CN102978654A - Low-resistance and high-strength ion exchange membrane for chlor-alkali industry and preparation method of low-resistance and high-strength ion exchange membrane - Google Patents
Low-resistance and high-strength ion exchange membrane for chlor-alkali industry and preparation method of low-resistance and high-strength ion exchange membrane Download PDFInfo
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Abstract
The invention relates to a low-resistance and high-strength ion exchange membrane for the chlor-alkali industry and a preparation method of the low-resistance and high-strength ion exchange membrane. The low-resistance and high-strength ion exchange membrane is a multi-layer composite membrane comprising a perfluorosulfonic ion exchange resin layer, a perfluoropropionate ion exchange resin layer, reinforced screen cloth and gas release coatings, wherein the perfluorosulfonic ion exchange resin layer with the thickness of 80-150 micrometers and the perfluoropropionate ion exchange resin layer with the thickness of 8-12 micrometers form a perfluorosulfonic ion exchange resin base membrane, the gas release coatings with 3-12 micrometers are arranged on two outer side surfaces of the base membrane, the reinforced screen cloth is arranged in the perfluorosulfonic ion exchange resin layer, and the perfluorosulfonic ion exchange resin layer is also internally provided with a nano pore and a nano cavity. The low-resistance and high-strength ion exchange membrane can be prepared through a melt co-extruding or multi-layer hot-pressing compounding process, can be used in an ion exchange membrane in the chlor-alkali industry, and has good mechanical property and electrochemical performance.
Description
Technical field
The present invention relates to a kind of chlorine industry with low resistance high strength ionic exchange membrane and preparation method thereof, belong to polymeric material field.
Background technology
Du pont company has been developed perfluorinated sulfonic resin and ion-exchange membrane thereof the sixties.The skeleton structure ion-exchange membrane of this perfluoro of the very fast discovery of people has extraordinary stability, is adapted at most using in the severe rugged environment of chlor-alkali electrolytic cells, thereby is used widely in chlorine industry rapidly.Be subjected to the inspiration of E.I.Du Pont Company's perfluorinated ion-exchange membrane, Japan AGC company and Japanese Asahi Kasei Corporation have also been developed the similar perfluorinated ion exchange resin of structure and ionic membrane in succession.Japanese Asahi Kasei Corporation had replaced the perfluoro sulfonic acid membrane of E.I.Du Pont Company with the perfluorocarboxylic acid film in 1976, and had developed carboxylic acid-sulfonic acid composite membrane.Beginning Shandong Dongyue Polymer Material Co., Ltd. researched and developed successfully domestic Membrane Used In Chlor-alkali Cell in 2009, and took the lead in dropping into Lanxing (Beijing) Chemical Machinery Co., Ltd. at the experimental installation (2.7m of Huanghua chlor-alkali company limited of Cangzhou Dahua Group company limited
2Electrolyzer) trial run obtains initial success.Subsequently again at ten thousand tons of devices of Dongyue Fluorine-Silicon Material Co., Ltd., Shandong's chlor-alkali plant, the middle salt Changzhou chemical industry chlor-alkali plant F of limited-liability company
2The successful Application such as device have been opened the new page of Chinese chlorine industry.
Present business-like chlorine industry is perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane with perfluorinated ion-exchange membrane (Membrane Used In Chlor-alkali Cell), and namely the anode side of film is that perfluorinated sulfonic acid layer, cathode side are the perfluorocarboxylic acid layer.Sulphonic layer has higher ion and sees through ability, and is that lower bath voltage is arranged in 20%～30% 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.
