CN103031566A - Fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nano-pore canal and preparation method thereof - Google Patents
Fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nano-pore canal and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a fiber-reinforced perfluorinated ion exchange membrane containing a non-continuous nano-pore canal and a preparation method thereof. A basic membrane of the membrane comprises a perfluorosulfonic acid ion exchange resin layer and a perfluorocarboxylic acid ion exchange resin layer, reinforcing fiber mesh cloth is arranged in the perfluorosulfonic acid resin layer, and gas release coatings are sprayed on the surfaces on the two outer sides of the basic membrane; and the fiber-reinforced perfluorinated ion exchange membrane is characterized in that the non-continuous nano-pore canal is further contained in the perfluorosulfonic acid resin layer. The membrane is prepared through a melting co-extrusion or multi-layer hot-pressing compounding process. The membrane is used for the ion exchange membrane in the chlor-alkali industry and has better mechanical properties and electrochemical properties.
Description
Technical field
The present invention relates to a kind of chlorine industry with containing fiber reinforcement perfluorinated ion-exchange membrane of discontinuous nano pore 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 the Nafio of 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 perfluor sulfonephthalein 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, does not also have functional inorganics to improve the Film conductivity energy 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 electric density natural circulation groove.CN101773788A 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 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 sacrificial fiber continuous and dense distribution in film.
Summary of the invention
For the deficiency that technology is arranged now, the invention provides a kind of fiber reinforcement perfluorinated ion-exchange membrane that contains discontinuous nano pore that has simultaneously better electro-chemical properties and physical strength, be the perfluorinated ion-exchange membrane that a kind of chlorine industry is used.The present invention also provides the preparation method of described chlorine industry with perfluorinated ion-exchange membrane.
Terminological interpretation:
Nano material of the present invention refers to that all the diameter of material is nano level, and nano pore refers to that also channel diameter is of a size of nano level.
Technical scheme of the present invention is as follows:
A kind of chlorine industry perfluorinated ion-exchange membrane forms basement membrane by perfluorinated sulfonic acid resinbed and perfluorinated carboxylic acid ion-exchange resin's layer, has the fortifying fibre screen cloth to insert the perfluorinated sulfonic resin layer, and basement membrane two outer surfaces are coated with the air release coating; Also contain discrete nano pore in the perfluorinated sulfonic resin layer.
According to the present invention, described nano pore is the hole that forms after the nanometer sacrificial fiber material breakdown that contains in the perfluorinated sulfonic resin in the film preparation process.
According to the present invention, described nanometer sacrificial fiber material is selected from nanometer trevira or nanometer polyamide fiber, preferred nanometer ethylene glycol terephthalate (PET) fiber or PA 66 (nylon 66) fiber, diameter 1-200 nanometer, 1～30 micron of length.
According to the present invention, described perfluorinated sulfonic resin layer thickness is the 80-150 micron, and perfluorinated carboxylic acid resin's layer thickness is the 8-12 micron, and the air release coat-thickness of film both side surface is the 3-12 micron.
The basement membrane total thickness of above-mentioned perfluorinated ion-exchange membrane is controlled between the 90-160 micron, preferred 100-125 micron;
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 0.9-1.05mmol/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 0.9-1.05mmol/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 0.88-1.05mmol/g.
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.
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, propyl alcohol or Virahol of lower alcohol wherein, the optional ZnO of nano inorganic oxide, TiO
2Or ZrO
2, preferred nano inorganic oxide is ZrO
2
Above-mentioned materials of the present invention is selected to be equally applicable among the following preparation method.
The present invention also provides the chlorine industry that the contains discontinuous nano pore preparation method of fiber reinforcement ion-exchange membrane.
A kind of chlorine industry preparation method of fiber reinforcement ion-exchange membrane comprises that step is as follows:
A, after 1～20:100 fully mixes in mass ratio with nanometer sacrificial fiber material and perfluorinated sulfonic resin powder by melt extruding the perfluorinated sulfonic resin master batch that obtains containing nanometer sacrificial fiber material; Nanometer sacrificial fiber material wherein is selected from nanometer trevira or nanometer polyamide fiber, diameter 1-200 nanometer, 1～30 micron of length;
With perfluorinated carboxylic acid resin, the described perfluorinated sulfonic resin master batch that contains nanometer sacrificial fiber material, prepare the perfluorinated ion exchange resin basement membrane by melting coextrusion or the compound technique of multi hot press;
B, perfluorinated sulfonic resin layer surface or inner formation of adopting the continous vacuum recombining process that the fortifying fibre screen cloth is inserted above-mentioned basement membrane 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 hours and make the transition; And divide and take off the nanometer sacrificial fiber material in the perfluorinated sulfonic resin layer in the film, form nano pore.
