CN103556178B - For the ion-exchange membrane and preparation method thereof of superhigh-current-density oxygen cathode electrolysis - Google Patents
For the ion-exchange membrane and preparation method thereof of superhigh-current-density oxygen cathode electrolysis Download PDFInfo
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Abstract
The present invention relates to a kind of ion-exchange membrane for the electrolysis of superhigh-current-density oxygen cathode and preparation method thereof.This ion-exchange membrane by perfluorinated carboxylic acid ion-exchange resin's layer, carbon nanotubes perfluorosulfonic acid ion exchange resin layer, strengthen the multilayer complex films that forms of screen cloth, sulfonic acid side air release coating and carboxylic acid side multi-functional coatings; The basement membrane total thickness of above-mentioned perfluorinated ion-exchange membrane is between 90-180 micron, and wherein perfluorinated sulfonic resin thickness 80-160 micron, perfluorinated carboxylic acid resin thickness 8-16 micron, film both side surface coat-thickness is all at 3-12 micron.This film can be prepared by the technique of melting coextrusion or multi hot press compound.This film is used for oxygen cathode electrolysis process, especially adopts the ion exchange membrane production of caustic soda of the oxygen cathode electrolysis process of superhigh-current-density, has good mechanical property and chemical property.
Description
Technical field
The invention belongs to macromolecular material and electrochemical field, particularly relate to a kind of ion-exchange membrane for superhigh-current-density oxygen cathode electrolysis process and preparation method thereof.
Background technology
Chlorine industry produces caustic soda and chlorine by electrolysis brackish water, and produce byproduct hydrogen gas, be the basic chemical industry primary industry occupying critical role in national economy simultaneously.Current domestic soda processes mainly ionic membrane method, in production cost, power consumption cost accounts for 60%, therefore reduces power consumption and has very important significance for raising chlor-alkali industry economic benefit tool.Fundamentally, the huge current consumption of chlorine industry determined by its chemical reaction itself.Therefore, fundamentally change the electrochemical reaction of electrolysis brackish water, thus reduce theoretical decomposition voltage, effectively can realize the reduction of power consumption.
The electrode reaction of conventional ion film electrolysis and electromotive force:
Anode: 2Cl
--2e → Cl
2↑
Negative electrode: 2H
2o+2e → H
2↑+2OH
-
So traditional electrolyte theoretical decomposition voltage difference is 1.36V-(-0.83V)=2.19V.
As far back as the eighties in 20th century, EletechSystems company of the U.S. 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 difference is 1.36V-0.40V=0.96V.
Theoretical decomposition voltage is poor: 2.19V-0.96V=1.23V, and oxygen cathode technique can energy-conservation more than 30% (certain oxygen cathode technology consumes oxygen, and not output H in theory
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.To produce 300000 tons of caustic soda projects per year, if all change oxygen cathode technology into, can economize on electricity 1.8 hundred million kWh every year.World's chlor-alkali aggregated capacity has reached about 8,000 ten thousand tons, and Chinese chlor-alkali aggregated capacity accounts for the nearly half of world's aggregated capacity, calculates by this energy-saving effect, and this technology, once commercially industrialization large-scale promotion, will produce great effect to world's chlor-alkali general layout.
Current business-like chlorine industry perfluorinated ion-exchange membrane (Membrane Used In Chlor-alkali Cell) is perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane, and namely the anode side of film is perfluorinated sulfonic acid layer, cathode side is perfluorocarboxylic acid layer.Sulphonic layer has higher ion permeable ability, and is have lower bath voltage in 20% ~ 30% at alkali concn, thus can save power consumption significantly; And carboxylic layer can stop OH
-the infiltration migration of ion anode, ensures higher current efficiency.In order to improve film strength, also can insert fortifying fibre screen cloth in existing perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane, such as CN101716472A provides a kind of fibre-reinforced ion-exchange membrane.But, traditional Membrane Used In Chlor-alkali Cell is when for oxygen cathode chloralkali process, there is the defect that some are difficult to overcome: because film itself does not have catalysis, even if oxygen is on ionic membrane surface, fully contact also can not in its surface reaction, and can only react at the catalytic electrode surface of electric groove and annex, this adds reaction resistance to a certain extent, improves bath voltage and reduces catalytic efficiency simultaneously.Especially, when the current density of chlorine industry electrolysis process is more and more higher, exploitation is applicable to superhigh-current-density (6-8kA/m
2even higher) the chlor-alkali film of electrolysis process is imperative.