Obtain high current density and keep simultaneously certain physical strength and dimensional stability for solving ionic membrane, usually adopt the physical strength of the Material reinforcement ionic membranes such as fiber, cloth, fabric, keep the dimensional stability of mould material.European patent EP 0875524B1 discloses and has utilized the glass fibre membrane of glass fibre non-woven technology preparation to strengthen Du Pont
The technology of series membranes is mentioned the oxide compounds such as silicon-dioxide simultaneously in this patent document.But non-woven glass fibre cloth is the base material that must use in this patent document, and this will limit the use range of film greatly.US Patent No. 6692858 discloses the technology that polytetrafluoroethylene fiber strengthens perfluorinated sulfonic resin, be with perfluorinated sulfonic acid fluoro-resin and polytetrafluoroethylene fiber mix, extrude, to make the transition make fibre-reinforced perfluorinated sulfonic resin.The method can not be produced continuously because transformation process is consuming time, and the surface does not have functional inorganics to improve the Film conductivity energy yet simultaneously.The perfluorinated ion-exchange membrane that is used for chlor-alkali industry need to satisfy: good electro-chemical properties, low membrane voltage, high mechanical strength and dimensional stability.Generally speaking, when the perfluorinated ion-exchange membrane loading capacity became large, membrane resistance can reduce, but physical strength can reduce.
Up-to-date Membrane Used In Chlor-alkali Cell generally contains " sacrifice core ".So-called " sacrifice core ", it is a kind of fiber, in the film manufacturing processed, be woven in fortifying fibre, after being shaped, film can be dissolved falls by aftertreatment, sacrifice the original occupied position of core, become water and ionic channel, namely increased the passage that the sodium ion on the unit surface passes through, thereby the reduction membrane voltage has the film of sacrificing core to be suitable for high current density natural circulation groove.
CN200910231445 discloses a kind of exchange membrane containing fluorine that strengthens with sacrificial fiber mesh cloth, and it comprises the ion exchange fluoro resin basement membrane, with screen cloth and the hydrophilic coating of sacrificial fiber; Wherein the ion exchange fluoro resin basement membrane comprises perfluorinated carboxylic acid resin's rete of 5-10 micron, the perfluorinated sulfonic resin rete of 90-120 micron, and the perfluorinated sulfonic acid/carboxyl acid copolymer of the 0-40 micron between perfluorocarboxylic acid rete and perfluorinated sulfonic acid rete or blending resin rete, screen cloth with sacrificial fiber is comprised of fortifying fibre and sacrificial fiber, can improve the electro-chemical properties of film, effectively reduce membrane resistance.
Sacrificial fiber is before dissolving or chemical degradation, and physical strength in the time of can guaranteeing film strength and first the driving is avoided damage.After electric groove operated steadily, sacrificial fiber was slowly dissolved disappearance, naturally reduced the resistance of film, but certainly also corresponding decline of film strength.This is that what in fact form in film after forming passage is a kind of continuous hole, thereby can reduce the physical strength of film owing to continuous in the film of sacrificial fiber and dense distribution.
Summary of the invention
For the deficiency that technology is arranged now, the invention provides a kind of chlorine industry low resistance high strength ionic exchange membrane and preparation method thereof, this film is to contain perfluor ion-exchange composite membranes multiple nano pore, that screen cloth strengthens, has simultaneously better electro-chemical properties and physical strength.
Terminological interpretation:
Nano material of the present invention refers to that all the diameter of filamentary material or the particle diameter of particle are nano level; Multiple nano pore refers to contain simultaneously at least two kinds of difform holes, and such as microscler and hollow ball shape, microscler duct diameter dimension is that nano level is called nano pore; The diameter of hollow ball shape hole is nano level, is called the nanometer hole.
Technical scheme of the present invention is as follows:
A kind of chlorine industry low resistance high strength ionic exchange membrane, the multilayer complex films that this film is comprised of perfluorinated sulfonic acid resinbed, perfluorinated carboxylic acid ion-exchange resin's layer, enhancing screen cloth and gas release coat; Wherein perfluorinated carboxylic acid resin's layer of the perfluorinated sulfonic resin layer of thickness 80-150 micron and thickness 8-12 micron consists of the perfluorinated ion exchange resin basement membrane, and two outer surfaces of film all have the air release coating of 3-12 micron thickness; The fortifying fibre screen cloth places in the perfluorinated sulfonic resin layer, also has nano pore and nanometer hole in the perfluorinated sulfonic resin layer.