D, carry out double-face spray painting with containing massfraction 3～10wt% perfluorinated sulfonic resin, the 5～15wt% nano inorganic oxide-lower alcohol dispersion liquid ionic membrane after to transition, form the air release coating after dry;
E, the complete film of spraying are immersed in massfraction 0.2%～2% aqueous sodium hydroxide solution, leave standstill aging 2～48 hours, namely obtain the chlorine industry that contains bar-shaped discontinuous nanochannel fiber reinforcement ion-exchange membrane of the present invention.
Among the above-mentioned steps a, the nanometer sacrificial fiber is 4～10:100 with perfluorinated sulfonic resin powder quality ratio; Nanometer sacrificial fiber material wherein is nanometer ethylene glycol terephthalate (PET) fiber or PA 66 (nylon 66) fiber preferably, diameter 1-200 nanometer, 1～30 micron of length;
Among the above-mentioned steps b, reinforcing fiber materials 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.The specification of fortifying fibre screen cloth is by prior art.
Organic solvent is a kind of in ethanol, Virahol or the dimethyl sulfoxide (DMSO) (DMSO) among the above-mentioned steps c.The mass percent concentration of KOH or NaOH is 12～28% in the mixing solutions, and the mass percent concentration that contains 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 a kind of in ethanol, propyl alcohol or the Virahol preferably.
Among the above-mentioned steps a, the described perfluorinated sulfonic resin layer thickness that contains nanometer sacrificial fiber 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 prepared chlorine industry of the present invention contains discontinuous nano pore (or claiming passage or cavity) with the fiber reinforcement ion-exchange membrane, 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, 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 fiber of 0.001dtex (about 10nm) with single screw rod method of polyblending.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) chlorine industry that contains discontinuous nano pore fiber reinforcement ion-exchange membrane 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) chlorine industry that contains discontinuous nano pore fiber reinforcement ion-exchange membrane of the present invention, contain more nano pore and have in other words higher porosity, reduced the transmission resistance of ion and water, thereby reduced the bath voltage of film, chlorine industry uses this film can be more energy-conservation with electrolyzer.
(3) the ion-exchange membrane preparation technology that contains of the present invention has avoided using expensive band to weave the enhancing screen cloth of 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 that contains the chlorine industry usefulness fiber reinforcement ion-exchange membrane of discontinuous nano pore.Wherein, 1 is perfluorinated carboxylic acid resin's layer, and 2 is the perfluorinated sulfonic resin layer, and 3 is discontinuous nano pore, 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.
(1) preparation of resin granular material
Melt extrude the pellet that granulation obtains containing the perfluorinated sulfonic resin of nanometer sacrificial fiber material after 4:100 fully mixes in mass ratio with above-mentioned perfluorinated sulfonic resin powder with diameter 20 ± 5 nanometers, long 10 ± 2 microns PET fiber (nanometer sacrificial fiber material).
Tetrafluoroethylene and perfluor 4, the powder that 7-dioxa-5 methyl-copolymerization of 8-nonenoic acid methyl esters obtains obtains perfluorinated carboxylic acid resin's pellet through melt extruding granulation; Loading capacity is 0.92mmol/g.
(2) preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, contain the perfluorinated sulfonic resin pellet of nanometer sacrificial fiber material, prepare the perfluorinated ion exchange resin basement membrane by the melting coextrusion processes; The perfluorinated sulfonic resin layer thickness that contains nanometer sacrificial fiber material is 100 microns, and perfluorinated carboxylic acid resin's layer thickness is 10 microns.Then adopt the continous vacuum recombining process that PTFE is strengthened screen cloth and insert the inner enhancing ionic membrane that forms of perfluorinated sulfonic resin layer in the perfluorinated ion exchange resin basement membrane;
(3) transition of film and spraying
Step (2) gained is strengthened ionic membrane hydrolysis in 90 ℃ KOH water-ethanol solution (KOH massfraction 20wt%, ethanol 30wt% in the mixing solutions) to make the transition and except the nanometer sacrificial fiber material in the striping, forms nano pore in 8 hours.Dry rear with containing 3wt% perfluorinated sulfonic resin, 5wt% nanometer ZrO
2-alcohol dispersion liquid is carried out double-face spray painting to the ionic membrane after making the transition, the dry rear air release coating that forms; The air release coat-thickness is 8 microns.Spray complete film and be immersed in massfraction 2% aqueous sodium hydroxide solution, leave standstill the aging chlorine industry fiber reinforcement ion-exchange membrane that namely obtains containing discontinuous nano pore after 4 hours.Structure as shown in Figure 1.
