acid resin's powder obtain pellet separately through melt extruding granulation respectively.
(2) preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, perfluorinated sulfonic resin pellet, by melting coextrusion processes, prepare perfluorinated ion exchange resin basement membrane; Then adopt continous vacuum recombining process that PTFE is strengthened to screen cloth and insert the inner enhancing ionic membrane that forms of perfluorinated ion exchange resin basement membrane;
(3) transition of film and surface treatment
Step (2) gained ionic membrane is hydrolyzed to 6 hours in the massfraction 25%NaOH-water-aqueous isopropanol of 90 ℃ to make the transition; With containing massfraction 5% perfluorinated sulfonic resin, 10% nano inorganic oxide-alcohol dispersion liquid, the dried ionic membrane sulfonic acid side that makes the transition being sprayed, the dry rear air release coating that forms; By the silver powder-alcohol dispersion liquid containing massfraction 5% perfluorinated sulfonic resin, 7% particle diameter 15nm, the dried ionic membrane carboxylic acid side that makes the transition is sprayed the dry rear multi-functional coatings that forms; Spray complete film and be immersed in massfraction 0.2% aqueous sodium hydroxide solution, after standing aging 24 hours, obtain oxygen cathode electrolysis ion-exchange membrane of the present invention.
The ionic membrane tensile strength of embodiment 1 preparation is 35MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2the oxygen cathode condition of current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out under the condition of groove salt solution NaCl concentration 210g/L, 85～87 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 2.16-2.19V, current efficiency 97.5%.
Embodiment 2:
(1) preparation of resin granular material
Perfluorinated sulfonic resin is tetrafluoroethylene, R 1216 and perfluor 3, the powder that the copolymerization of 6-dioxa-4-methyl-7-octene sulfonic acid fluoride obtains, and loading capacity is 0.98mmol/g, resin powder is melt extruded to granulation and obtain the pellet containing perfluorinated sulfonic resin.Tetrafluoroethylene and perfluor 4, the powder that the methyl-8-nonenoic acid methyl esters copolymerization of 7-dioxa-5 obtains, loading capacity is 0.93mmol/g, obtains perfluorinated carboxylic acid resin's pellet through melt extruding granulation.
(2) preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, perfluorinated sulfonic resin pellet, by melt extruding, obtain respectively perfluorocarboxylic acid and perfluorinated sulfonic acid ion exchange resin membrane; Then adopt the compound screen cloth that again PTFE strengthened of multi hot press to insert the inner enhancing ionic membrane that forms of perfluorinated ion exchange resin basement membrane;
(3) transition of film and surface treatment
Step (2) gained enhancing ionic membrane is hydrolyzed to 12 hours in massfraction 25%KOH water-DMSO solution of 90 ℃ to make the transition; Respectively with contain massfraction 4% perfluorinated sulfonic resin, 8% nano inorganic oxide-alcohol dispersion liquid and make the transition dried ionic membrane sulfonic acid side and carboxylic acid side are sprayed, are dried containing long 10～25 μ m silver line-propanol dispersion liquors (mass ratio 6:8:86) of perfluorinated sulfonic resin-diameter 25nm simultaneously; Spray complete film and be immersed in 2% aqueous sodium hydroxide solution, after standing aging 4 hours, obtain oxygen cathode electrolysis ion-exchange membrane of the present invention.
The ionic membrane tensile strength of embodiment 2 preparations is 34MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 5.5kA/m
2the oxygen cathode condition of current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 205g/L, test under the condition of 85～87 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.26-2.32V, current efficiency 97.7%.
Embodiment 3:
Step (1), step (2) are identical with embodiment 1 with step (3), and the size distribution of different is nano-silver powder in step (1) is in 25-45 nanometer.
The ionic membrane tensile strength of embodiment 3 preparations is 33MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 5.5kA/m
2current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out under the condition of groove salt solution NaCl concentration 210g/L, 85～87 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 2.24-2.31V, current efficiency 96.7%.Embodiment 4:
Step (1), step (2) are identical with embodiment 1 with step (3), and different is in step (3), with containing massfraction 9% perfluorinated sulfonic resin, 8wt% nano inorganic oxide-alcohol dispersion liquid, the dried ionic membrane that makes the transition being carried out to double-face spray painting.
The ionic membrane tensile strength of embodiment 4 preparations is 32MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 5kA/m
2current density under, negative electrode NaOH liquid quality fraction 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 205g/L, test under the condition of 85～87 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.21-2.25V, current efficiency 96.8%.
Embodiment 5:
Step (1), step (2) are identical with embodiment 1 with step (3), and different is in step (1), and perfluorinated sulfonic resin loading capacity is that 1.15mmol/g, perfluorinated carboxylic acid resin's loading capacity are 0.99mmol/g.
The ionic membrane tensile strength of embodiment 5 preparations is 30MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.8kA/m
2current density under, negative electrode NaOH liquid quality fraction 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 210g/L, test under the condition of 86 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.18-2.21V, current efficiency 96.5%.
Embodiment 6:
Step (1), step (2) are identical with embodiment 2 with step (3), and different is in step (1), and perfluorinated sulfonic resin loading capacity is that 0.94mmol/g, perfluorinated carboxylic acid resin's loading capacity are 1.05mmol/g.
The ionic membrane tensile strength of embodiment 6 preparations is 32MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 5kA/m
2current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 205g/L, test under the condition of 85～87 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.19-2.24V, current efficiency 97.4%.