Described nano pore and nanometer hole are that the mixing nanometer expendable material that contains in the perfluorinated sulfonic resin in the film preparation process decomposes or the rear hole that forms of sacrifice.Described mixing nanometer expendable material is the combination of nanometer sacrificial fiber and nano inorganic particle arbitrary proportion, wherein the nanometer sacrificial fiber is selected from one of nanometer ethylene glycol terephthalate (PET) fiber, PA 66 (nylon 66) fiber or combination, diameter 1-200 nanometer, length 1-30 micron; The nano inorganic particle is the nano-carbonate powder, is preferably nano-calcium carbonate, particle diameter 20-100 nanometer.
The basement membrane total thickness of above-mentioned perfluorinated ion-exchange membrane between the 90-160 micron, preferred 100-125 micron.
Above-mentioned perfluorinated sulfonic resin adopts present disclosed perfluorinated sulfonic resin material, the perfluorinated sulfonic resin that obtains of tetrafluoroethylene and the copolymerization of perfluor sulfonyl base vinyl ether preferably, and exchange capacity is 0.9-1.05mmo1/g.Further preferred tetrafluoroethylene and perfluor 3,6-dioxa-4-methyl-7-octene sulfonic acid fluoride (CF
2=CFOCF
2CF (CF
3) OCF
2CF
2SO
2F) perfluorinated sulfonic resin that obtains of copolymerization, exchange capacity is 0.9-1.00mmo1/g.
Above-mentioned perfluorinated carboxylic acid resin adopts present disclosed perfluorinated carboxylic acid resin's material, the polymkeric substance that forms of tetrafluoroethylene and a small amount of perfluorocarboxylic acid ester vinyl ether copolymerization preferably, and loading capacity is 0.88-1.05mmo1/g.Further preferred 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 that copolymerization forms, loading capacity is 0.9-1.00mmo1/g.
Above-mentioned air release coating is that drying forms after being coated in the ion exchange resin membrane surface by the nano inorganic oxide that contains perfluorinated sulfonic resin-lower alcohol dispersion liquid, preferably ethanol or propyl alcohol or Virahol of lower alcohol wherein, the optional ZnO of nano inorganic oxide, TiO
2Or ZrO
2, be preferably ZrO
2
Above-mentioned 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, the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fibre fluorocarbon polymer fiber.
According to the present invention, a kind of chlorine industry preparation method of low resistance high strength ionic exchange membrane comprises that step is as follows:
A, adopt the perfluorinated carboxylic acid resin, contain the perfluorinated sulfonic resin that mixes the nanometer expendable material, prepare the perfluorinated ion exchange resin basement membrane by melting coextrusion or the compound technique of multi hot press;
Described mixing nanometer expendable material is the combination of nanometer sacrificial fiber and nano inorganic particle arbitrary proportion, wherein the nanometer sacrificial fiber is selected from one of nanometer ethylene glycol terephthalate (PET) fiber, PA 66 (nylon 66) fiber or combination, diameter 1-200 nanometer, length 1-30 micron; The nano inorganic particle is the nano-carbonate powder, is preferably nano-calcium carbonate, particle diameter 20-100 nanometer.
B, get the basement membrane that step a makes, adopt the continous vacuum recombining process that the fortifying fibre screen cloth is inserted ambiguity and close perfluorinated sulfonic resin layer surface or inner formation of nanometer expendable material and strengthen ionic membrane;
C, step b gained is strengthened ionic membrane in the mixing solutions of KOH or the NaOH aqueous solution and organic solvent, under 90 ℃ of temperature, be hydrolyzed 6-12 hour and make the transition; And divide the mixing nanometer expendable material of taking off in the film, nanometer sacrificial fiber to divide and take off the rear nano pore that in film, forms, the nano inorganic particle breakdown is fallen to form the nanometer hole in the film.
D, carry out double-face spray painting with the ionic membrane of the lower alcohol dispersion liquid that contains massfraction 3-10wt% perfluorinated sulfonic resin and 5-15wt% nano inorganic oxide after to transition, form the air release coating after dry;
E, the complete film of spraying are immersed in the massfraction 0.2%-2% aqueous sodium hydroxide solution, leave standstill aging 2-48 hour, take out.Namely obtain chlorine industry of the present invention low resistance high strength ionic exchange membrane.