The prepared ionic membrane tensile strength of present embodiment is 32MPa, 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 3.13-3.16V, negative electrode alkali current efficiency 97.4%.
Embodiment 2:
Perfluorinated sulfonic resin, perfluorinated carboxylic acid resin's powder raw material are with embodiment 1.
(1) preparation of resin granular material
Melt extrude the pellet that granulation obtains containing the perfluorinated sulfonic resin of nano-fiber material after 10:100 fully mixes in mass ratio with above-mentioned perfluorinated sulfonic resin powder with diameter 20 ± 5 nanometers, long 15 ± 5 microns nylon 66 fiber.Perfluorinated carboxylic acid resin's the logical embodiment 1 of pellet preparation.
(2) preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, contain the perfluorinated sulfonic resin pellet of nano-fiber material, by melt extruding the perfluorinated ion exchange resin basement membrane that obtains respectively containing perfluorinated carboxylic acid ion-exchange resin's film and perfluorinated sulfonic acid ion exchange resin membrane; The perfluorinated sulfonic resin layer thickness that contains nanometer sacrificial fiber material is 95 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 the inner enhancing ionic membrane that forms of perfluorinated sulfonic resin layer;
(3) transition of film and spraying
Step (2) gained strengthened that ionic membrane hydrolysis in 90 ℃ NaOH water-DMSO solution (mixing solutions NaOH massfraction 15wt%, ethanol 25wt%) made the transition in 12 hours and except the nanometer sacrificial fiber material in the striping, the formation nanochannel.Dry rear with containing massfraction 5% perfluorinated sulfonic resin, 12% nanometer ZrO
2-Virahol dispersion liquid carries out double-face spray painting to the ionic membrane after making the transition, the dry rear air release coating that forms; 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 chlorine industry that the contains discontinuous nano pore fiber reinforcement ion-exchange membrane of the present invention that namely obtains after 36 hours.
The prepared ionic membrane tensile strength of present embodiment is 33MPa, 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 3.13-3.16V, negative electrode alkali current efficiency 97.6%.
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 34MPa, 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 210g/L, 85～87 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 3.11-3.14V, negative electrode alkali current efficiency 96.6%.
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 prepared ionic membrane tensile strength of present embodiment is 30MPa, 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 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 selecting the perfluorinated sulfonic resin loading capacity 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, 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 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 of PET fiber and described perfluorinated sulfonic resin powder is 20:100.
The prepared ionic membrane tensile strength of present embodiment is 23MPa, 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 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 selecting 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, 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 3.10-3.12V, negative electrode alkali current efficiency 97.2%.
Embodiment 8:
Step (1), step (2) are identical with embodiment 2 with step (3), different is in the step (1), melt extrudes the pellet that granulation obtains containing the perfluorinated sulfonic resin of nano-fiber material after 16:100 fully mixes in mass ratio with nylon 66 fiber and the described perfluorinated sulfonic resin powder of diameter 5-30 nanometer, long 5-20 micron.
The prepared ionic membrane tensile strength of present embodiment is 24MPa, 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 3.03-3.05V, negative electrode alkali current efficiency 97.3%.
Embodiment 9:
Step (1), step (2) are identical with embodiment 2 with step (3), and different is in the step (3), and selecting 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 26MPa, 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 3.09-3.13V, negative electrode alkali current efficiency 97.4%.
Claims (11)
1. a chlorine industry perfluorinated ion-exchange membrane forms basement membrane by perfluorinated sulfonic acid resinbed and perfluorinated carboxylic acid ion-exchange resin's layer, has the fortifying fibre screen cloth to insert the perfluorinated sulfonic resin layer, and basement membrane two outer surfaces are coated with the air release coating; It is characterized in that also containing in the perfluorinated sulfonic resin layer discrete nano pore.
2. chlorine industry perfluorinated ion-exchange membrane as claimed in claim 1 is characterized in that described nano pore is the hole that forms after the nanometer sacrificial fiber material breakdown that contains in the perfluorinated sulfonic resin in the film preparation process.
3. chlorine industry perfluorinated ion-exchange membrane as claimed in claim 2 is characterized in that described nanometer sacrificial fiber material is selected from nanometer trevira or nanometer polyamide fiber, diameter 1-200 nanometer, 1～30 micron of length.
4. chlorine industry perfluorinated ion-exchange membrane as claimed in claim 2 is characterized in that described nanometer sacrificial fiber material is selected from nanometer ethylene glycol terephthalate (PET) fiber or PA 66 (nylon 66) fiber.
5. chlorine industry perfluorinated ion-exchange membrane as claimed in claim 1 is characterized in that described perfluorinated sulfonic resin layer thickness is the 80-150 micron, and perfluorinated carboxylic acid resin's layer thickness is the 8-12 micron, and the air release coat-thickness of film both side surface is the 3-12 micron.