Embodiment 7:
Step (1), step (2) are identical with embodiment 2 with step (3), and different is in step (1), nano-silver thread diameter 55nm, long 30～180 μ m).
The ionic membrane tensile strength of embodiment 7 preparations is 35MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 205g/L, test under the condition of 85～87 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.12-2.14V, current efficiency 97.5%.Embodiment 8:
Step (1), step (2) are identical with embodiment 2 with step (3), and different is in step (3), and nano-silver thread is changed to particle diameter 30nm nano-silver powder and nano-silver thread (diameter 25nm, long 10～25 μ m) mixture (mass ratio 1:1).
The ionic membrane tensile strength of embodiment 8 preparations is 34MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 205g/L, test under the condition of 85～87 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.10-2.12V, current efficiency 97.6%.
Claims (10)
1. for an ion-exchange membrane for oxygen cathode electrolysis, it is characterized in that the multilayer complex films that it is comprised of perfluorinated sulfonic acid resinbed, perfluorinated carboxylic acid ion-exchange resin's layer, enhancing screen cloth, hydrophilic coating and multi-functional coatings; The basement membrane total thickness of wherein said perfluorinated ion-exchange membrane is between 90-189 micron, perfluorinated sulfonic resin bed thickness 80-150 micron, perfluorinated carboxylic acid resin's layer is thick 8-15 micron, film anode-side surface applies the hydrophilic coating of 3-12 micron thick, and film cathode-side surface applies the multi-functional coatings of 3-12 micron thick.
2. the ion-exchange membrane for oxygen cathode electrolysis according to claim 1; it is characterized in that; described perfluorinated sulfonic acid resinbed is the perfluorinated sulfonic resin that tetrafluoroethylene and the copolymerization of perfluor sulfonyl base vinyl ether obtain, and exchange capacity is 0.9-1.20mmo1/g.
3. the ion-exchange membrane for oxygen cathode electrolysis according to claim 1, it is characterized in that, described perfluorinated carboxylic acid ion-exchange resin's layer is the polymkeric substance that tetrafluoroethylene and the copolymerization of perfluorocarboxylic acid ester vinyl ether form, and loading capacity is 0.9-1.05mmol/g.
4. the ion-exchange membrane for oxygen cathode electrolysis according to claim 1, it is characterized in that, described hydrophilic coating is by be coated in dry forming after ion exchange resin membrane surface containing nano inorganic oxide-lower alcohol dispersion liquid of perfluorinated sulfonic resin, wherein lower alcohol is ethanol or propyl alcohol, and nano inorganic oxide is ZrO
2.
5. the ion-exchange membrane for oxygen cathode electrolysis according to claim 1, it is characterized in that, described multi-functional coatings is by be coated in dry forming after ion exchange resin membrane surface containing nano inorganic oxide-catalyzer-lower alcohol dispersion liquid of perfluorinated sulfonic resin.
6. the ion-exchange membrane for oxygen cathode electrolysis according to claim 5, it is characterized in that, the described mass ratio containing three kinds of materials in nano inorganic oxide-catalyzer-lower alcohol dispersion liquid of perfluorinated sulfonic resin is: the nano inorganic oxide that contains perfluorinated sulfonic resin: catalyzer; Lower alcohol=(3-12): (1-10): (88-96).
7. the ion-exchange membrane for oxygen cathode electrolysis according to claim 5, is characterized in that, described catalyzer is redox catalyst, and the nano-silver powder of 10-60nm or diameter are 15～300nm, length 10～200 μ m silver lines; Lower alcohol is ethanol or propyl alcohol, and nano inorganic oxide is ZrO
2.
8. according to the ion-exchange membrane for oxygen cathode electrolysis described in claim 1-7 any one, its preparation method is: a, described perfluorinated carboxylic acid resin, the perfluorinated sulfonic resin of employing, by melting co-extrusion or the compound technique of multi hot press, prepare perfluorinated ion exchange resin basement membrane;
Enhancing screen cloth is inserted to ion exchange fluoro resin membrane surface for b, employing continous vacuum recombining process or inner formation strengthens ionic membrane;
C, the enhancing ionic membrane of step b gained is hydrolyzed to 6-12 hour in the KOH of the massfraction 25% of 90 ℃ (or NaOH) water-organic solvent solution makes the transition;
D, with containing massfraction 3-10% perfluorinated sulfonic resin, 5-15% nano inorganic oxide-lower alcohol dispersion liquid, the ionic membrane sulfonic acid side after to transition sprays, form hydrophilic coating after dry;
E, with containing nano inorganic oxide-catalyzer-lower alcohol dispersion liquid of perfluorinated sulfonic resin, the ionic membrane carboxylic acid side after to transition sprays, form multi-functional coatings after dry;
F, spray complete film and be immersed in massfraction 0.2%-2% aqueous sodium hydroxide solution, after standing aging 2-24 hour, obtain oxygen cathode electrolysis ion-exchange membrane of the present invention.
9. the preparation method of the ion-exchange membrane for oxygen cathode electrolysis according to claim 8, is characterized in that: in described step c, organic solvent is a kind of in ethanol, Virahol or DMSO.
10. the preparation method of the ion-exchange membrane for oxygen cathode electrolysis according to claim 8, it is characterized in that: in described step e, the mass ratio that contains three kinds of materials in nano inorganic oxide-catalyzer-lower alcohol dispersion liquid of perfluorinated sulfonic resin is: the nano inorganic oxide that contains perfluorinated sulfonic resin: catalyzer; Lower alcohol=(3-12): (1-10): (88-96).
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