Among the above-mentioned steps a, mix the nanometer expendable material and be preferably 4～10:100 with perfluorinated sulfonic resin powder quality ratio, obtain containing the perfluorinated sulfonic resin master batch that mixes the nanometer expendable material by melt extruding after fully mixing.
Among the above-mentioned steps a, nano-carbonate is preferably nano-calcium carbonate, particle diameter 20-100 nanometer.
Among the above-mentioned steps a, the mass ratio of nanometer sacrificial fiber and nano inorganic particle is (1 ~ 99): (99 ~ 1), the mass ratio of further preferred nanometer sacrificial fiber and nano inorganic particle is (30 ~ 80): (70 ~ 20).
Among the above-mentioned steps c, organic solvent is a kind of in ethanol, Virahol or the dimethyl sulfoxide (DMSO) (DMSO).The mass percent concentration of KOH or NaOH is 12 ~ 28% in the mixing solutions, and the mass percent concentration of organic solvent is 10 ~ 40%; The mass percent concentration of KOH or NaOH is 15 ~ 20% in the further preferred mixing solutions, and the mass percent concentration of organic solvent is 20 ~ 30%.
Among the above-mentioned steps d, nano inorganic oxide is ZrO preferably
2, lower alcohol is ethanol, propyl alcohol or Virahol preferably.
Among the above-mentioned steps a, the described perfluorinated sulfonic resin layer thickness that contains mixing nanometer expendable material is the 80-150 micron, and perfluorinated carboxylic acid resin's layer thickness is the 8-12 micron; The basement membrane total thickness of above-mentioned perfluorinated ion-exchange membrane is controlled between the 90-160 micron, preferred 100-125 micron.
Among the above-mentioned steps d, the air release coat-thickness is the 3-12 micron.
The low resistance high strength ionic exchange membrane of the discontinuous passage that contains the various shape holes such as nano aperture and hole that the present invention is prepared can be used on the at present general Membrane Used In Chlor-alkali Cell electrolyzer.The present invention has realized utilizing nanometer sacrificial fiber material to make discrete hollow duct in film, utilizes the nano inorganic particulate material to make discrete spherically-shaped cavity in film, and the chemical property of film and mechanical property are comprehensively improved.Nanometer sacrificial fiber material generally refers to the fiber of diameter between 1～100nm, has surface effects, small-size effect and macro quanta tunnel effect.Can prepare by spinning, such as polymeric spray electrostatic stretch spin processes, fabric of island-in-sea type polycomponent spinning method and the single screw rod method of polyblending.Can make the about 10nm of 0.001dtex(with single screw rod method of polyblending) fiber.The present invention has also obtained the chlor-alkali electrolytic cells ion-exchange membrane of mechanical property and chemical property high comprehensive performance by the preferred collocation of each layer resin material, the particular combinations of each processing parameter.
Advantage of the present invention is:
(1) the low resistance high strength chlorine industry fiber reinforcement ion-exchange membrane that contains the various shape nano aperture of the present invention because of the continuous hole of having avoided traditional sacrificial fiber to form, has further improved the physical strength of film, and is more safe and reliable.
(2) the low resistance high strength chlorine industry fiber reinforcement ion-exchange membrane that contains the various shape nano aperture of the present invention, contain multiple nano pore and hole, has higher porosity, reduced the transmission resistance of ion and water, thereby reduced the bath voltage of film, used this film more energy-conservation at the Membrane Used In Chlor-alkali Cell electrolyzer.
(3) ion-exchange membrane preparation technology of the present invention has avoided using the enhancing screen cloth of expensive band braiding sacrificial fiber, and adopts nano-fiber material in conjunction with enhancing screen cloth cheap and easy to get, has reduced manufacturing cost, has avoided harsh weaving condition.