6. a chlorine industry comprises that step is as follows with the preparation method of fiber reinforcement ion-exchange membrane:
A, after 1～20:100 fully mixes in mass ratio with nanometer sacrificial fiber material and perfluorinated sulfonic resin powder by melt extruding the perfluorinated sulfonic resin master batch that obtains containing nanometer sacrificial fiber material; Nanometer sacrificial fiber material wherein is selected from nanometer trevira or nanometer polyamide fiber, diameter 1-200 nanometer, 1～30 micron of length;
With perfluorinated carboxylic acid resin, the described perfluorinated sulfonic resin master batch that contains nanometer sacrificial fiber material, prepare the perfluorinated ion exchange resin basement membrane by melting coextrusion or the compound technique of multi hot press;
B, perfluorinated sulfonic resin layer surface or inner formation of adopting the continous vacuum recombining process that the fortifying fibre screen cloth is inserted above-mentioned basement membrane 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 hours and make the transition; And divide and take off the nanometer sacrificial fiber material in the perfluorinated sulfonic resin layer in the film, form nano pore.
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 massfraction 0.2%～2% aqueous sodium hydroxide solution, leave standstill aging 2～48 hours, and get final product.
7. the preparation method of ion-exchange membrane as claimed in claim 5 is characterized in that among the step a, and the nanometer sacrificial fiber is 4～10:100 with perfluorinated sulfonic resin powder quality ratio; Nanometer sacrificial fiber material wherein is preferably nanometer ethylene glycol terephthalate (PET) fiber or PA 66 (nylon 66) fiber, diameter 1-200 nanometer, 1～30 micron of length.
8. the preparation method of ion-exchange membrane as claimed in claim 5, it is characterized in that reinforcing fiber materials is selected among the step b: one or more in tetrafluoroethylene (PTFE) fiber, perfluoroethylene-propylene fiber, poly-perfluoro propyl vinyl ether fiber, the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fibre fluorocarbon polymer fiber.
9. the preparation method of ion-exchange membrane as claimed in claim 5 is characterized in that organic solvent is ethanol, Virahol or dimethyl sulfoxide (DMSO) among the step c.
10. the preparation method of ion-exchange membrane as claimed in claim 5 is characterized in that the mass percent concentration of KOH in the mixing solutions among the step c or NaOH is 12 ~ 28%, and the mass percent concentration of organic solvent is 10 ~ 40%.
11. the preparation method of ion-exchange membrane as claimed in claim 5 is characterized in that in the steps d, nano inorganic oxide is ZrO
2, lower alcohol is ethanol, propyl alcohol or Virahol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210540972.0A CN103031566B (en) | 2012-12-14 | 2012-12-14 | Fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nano-pore canal and preparation method thereof |
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|---|---|---|---|
| CN201210540972.0A CN103031566B (en) | 2012-12-14 | 2012-12-14 | Fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nano-pore canal and preparation method thereof |
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| CN103556178A (en) * | 2013-11-04 | 2014-02-05 | 山东东岳高分子材料有限公司 | Ion exchange membrane for superhigh-current-density oxygen cathode electrolysis and preparation method thereof |
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| CN104592540A (en) * | 2013-11-04 | 2015-05-06 | 北京化工大学 | A preparing method of a perfluorosulfonic acid-carboxylic acid composite membrane by multilayer solution tape casting |
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| CN103556178B (en) * | 2013-11-04 | 2016-04-06 | 山东东岳高分子材料有限公司 | For the ion-exchange membrane and preparation method thereof of superhigh-current-density oxygen cathode electrolysis |
| CN103540951A (en) * | 2013-11-04 | 2014-01-29 | 山东东岳高分子材料有限公司 | Ion exchange membrane for electrolysis of oxygen cathode and preparation method thereof |
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| CN107208286A (en) * | 2015-01-21 | 2017-09-26 | 株式会社东芝 | Porous barrier film, its manufacture method, hypochloric acid water manufacture electrode unit and its hypochloric acid water manufacture device is used |
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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 |
| CN112387109A (en) * | 2019-08-13 | 2021-02-23 | 深圳市美兆环境股份有限公司 | Perfluoropolymer-based titanium dioxide air purification coating and preparation method thereof |
| CN110699706A (en) * | 2019-11-27 | 2020-01-17 | 山东东岳高分子材料有限公司 | Fluoride ion exchange membrane for alkali chloride electrolysis |
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| CN111188065A (en) * | 2019-12-31 | 2020-05-22 | 山东东岳未来氢能材料有限公司 | Enhanced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis and preparation method thereof |
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