Summary of the invention
For the deficiency having now technology, the invention provides a kind of fiber reinforcement ion-exchange membrane simultaneously with better catalytic performance and physical strength and preparation method thereof, is the perfluorinated ion-exchange membrane being applicable to superhigh-current-density oxygen cathode electrolysis process.
Term illustrates:
Superhigh-current-density: refer to 6-8kA/m
2even higher current density condition.
Perfluorosulfonic acid ion exchange resin layer: the anode side being perfluorinated ion-exchange membrane, also claims sulfonic acid side;
Perfluorinated carboxylic acid ion-exchange resin's layer: the cathode side being perfluorinated ion-exchange membrane, also claims carboxylic acid side;
Perfluorosulfonic acid ion exchange resin layer and perfluorinated carboxylic acid ion-exchange resin's layer are the major portions forming perfluorinated ion-exchange membrane basement membrane.
The model of carbon nanotube: carbon nanotube has armchair (Armchair type), prionodont (Zigzag type) and other chirality types, by diameter, the helicity of carbon nanotube, usual use (n, m) index represents the model of (general n >=m) carbon nanotube, concrete meaning is shown in the works " carbon nanotube " such as Zhu Hongwei, China Machine Press, 2003, p60.
Technical scheme of the present invention is as follows:
For a perfluorinated ion-exchange membrane for superhigh-current-density oxygen cathode electrolysis, the composite membrane that the second layer of the first layer of this ion-exchange membrane by perfluorinated carboxylic acid ion-exchange resin, perfluorosulfonic acid ion exchange resin containing carbon nanotube, fortifying fibre screen cloth, air release coating, multi-functional coatings form; Wherein, described the first layer and the second layer are complex as basement membrane, and fortifying fibre screen cloth inserts described membrane surface or inside;
Described air release coating is coated on described second layer surface, and thickness is 3-12 micron;
Described multi-functional coatings is formed in described the first layer surface by the C1-C3 lower alcohol dispersion containing perfluorinated sulfonic resin, redox catalyst, and thickness is 3-12 micron.
Preferred according to the present invention, described the first layer (carboxylic layer) thickness is 80-160 micron, and the described second layer (sulphonic layer) thickness is 8-16 micron; And described basement membrane total thickness is 90-180 micron, preferably basement membrane total thickness is 100-135 micron further.
Preferred according to the present invention, described carbon nanotube is selected from one or more in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, the carbon nanotube fluoridized.In perfluorosulfonic acid ion exchange resin containing carbon nanotube, the content of carbon nanotube is 0.1 ~ 10wt%.Carbon nanotube diameter 0.72-3.2 nanometer.The carbon nanotube in this aperture is significant for the ionic flux and water flux improving ion-exchange membrane.
Preferred according to the present invention, described air release coating is by containing the nano inorganic oxide of perfluorinated sulfonic resin and the dispersion of C1-C3 lower alcohol, drying behind the described second layer (sulphonic layer) surface forms.In the dispersion liquid of this lower alcohol, the perfluorinated sulfonic resin containing 3-10wt%, the nano inorganic oxide of 5-15wt%.Wherein, described perfluorinated sulfonic resin is identical with the perfluorinated sulfonic resin of the second layer, and C1-C3 lower alcohol is preferably ethanol or propyl alcohol, and described nano inorganic oxide is preferably zirconium white (ZrO
2) nano powder, titanium dioxide (TiO
2) nano powder or aluminum oxide (Al
2o
3) one in nano powder or its mixture.