Description of drawings
Fig. 1 is the cross section structure synoptic diagram of ion-exchange membrane of the present invention.Wherein, 1 is perfluorinated carboxylic acid resin's layer, and 2 is the perfluorinated sulfonic resin layer, and 3A is the ball shaped nano hole, and 3B is the rod-like nano duct, and 4 is the air release coating, and 5 for strengthening the fiber in the screen cloth.
Embodiment
By the following examples the present invention is further specified, but the present invention is not limited only to following examples.But the raw material perfluorinated sulfonic resin of selecting among the embodiment, perfluorinated carboxylic acid resin's powder and pellet all market are bought, and Shandong Huaxia Shenzhou New Material Co., Ltd. is on sale.
Embodiment 1:
Perfluorinated sulfonic resin loading capacity in the present embodiment is 0.95mmol/g, is tetrafluoroethylene and perfluor 3, the powder that 6-dioxa-4-methyl-copolymerization of 7-octene sulfonic acid fluoride obtains.
Perfluorinated carboxylic acid resin's loading capacity in the present embodiment is 0.93mmol/g, tetrafluoroethylene and perfluor 4, the powder that 7-dioxa-5 methyl-copolymerization of 8-nonenoic acid methyl esters obtains.
(1) preparation of resin granular material
Cut-off footpath 20 ± 5 nanometers, long 10 ± 2 microns PET fiber and median size 25 nanometers calcium carbonate in mass ratio 80:20 mix, must mix the nanometer expendable material.
Melt extrude the pellet that granulation obtains containing the perfluorinated sulfonic resin that mixes the nanometer expendable material after 4:100 fully mixes in mass ratio with above-mentioned perfluorinated sulfonic resin powder with described mixing nanometer expendable material;
Other gets above-mentioned perfluorinated carboxylic acid resin obtains the perfluorinated carboxylic acid resin through melt extruding granulation pellet.
(2) preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, contain the perfluorinated sulfonic resin pellet that mixes the nanometer expendable material, contain the perfluorinated ion exchange resin basement membrane of perfluorinated sulfonic resin layer and perfluorinated sulfonic resin layer by the preparation of melting coextrusion processes; Wherein containing the perfluorinated sulfonic resin layer thickness that mixes the nanometer expendable material is 110 microns, and perfluorinated carboxylic acid resin's layer thickness is 10 microns.Then adopt the continous vacuum recombining process that PTFE is strengthened the inner enhancing ionic membrane that forms of perfluorinated sulfonic resin layer that screen cloth is inserted this basement membrane;
(3) transition of film and spraying
Step (2) gained is strengthened ionic membrane in the KOH water-ethanol solution (ethanol content 30wt%) of 90 ℃ massfraction 20%, be hydrolyzed the mixing nanometer expendable material that made the transition and removed in the striping in 8 hours, except forming nano pore behind the PET fiber in the striping, the geomery of nano pore and PET Fiber Phase adapt to; Except forming the nanometer hole behind the nano-calcium carbonate in the striping, geomery and the nano-calcium carbonate particles in nanometer hole adapt.
(4) dry rear with containing 3wt% perfluorinated sulfonic resin and 5wt% nanometer ZrO
2The ionic membrane of alcohol dispersion liquid after to transition carry out double-face spray painting, form the air release coating after dry; The air release coat-thickness is 8 microns.
Spray complete film and be immersed in massfraction 2% aqueous sodium hydroxide solution, leaving standstill wears out namely got ion-exchange membrane of the present invention after 4 hours.
The prepared ion-exchange membrane tensile strength of present embodiment is 31MPa, can be used for the ion-exchange membrane of ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2Current density under, negative electrode NaOH solution quality specific concentration 32%, anode advance groove salt solution NaCl concentration 305g/L, go out under the condition of groove salt solution NaCl concentration 205g/L, 85～87 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 3.11-3.13V, negative electrode alkali current efficiency 97.7%.
Embodiment 2: the perfluorinated sulfonic resin in the present embodiment, perfluorinated carboxylic acid resin's powder are identical with embodiment 1.
(1) preparation of resin granular material
Mixing the nanometer expendable material is: diameter 20 ± 5 nanometers, long 10 ± 2 microns the calcium carbonate granule mixture of 30:70 in mass ratio of nylon 66 and median size 80 nanometers.
To melt extrude granulation after mixing the nanometer expendable material 10:100 fully mixing in mass ratio with above-mentioned perfluorinated sulfonic resin powder and obtain containing the pellet of the perfluorinated sulfonic resin of nano-fiber material, perfluorinated carboxylic acid resin's powder 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, contain the perfluorinated sulfonic resin pellet that mixes the nanometer expendable material, by melt extruding the ion exchange resin basement membrane that obtains respectively containing perfluorinated carboxylic acid resin's layer and perfluorinated sulfonic resin layer; Containing the perfluorinated sulfonic resin layer thickness that mixes the nanometer expendable material is 115 microns, and perfluorinated carboxylic acid resin's layer thickness is 8 microns.
Then adopt the compound screen cloth that again PTFE strengthened of multi hot press to insert inner formation of perfluorinated sulfonic resin layer of perfluorinated ion exchange resin basement membrane and strengthen ionic membrane;
(3) transition of film and spraying
Step (2) gained is strengthened ionic membrane in the NaOH of 90 ℃ massfraction 15% water-DMSO solution (containing 25% DMSO), be hydrolyzed mixing nanometer expendable material nylon 66 fiber and the calcium carbonate granule that made the transition and removed in the striping in 12 hours, formation nano pore and hole.
(4) dry rear with containing massfraction 5% perfluorinated sulfonic resin and 12% nanometer ZrO
2The ionic membrane of Virahol dispersion liquid after to transition carry out double-face spray painting, form the air release coating after dry; The air release coat-thickness is 6 microns.
Spray complete film and be immersed in massfraction 0.2% aqueous sodium hydroxide solution, leave standstill the aging low resistance high strength chlorine industry fiber reinforcement ion-exchange membrane that contains the various shape nano aperture of the present invention that namely obtains after 36 hours.
The prepared ionic membrane tensile strength of present embodiment is 35MPa, is used for the ion-exchange membrane of ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2Current density under, negative electrode NaOH solution quality specific concentration 32%, anode advance 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 3.12-3.14V, negative electrode alkali current efficiency 97.5%.
Embodiment 3:
Step (1), step (2) are identical with embodiment 1 with step (3), the diameter of PET fiber is 50 ± 5 nanometers that different is in the step (1), long 20 ± 2 microns.
The prepared ionic membrane tensile strength of present embodiment is 33MPa, is used for the ion-exchange membrane of ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2Current density under, negative electrode NaOH solution quality specific concentration 32%, anode advance 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 3.10-3.12V, negative electrode alkali current efficiency 96.7%.
Embodiment 4:
Step (1), step (2) are identical with embodiment 1 with step (3), and different is in the step (3), with containing massfraction 9% perfluorinated sulfonic resin, 8wt% nanometer ZrO
2-alcohol dispersion liquid is carried out double-face spray painting to the dried ionic membrane that makes the transition.The air release coat-thickness is 4 microns.
The prepared ionic membrane tensile strength of present embodiment is 32MPa, is used for the ion-exchange membrane of ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2Current density under, negative electrode NaOH liquid quality fraction 32%, anode advance groove salt solution NaCl concentration 305g/L, go out under the condition of groove salt solution NaCl concentration 205g/L, 85～87 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 3.09-3.12V, negative electrode alkali current efficiency 96.4%.
Embodiment 5:
Step (1), step (2) are identical with embodiment 1 with step (3), and different is in the step (1), and the perfluorinated sulfonic resin loading capacity of selecting is that 0.91mmol/g, perfluorinated carboxylic acid resin's loading capacity are 0.99mmol/g.
The prepared ionic membrane tensile strength of present embodiment is 25MPa, is used for the ion-exchange membrane of ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2Current density under, negative electrode NaOH liquid quality fraction 32%, anode advance groove salt solution NaCl concentration 305g/L, go out under the condition of groove salt solution NaCl concentration 210g/L, 86 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 3.06-3.10V, negative electrode alkali current efficiency 96.5%.