Preferred according to the present invention, described multi-functional coatings is formed by the drying behind described the first layer (carboxylic layer) surface of the dispersion of the C1-C3 lower alcohol containing perfluorinated sulfonic resin and redox catalyst.Wherein, described perfluorinated sulfonic resin is identical with the perfluorinated sulfonic resin of the second layer, and described redox catalyst is the silver-colored line of the nano-silver powder of particle diameter 10-60nm or 15 ~ 300nm, length 10 ~ 200 μm, and C1-C3 lower alcohol is ethanol, propyl alcohol or Virahol.
Perfluorinated sulfonic resin of the present invention, perfluorinated carboxylic acid resin, fortifying fibre screen cloth all adopt state of the art.Such as,
Above-mentioned perfluorinated sulfonic resin, (as perfluor 3,6-dioxa-4-methyl-7-octene sulfonyl fluoride, structural formula is CF for preferred tetrafluoroethylene and/or R 1216 and perfluor sulfonyl base vinyl ether
2=CFOCF
2cF (CF
3) OCF
2cF
2sO
2f) perfluorinated sulfonic resin that obtains of copolymerization, exchange capacity is 0.91-1.20mmo1/g.
Above-mentioned perfluorinated carboxylic acid resin, (as perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters, structural formula is CF for preferred tetrafluoroethylene and perfluorocarboxylic acid ester vinyl ether
2=CFOCF
2cF (CF
3) OCF
2cF
2cOOCH
3) polymkeric substance of copolymerization, loading capacity is 0.9-1.10mmo1/g.
Above-mentioned fortifying fibre is selected from Ion Exchange Fiber disclosed in tetrafluoroethylene (PTFE) fiber, perfluoroethylene-propylene fiber, CN101003588A, gathers one or more in perfluoro propyl vinyl ether fiber, tetrafluoroethylene-perfluoro vinyl ether co-polymer fiber fluorocarbon polymer fiber.
According to the present invention, a kind of preparation method of the fiber reinforcement perfluorinated ion-exchange membrane for the electrolysis of superhigh-current-density oxygen cathode, comprises step as follows:
A, adopt described in perfluorinated carboxylic acid resin, carbon nanotubes perfluorinated sulfonic resin, prepare perfluorinated ion exchange resin basement membrane by the technique of melting co-extrusion or multi hot press compound;
Enhancing screen cloth is inserted ion exchange fluoro resin membrane surface or inner formation enhancing ionic membrane by b, employing continous vacuum recombining process;
C, the enhancing ionic membrane of step b gained is hydrolyzed 6-12 hour in the water-organic solvent solution of KOH or NaOH of the massfraction 25% of 90 DEG C makes the transition;
D, with the C1-C3 lower alcohol dispersion liquid containing massfraction 3-10% perfluorinated sulfonic resin, 5-15% nano inorganic oxide, the sulphonic layer surface of ionic membrane after transition to be sprayed, after dry, form air release coating;
E, use spray the ionic membrane carboxylic layer surface after transition containing the dispersion liquid of perfluorinated sulfonic resin, redox catalyst, C1-C3 lower alcohol, form multi-functional coatings after drying; Described perfluorinated sulfonic resin: redox catalyst: the mass ratio of C1-C3 lower alcohol is (3-12): (1-10): (88-96);
After f, spraying, film is immersed in massfraction 0.2%-2% aqueous sodium hydroxide solution, leaves standstill aging 2-24 hour, obtain the fiber reinforcement ion-exchange membrane for superhigh-current-density oxygen cathode electrolysis process of the present invention.
Preferably, in above-mentioned steps a, the perfluorinated sulfonic resin of carbon nanotubes, it is carbon nanotube and the perfluorinated sulfonic resin comonomer powder through in-situ polymerization, or by melt extruding the perfluorinated sulfonic resin master batch obtained after carbon nanotube mixes with perfluorinated sulfonic resin, carbon nanotube mass content is 0.1% ~ 10%, preferably 3 ~ 6wt%; Described carbon nanotube is selected from one or more in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, chemical modification carbon nanotube, preferably the both ends open type carbon nanotube of fluorinated modified, hydrophilic modifying and ion exchanging function.Preferred carbon nanotube sizes is diameter 0.72-3.2 nanometer, length 5-80 micron.