Embodiment 6:
Step (1), step (2) are identical with embodiment 1 with step (3), and different is in the step (1), and the mass ratio that mixes expendable material and described perfluorinated sulfonic resin powder is 40:60.
The prepared ionic membrane tensile strength of present embodiment is 23MPa, can be used for the ion-exchange membrane in the ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2Current density under, negative electrode NaOH liquid quality fraction 32%, anode advance groove salt solution NaCl concentration 305g/L, go out under the condition of groove salt solution NaCl concentration 210g/L, 86 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 3.02-3.06V, negative electrode alkali current efficiency 96.3%.
Embodiment 7:
Step (1), step (2) are identical with embodiment 2 with step (3), and different is in the step (1), and the perfluorinated sulfonic resin loading capacity is that 0.93mmol/g, perfluorinated carboxylic acid resin's loading capacity are 1.03mmol/g.
The prepared ionic membrane tensile strength of present embodiment is 29MPa, is used for the ion-exchange membrane of ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2Current density under, negative electrode NaOH solution quality specific concentration 32%, anode advance groove salt solution NaCl concentration 305g/L, go out under the condition of groove salt solution NaCl concentration 205g/L, 85～87 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 3.06-3.09V, negative electrode alkali current efficiency 97.5%.
Embodiment 8:
Step (1), step (2) are identical with embodiment 2 with step (3), different is in the step (1), mix the nanometer expendable material and be diameter 25 ± 5 nanometers, long 10 ± 2 microns the mixture of nylon 66 and the calcium carbonate of median size 80 nanometers, mass ratio 50:50.
The prepared ionic membrane tensile strength of present embodiment is 26MPa, is used for the ion-exchange membrane of ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2Current density under, negative electrode NaOH solution quality specific concentration 32%, anode advance groove salt solution NaCl concentration 305g/L, go out under the condition of groove salt solution NaCl concentration 205g/L, 85～87 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 3.04-3.07V, negative electrode alkali current efficiency 97.4%.
Embodiment 9:
Step (1), step (2) are identical with embodiment 2 with step (3), and different is in the step (3), and the perfluorinated sulfonic resin loading capacity is that 0.93mmol/g, perfluorinated carboxylic acid resin's loading capacity are 1.03mmol/g.
The prepared ionic membrane tensile strength of present embodiment is 25MPa, can be used for the ion-exchange membrane in the ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2Current density under, negative electrode NaOH solution quality specific concentration 32%, anode advance groove salt solution NaCl concentration 305g/L, go out under the condition of groove salt solution NaCl concentration 205g/L, 85～87 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 3.05-3.08V, negative electrode alkali current efficiency 97.2%.
Claims (10)
1. a chlorine industry is with low resistance high strength ionic exchange membrane, this film by perfluorinated sulfonic acid resinbed, perfluorinated carboxylic acid ion-exchange resin's layer, strengthen the multilayer complex films that screen cloth and gas release coat form; Wherein, perfluorinated carboxylic acid resin's layer of the perfluorinated sulfonic resin layer of thickness 80-150 micron and thickness 8-12 micron consists of the perfluorinated ion exchange resin basement membrane, and two outer surfaces of basement membrane all have the air release coating of 3-12 micron thickness; The fortifying fibre screen cloth places in the perfluorinated sulfonic resin layer, also has nano pore and nanometer hole in the perfluorinated sulfonic resin layer.
2. ion-exchange membrane as claimed in claim 1 is characterized in that, described nano pore and nanometer hole are that the mixing nanometer expendable material that contains in the perfluorinated sulfonic resin in the film preparation process decomposes or the rear hole that forms of sacrifice; Described mixing nanometer expendable material is the combination of nanometer sacrificial fiber and nano inorganic particle arbitrary proportion, wherein the nanometer sacrificial fiber is selected from one of nanometer ethylene glycol terephthalate (PET) fiber, PA 66 (nylon 66) fiber or combination, the diameter 1-200 nanometer of fiber, length 1-30 micron; The nano inorganic particle is the nano-carbonate powder, particle diameter 20-100 nanometer.