Preferably, the organic solvent described in above-mentioned steps c is ethanol, Virahol or dimethyl sulfoxide (DMSO) (DMSO).
Preferably, in above-mentioned steps d, described nano inorganic oxide is zirconium white (ZrO
2) nano powder, titanium dioxide (TiO
2) nano powder or aluminum oxide (Al
2o
3) nano powder or combination, such as, titanium dioxide and zirconia nano-powder mass ratio 1:1; Described C1-C3 lower alcohol is ethanol, propyl alcohol or Virahol.Preferably, in above-mentioned steps e, described redox catalyst is the nano-silver powder of particle diameter 10-60nm or diameter is 15 ~ 300nm, length 10 ~ 200 μm of silver-colored lines.
Preferably, in above-mentioned steps a, described perfluorinated sulfonic resin is tetrafluoroethylene and perfluor 3,6-dioxa-4-methyl-7-octene sulfonyl fluoride (CF
2=CFOCF
2cF (CF
3) OCF
2cF
2sO
2f) perfluorinated sulfonic resin that obtains of copolymerization, exchange capacity is 0.91-1.20mmo1/g; Perfluorinated carboxylic acid resin is tetrafluoroethylene and perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters (CF
2=CFOCF
2cF (CF
3) OCF
2cF
2cOOCH
3) polymkeric substance of copolymerization, loading capacity is 0.9-1.10mmo1/g.
Perfluorinated ion-exchange membrane prepared by the present invention, is particularly useful for 6-8kA/m
2on the Membrane Used In Chlor-alkali Cell electrolyzer of even higher superhigh-current-density oxygen cathode electrolysis process.Superhigh-current-density refers to 6-8kA/m
2even higher.
For superhigh-current-density oxygen cathode electrolysis process intermediate ion exchange membrane prior art Problems existing, the present invention by catalytic structure and function endowing ionic membrane surface, keeps ion film strength and thickness first simultaneously.Like this, both can keep ion film strength and conductivity, and make again ionic membrane surface have catalytic performance, and can fully adapt to oxygen cathode chloralkali process.
Excellent results of the present invention:
1, the chlorine industry fiber reinforcement ion-exchange membrane of carbon nanotubes of the present invention, because avoiding the fibroplastic continuous hole of traditional sacrificial, further increases the physical strength of film, more safe and reliable.
2, the chlorine industry fiber reinforcement ion-exchange membrane of carbon nanotubes of the present invention, by regulating the aperture of carbon nanotube used, can effectively improve its ionic flux and water flux, thus improve the electrochemical flux of chlor-alkali film, be particularly useful for superhigh-current-density electrolysis process.
3, the fiber reinforcement perfluorinated ion-exchange membrane for the electrolysis of superhigh-current-density oxygen cathode of the present invention, because constructing catalytic structure at cathode side (carboxylic acid side), thus having good catalysis, being particularly useful for oxygen cathode electrolysis process.
4, the fiber reinforcement perfluorinated ion-exchange membrane for the electrolysis of superhigh-current-density oxygen cathode of the present invention, the thickness not changing film, do not increase film the condition of structural complexity under, achieving the variation of function, is a kind of substantial improvements to traditional perfluorinated ion-exchange membrane.
Accompanying drawing explanation
Fig. 1 is the cross section structure schematic diagram of the fiber reinforcement perfluorinated ion-exchange membrane for the electrolysis of superhigh-current-density oxygen cathode.
Wherein, 1 is perfluorinated carboxylic acid resin's layer, and 2 is perfluorinated sulfonic resin layer, and 3 is carbon nanotube, and 4 is air release coating, and 5 is multi-functional coatings, and 6 is strengthen the fiber in screen cloth.This figure is only a structural representation, and wherein the shape of carbon nanotube is as the criterion with reality nanotube shape used.
Embodiment
By the following examples the present invention is further described, but the present invention is not limited only to following examples.
(6,6) type Single Walled Carbon Nanotube in embodiment, (12,4) type Single Walled Carbon Nanotube, (9,9) type Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, the carbon nanotube fluoridized are commercial products.
Embodiment 1:
(1) preparation of resin granular material
Perfluorinated sulfonic resin used is the powder that tetrafluoroethylene and perfluor 3,6-dioxa-4-methyl-7-octene sulfonyl fluoride carry out in-situ polymerization and obtain under carbon nanotube exists, and loading capacity is 0.99mmol/g.Carbon nanotube is wherein (6,6) type single-walled pipe, length 5-15 micron, mass content 4.5%.Perfluorinated carboxylic acid resin used is the powder that tetrafluoroethylene and the copolymerization of perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters obtain, and loading capacity is 0.95mmol/g.
The perfluorinated sulfonic resin powder of above-mentioned carbon nanotubes and perfluorinated carboxylic acid resin's powder are obtained respective masterbatch resin pellet through melt extruding granulation respectively.
(2) preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, the perfluorinated sulfonic resin pellet of carbon nanotubes, prepare perfluorinated ion exchange resin basement membrane by melting coextrusion processes; Then adopt continous vacuum recombining process PTFE fortifying fibre screen cloth to be inserted perfluorinated ion exchange resin basement membrane inside and form enhancing ionic membrane;
(3) transition of film and surface treatment
Step (2) gained enhancing ionic membrane is hydrolyzed 6 hours in massfraction 25%NaOH-water-Virahol (water and the Virahol mass ratio 1:1) solution of 90 DEG C make the transition;
With containing massfraction 5% perfluorinated sulfonic resin (multipolymer of tetrafluoroethylene and perfluor 3,6-dioxa-4-methyl-7-octene sulfonyl fluoride), 10% nanometer ZrO
2alcohol dispersion liquid dried ionic membrane sulphonic layer surface transition is sprayed, form air release coating after dry;
With containing massfraction 5% perfluorinated sulfonic resin, 7% silver powder (particle diameter 15nm) alcohol dispersion liquid to transition dried ionic membrane carboxylic layer surface spray, form multi-functional coatings after drying;
(4) spraying complete film is immersed in massfraction 0.2% aqueous sodium hydroxide solution, leaves standstill and namely obtains the fiber reinforcement perfluorinated ion-exchange membrane for the electrolysis of superhigh-current-density oxygen cathode of the present invention after aging 24 hours.
Ionic membrane tensile strength prepared by the present embodiment is 34MPa, can be used as the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density oxygen cathode condition under, negative electrode NaOH solution quality enters groove salt solution NaCl concentration 306g/L than concentration 32%, anode, go out the condition of groove salt solution NaCl concentration 203g/L, groove temperature 85 ~ 87 DEG C, activated cathode, 1mm pole span under test, bath voltage is 2.11-2.14V, current efficiency 97.6%.
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 sulfonyl fluoride obtains, loading capacity is 1.08mmol/g, the pellet that granulation obtains the perfluorinated sulfonic resin of carbon nanotubes is melt extruded after (6,6) type Single Walled Carbon Nanotube of length about 40 microns fully being mixed with above-mentioned perfluorinated sulfonic resin powder (mass ratio 10:100).Perfluorinated carboxylic acid resin used is the powder that tetrafluoroethylene and the copolymerization of perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters obtain, and loading capacity is 0.97mmol/g, obtains the pellet of perfluorinated carboxylic acid resin through melt extruding granulation.