3. a chlorine industry comprises that step is as follows with the preparation method of ion-exchange membrane:
A, adopt the perfluorinated carboxylic acid resin, contain the perfluorinated sulfonic resin that mixes the nanometer expendable material, prepare the perfluorinated ion exchange resin basement membrane by melting coextrusion or the compound technique of multi hot press;
Described mixing nanometer expendable material is the combination of nanometer sacrificial fiber and nano inorganic particle arbitrary proportion, wherein the nanometer sacrificial fiber is selected from one of nanometer ethylene glycol terephthalate (PET) fiber, PA 66 (nylon 66) fiber or combination, diameter 1-200 nanometer, length 1-30 micron; The nano inorganic particle is the nano-carbonate powder, particle diameter 20-100 nanometer;
Mass ratio 1～the 20:100 of described mixing nanometer expendable material and perfluorinated sulfonic resin powder;
B, get the basement membrane that step a makes, adopt the continous vacuum recombining process that the fortifying fibre screen cloth is inserted ambiguity and close perfluorinated sulfonic resin layer surface or inner formation of nanometer expendable material and strengthen ionic membrane;
C, step b gained is strengthened ionic membrane in the mixing solutions of KOH or the NaOH aqueous solution and organic solvent, under 90 ℃ of temperature, be hydrolyzed 6-12 hour and make the transition; And divide the mixing nanometer expendable material of taking off in the film, nanometer sacrificial fiber to divide and take off the rear nano pore that in film, forms, the nano inorganic particle breakdown is fallen to form the nanometer hole in the film;
D, carry out double-face spray painting with the ionic membrane of the lower alcohol dispersion liquid that contains massfraction 3-10wt% perfluorinated sulfonic resin and 5-15wt% nano inorganic oxide after to transition, form the air release coating after dry;
E, the complete film of spraying are immersed in the massfraction 0.2%-2% aqueous sodium hydroxide solution, leave standstill aging 2-48 hour, take out.
4. the preparation method of ion-exchange membrane as claimed in claim 3, it is characterized in that among the step a, mixing the nanometer expendable material is 4～10:100 with perfluorinated sulfonic resin powder quality ratio, obtains containing the perfluorinated sulfonic resin master batch that mixes the nanometer expendable material by melt extruding after fully mixing.
5. the preparation method of ion-exchange membrane as claimed in claim 3 is characterized in that among the step a, and nano-carbonate is nano-calcium carbonate, particle diameter 20-100 nanometer.
6. the preparation method of ion-exchange membrane as claimed in claim 3 is characterized in that among the above-mentioned steps a, and the mass ratio of nanometer sacrificial fiber and nano inorganic particle is (1 ~ 99): (99 ~ 1); The mass ratio of further preferred nanometer sacrificial fiber and nano inorganic particle is (30 ~ 80): (70 ~ 20).
7. the preparation method of ion-exchange membrane as claimed in claim 3 is characterized in that among the step c, and organic solvent is ethanol, Virahol or dimethyl sulfoxide (DMSO).
8. the preparation method of ion-exchange membrane as claimed in claim 3 is characterized in that among the step c, and the mass percent concentration of KOH or NaOH is 12 ~ 28% in the mixing solutions, and the mass percent concentration of organic solvent is 10 ~ 40%.
9. the preparation method of ion-exchange membrane as claimed in claim 3 is characterized in that in the steps d, and nano inorganic oxide is ZrO
2Lower alcohol is ethanol, propyl alcohol or Virahol.
10. the preparation method of ion-exchange membrane as claimed in claim 3 is characterized in that among the step a, and the described perfluorinated sulfonic resin layer thickness that contains mixing nanometer expendable material is the 80-150 micron, and perfluorinated carboxylic acid resin's layer thickness is the 8-12 micron; In the steps d, the air release coat-thickness is the 3-12 micron.
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