(2) preparation of film and enhancing
Adopting above-mentioned perfluorinated carboxylic acid resin's pellet, the perfluorinated sulfonic resin pellet of carbon nanotubes, obtaining perfluorinated ion exchange resin basement membrane respectively by melt extruding; Then adopt multi hot press compound again PTFE to be strengthened screen cloth and insert perfluorinated ion exchange resin basement membrane inside formation enhancing ionic membrane;
(3) transition of film and surface treatment
By the water-DMSO(1:1 mass ratio of step (2) gained ionic membrane at the massfraction 25%KOH of 90 DEG C) be hydrolyzed in solution and make the transition for 12 hours; Respectively with the alcohol dispersion liquid containing massfraction 4% perfluorinated sulfonic resin, 8% nano-oxide mixture (wherein titanium dioxide and zirconia nano-powder mass ratio 1:1) and containing long 10 ~ 25 μm of silver-colored line-propanol dispersion liquors (mass ratio 6:8:86) of perfluorinated sulfonic resin-diameter 25nm simultaneously to making the transition dried ionic membrane sulfonic acid side and carboxylic acid side sprays, drying; Form air release coating, multi-functional coatings respectively.
(4) spraying complete film is immersed in 2% aqueous sodium hydroxide solution, leaves standstill and namely obtains the fiber reinforcement perfluorinated ion-exchange membrane for the electrolysis of superhigh-current-density oxygen cathode of the present invention after aging 4 hours.
Ionic membrane tensile strength prepared by the present embodiment is 35MPa, can be used as the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 5.5kA/m
2current density oxygen cathode condition under, negative electrode NaOH solution quality enters groove salt solution NaCl concentration 304g/L than concentration 32%, anode, go out the condition of groove salt solution NaCl concentration 202g/L, groove temperature 85 ~ 87 DEG C, activated cathode, zero pole span under test, bath voltage is 2.22-2.28V, current efficiency 97.7%.
Embodiment 3:
Step (1), step (2) are identical with embodiment 1 with step (3), unlike the size distribution of nano-silver powder in step (3) in 25-45 nanometer.
Ionic membrane tensile strength prepared by the present embodiment is 33MPa, may be used 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 enters groove salt solution NaCl concentration 305g/L than concentration 32%, anode, go out the condition of groove salt solution NaCl concentration 210g/L, groove temperature 85 ~ 87 DEG C, activated cathode, 1mm pole span under 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), are (12,4) type Single Walled Carbon Nanotube unlike carbon nanotube in step (1).
Ionic membrane tensile strength prepared by the present embodiment is 33.5MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 7.5kA/m
2current density under, negative electrode NaOH solution massfraction 32%, anode enter groove salt solution NaCl concentration 305g/L, go out the condition of groove salt solution NaCl concentration 205g/L, groove temperature 85 ~ 87 DEG C, activated cathode, 1mm pole span under test, bath voltage is 2.35-2.45V, current efficiency 96.8%.
Embodiment 5:
Step (1), step (2) are identical with embodiment 1 with step (3), and unlike in step (1), perfluorinated sulfonic resin loading capacity is 1.15mmol/g, perfluorinated carboxylic acid resin's loading capacity is 1.05mmol/g.
Ionic membrane tensile strength prepared by the present embodiment is 36MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 6.8kA/m
2current density under, negative electrode NaOH solution massfraction 32%, anode enter groove salt solution NaCl concentration 306g/L, go out the condition of groove salt solution NaCl concentration 203g/L, groove temperature 87 DEG C, activated cathode, 1mm pole span under test, bath voltage is 2.25-2.29V, current efficiency 97.4%.
Embodiment 6:
Step (1), step (2) are identical with embodiment 2 with step (3), unlike in step (1), described carbon nanotube replaces with the carbon nanotube fluoridized, with described perfluorinated sulfonic resin powder in mass ratio 8:100 melt extrude the pellet of the perfluorinated sulfonic resin that granulation obtains after fully mixing.
Carbon fluoride nano-tube can be commercial, also can prepare by prior art, see CN101284659A carbon fluoride nano-tube and preparation method thereof.
Ionic membrane tensile strength prepared by the present embodiment is 34MPa, may be used 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 enters groove salt solution NaCl concentration 305g/L than concentration 32%, anode, go out the condition of groove salt solution NaCl concentration 205g/L, groove temperature 85 ~ 87 DEG C, activated cathode, 1mm pole span under test, 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), unlike in step (3), and nano-silver thread diameter 55nm, length 30 ~ 180 μm.
Ionic membrane tensile strength prepared by the present embodiment is 35MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 6.5kA/m
2current density under, negative electrode NaOH solution quality enters groove salt solution NaCl concentration 305g/L than concentration 32%, anode, go out the condition of groove salt solution NaCl concentration 205g/L, groove temperature 85 ~ 87 DEG C, activated cathode, 1mm pole span under test, bath voltage is 2.32-2.34V, current efficiency 97.6%.
Embodiment 8:
Step (1), step (2) are identical with embodiment 2 with step (3), unlike in step (1), carbon nanotube used is the mixture of multi-walled carbon nano-tubes mass ratio 1:2 that length is about (9,9) the type Single Walled Carbon Nanotube of 20-50 micron and diameter 1.9 nanometer, length 35-70 micron.
Ionic membrane tensile strength prepared by the present embodiment is 34MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 8.5kA/m
2current density under, negative electrode NaOH solution quality enters groove salt solution NaCl concentration 305g/L than concentration 32%, anode, go out the condition of groove salt solution NaCl concentration 205g/L, groove temperature 85 ~ 87 DEG C, activated cathode, 1mm pole span under test, bath voltage is 2.48-2.51V, current efficiency 97.5%.
Claims (10)
1., for a perfluorinated ion-exchange membrane for superhigh-current-density oxygen cathode electrolysis, it is characterized in that the composite membrane that the second layer of the first layer of this ion-exchange membrane by perfluorinated carboxylic acid ion-exchange resin, perfluorosulfonic acid ion exchange resin containing carbon nanotube, fortifying fibre screen cloth, air release coating, multi-functional coatings form; Wherein, described the first layer and the second layer are complex as basement membrane, and fortifying fibre screen cloth inserts described membrane surface or inside;
Described air release coating is coated on described second layer surface, and thickness is 3-12 micron;
Described multi-functional coatings is formed in described the first layer surface by the C1-C3 lower alcohol dispersion containing perfluorinated sulfonic resin, redox catalyst, and thickness is 3-12 micron; Redox catalyst in described multi-functional coatings is the silver-colored line of the nano-silver powder of particle diameter 10-60nm or diameter 15 ~ 300nm, length 10 ~ 200 μm, and C1-C3 lower alcohol is ethanol, propyl alcohol or Virahol; Above-mentioned superhigh-current-density refers to 6kA/m
2above current density.
2. perfluorinated ion-exchange membrane as claimed in claim 1, it is characterized in that described the first layer thickness is 80-160 micron, described second layer thickness is 8-16 micron; And described basement membrane total thickness is 90-180 micron.
3. perfluorinated ion-exchange membrane as claimed in claim 1, is characterized in that described basement membrane total thickness is 100-135 micron.
4. perfluorinated ion-exchange membrane as claimed in claim 1, is characterized in that one or more that described carbon nanotube is selected from Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, carbon fluoride nano-tube.
5. the perfluorinated ion-exchange membrane as described in claim 1 or 4, is characterized in that the content of described carbon nanotube in perfluorosulfonic acid ion exchange resin is 0.1 ~ 10wt%; Carbon nanotube diameter is 0.72-3.2 nanometer.
6. the preparation method of the perfluorinated ion-exchange membrane described in any one of claim 1-5, comprises the steps:
A, adopt described in perfluorinated carboxylic acid resin, carbon nanotubes perfluorinated sulfonic resin, prepare perfluorinated ion exchange resin basement membrane by the technique of melting co-extrusion or multi hot press compound;
Enhancing screen cloth is inserted ion exchange fluoro resin membrane surface or inner formation enhancing ionic membrane by b, employing continous vacuum recombining process;
C, the enhancing ionic membrane of step b gained is hydrolyzed 6-12 hour in the water-organic solvent solution of KOH or NaOH of the massfraction 25% of 90 DEG C makes the transition;
D, with the C1-C3 lower alcohol dispersion liquid containing massfraction 3-10% perfluorinated sulfonic resin, 5-15% nano inorganic oxide, the sulphonic layer surface of ionic membrane after transition to be sprayed, after dry, form air release coating;
E, use spray the ionic membrane carboxylic layer surface after transition containing the dispersion liquid of perfluorinated sulfonic resin, redox catalyst, C1-C3 lower alcohol, form multi-functional coatings after drying; Described perfluorinated sulfonic resin: redox catalyst: the mass ratio of C1-C3 lower alcohol is (3-12): (1-10): (88-96);
After f, spraying, film is immersed in massfraction 0.2%-2% aqueous sodium hydroxide solution, leaves standstill aging 2-24 hour, obtain the perfluorinated ion-exchange membrane for superhigh-current-density oxygen cathode electrolysis process.
7. the preparation method of perfluorinated ion-exchange membrane as claimed in claim 6, it is characterized in that, in step a, the perfluorinated sulfonic resin of carbon nanotubes is carbon nanotube and the perfluorinated sulfonic resin comonomer powder through in-situ polymerization, or carbon nanotube mix with perfluorinated sulfonic resin after by melt extruding the perfluorinated sulfonic resin master batch obtained.
8. the preparation method of perfluorinated ion-exchange membrane as claimed in claim 6, it is characterized in that, the organic solvent described in step c is ethanol, Virahol or dimethyl sulfoxide (DMSO); In steps d, described nano inorganic oxide is zirconia nano-powder, one of titanic oxide nano or alumina nano powder or combination; C1-C3 lower alcohol is ethanol, propyl alcohol or Virahol.
9. the preparation method of perfluorinated ion-exchange membrane as claimed in claim 6, it is characterized in that, described perfluorinated sulfonic resin is tetrafluoroethylene and perfluor 3,6-dioxa-4-methyl-7-octene sulfonyl fluoride (CF
2=CFOCF
2cF (CF
3) OCF
2cF
2sO
2f) perfluorinated sulfonic resin that obtains of copolymerization, exchange capacity is 0.91-1.20mmo1/g; Described perfluorinated carboxylic acid resin is tetrafluoroethylene and perfluor 4,7-dioxa-5-methyl-8-nonenoic acid methyl esters (CF
2=CFOCF
2cF (CF
3) OCF
2cF
2cOOCH
3) polymkeric substance of copolymerization, loading capacity is 0.9-1.10mmo1/g.
10. the application of the perfluorinated ion-exchange membrane described in any one of claim 1-5, for 6kA/m
2on the Membrane Used In Chlor-alkali Cell electrolyzer of the oxygen cathode electrolysis process of above superhigh-current-density.
Priority Applications (1)
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| CN106268363A (en) * | 2016-08-02 | 2017-01-04 | 巨化集团技术中心 | A kind of screen cloth strengthens fluoride ion exchange composite membrane and preparation method thereof |
| JP7104928B2 (en) * | 2017-04-10 | 2022-07-22 | 透 北村 | coating composition |
| CN111101152B (en) * | 2019-12-31 | 2021-07-09 | 山东东岳高分子材料有限公司 | Perfluorocarboxylic acid ion exchange membrane with rough coating and preparation method thereof |
| CN111020630B (en) * | 2019-12-31 | 2021-07-13 | 山东东岳高分子材料有限公司 | Ultrathin perfluorocarboxylic acid ion exchange membrane with bubble-dispelling function and preparation method thereof |
| CN112323095B (en) * | 2020-09-24 | 2021-12-07 | 山东东岳高分子材料有限公司 | High-strength low-cell-pressure perfluorinated ion exchange membrane for chlor-alkali industry and preparation method thereof |
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