CN103031566B - 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
- Publication number
- CN103031566B CN103031566B CN201210540972.0A CN201210540972A CN103031566B CN 103031566 B CN103031566 B CN 103031566B CN 201210540972 A CN201210540972 A CN 201210540972A CN 103031566 B CN103031566 B CN 103031566B
- Authority
- CN
- China
- Prior art keywords
- fiber
- nanometer
- membrane
- exchange membrane
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 fiber reinforcement perfluorinated ion-exchange membrane containing discontinuous nano pore and preparation method thereof, belong to polymeric material field.
Background technology
Du pont company develops perfluorinated sulfonic resin and ion-exchange membrane thereof the sixties.People find that the skeleton structure ion-exchange membrane of this perfluoro has extraordinary stability very soon, are adapted at most using in the severe rugged environment of chlor-alkali electrolytic cells, are used widely in chlorine industry thus rapidly.By the inspiration of E.I.Du Pont Company's perfluorinated ion-exchange membrane, Japan AGC company and Japanese Asahi Kasei Corporation also develop perfluorinated ion exchange resin and the ionic membrane of similar in succession.Within 1976, Japanese Asahi Kasei Corporation instead of the perfluoro sulfonic acid membrane of E.I.Du Pont Company with perfluorocarboxylic acid film, and develops carboxylic acid-sulfonic acid composite membrane.Within 2009, start Shandong Dongyue Polymer Material Co., Ltd. and research and develop successfully domestic Membrane Used In Chlor-alkali Cell, and take the lead in dropping into the experimental installation (2.7m of Lanxing (Beijing) Chemical Machinery Co., Ltd. in Huanghua chlor-alkali company limited of Cangzhou Dahua Group company limited
2electrolyzer) trial run, obtain initial success.Subsequently again at Dongyue Fluorine-Silicon Material Co., Ltd., Shandong's chlor-alkali plant ten thousand tons of devices, Zhong Yan Changzhou chemical industry limited-liability company chlor-alkali plant F
2the successful Application such as device, have opened the new page of Chinese chlorine industry.
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.
Obtain high current density for solving ionic membrane and maintain certain physical strength and dimensional stability simultaneously, usually adopting the physical strength of the Material reinforcement ionic membranes such as fiber, cloth, fabric, maintain the dimensional stability of mould material.European patent EP 0875524B1 discloses the glass fibre membrane utilizing glass fiber non-woven technology to prepare and strengthens Du Pont Nafio
the technology of series membranes, mentions the oxide compounds such as silicon-dioxide in this patent document simultaneously.But non-woven glass fibre cloth is the base material that must use in this patent document, this will limit the use range of film greatly.US Patent No. 6692858 discloses polytetrafluoroethylene fiber and strengthens the technology of perfluorinated sulfonic resin, be perfluor sulfonephthalein fluoro-resin and polytetrafluoroethylene fiber mixed, extrude, make the transition obtained fibre-reinforced perfluorinated sulfonic resin.The method due to transformation process consuming time and can not continuous seepage, do not have functional inorganics to improve the conductivity of film simultaneously yet.Perfluorinated ion-exchange membrane demand fulfillment for chlor-alkali industry: excellent electro-chemical properties, low membrane voltage, high mechanical strength and dimensional stability.Generally speaking, when perfluorinated ion-exchange membrane loading capacity becomes large, membrane resistance can reduce, but physical strength can reduce.
Up-to-date Membrane Used In Chlor-alkali Cell is generally containing " sacrifice core ".So-called " sacrifice core ", it is a kind of fiber, be woven in together with fortifying fibre in film manufacturing processed, film can be dissolved by aftertreatment after being shaped, sacrifice the original occupied position of core, become water and ionic channel, namely add the passage that the sodium ion in unit surface passes through, thus reduction membrane voltage, there is the film of sacrificing core to be suitable for high electric density natural circulation groove.CN101773788A discloses a kind of exchange membrane containing fluorine strengthened with sacrificial fiber mesh cloth, and it comprises ion exchange fluoro resin basement membrane, the screen cloth being with sacrificial fiber and hydrophilic coating; Wherein 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 0-40 micron between perfluorocarboxylic acid rete and perfluorinated sulfonic acid rete or blending resin rete, screen cloth with sacrificial fiber is made up of fortifying fibre and sacrificial fiber, the electro-chemical properties of film can be improved, effectively reduce membrane resistance.Sacrificial fiber is before dissolving or chemical degradation, and physical strength when can ensure film strength and drive for the first time, avoids damage.After electric groove operates steadily, sacrificial fiber slowly dissolves disappearance, naturally reduces the resistance of film, but film strength also corresponding decline.This be due to sacrificial fiber in film continuously and dense distribution, what in fact formed in film after forming passage is a kind of continuous print hole, thus can reduce the physical strength of film.
Summary of the invention
For the deficiency having now technology, the invention provides a kind of fiber reinforcement perfluorinated ion-exchange membrane containing discontinuous nano pore simultaneously with better electro-chemical properties and physical strength, is a kind of perfluorinated ion-exchange membrane of chlorine industry.The present invention also provides the preparation method of described chlorine industry perfluorinated ion-exchange membrane.
Terminological interpretation:
Nano material of the present invention all refers to that the diameter of material is nano level, and nano pore also refers to that 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, form basement membrane by perfluorosulfonic acid ion exchange resin layer and perfluorinated carboxylic acid ion-exchange resin's layer, have fortifying fibre screen cloth to insert perfluorinated sulfonic resin layer, basement membrane two outer surface is coated with air release coating; Also containing discrete nano pore in perfluorinated sulfonic resin layer.
According to the present invention, described nano pore is the hole formed after the nanometer sacrificial fiber material breakdown contained in perfluorinated sulfonic resin in 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 (nylon66 fiber) fiber, diameter 1-200 nanometer, length 1 ~ 30 micron.
According to the present invention, described perfluorinated sulfonic resin layer thickness is 80-150 micron, and perfluorinated carboxylic acid resin's layer thickness is 8-12 micron, and the air release coat-thickness of film both side surface is 3-12 micron.
The basement membrane total thickness of above-mentioned perfluorinated ion-exchange membrane controls between 90-160 micron, preferred 100-125 micron;
Above-mentioned perfluorinated sulfonic resin, adopts at present disclosed perfluorinated sulfonic resin material, preferably the perfluorinated sulfonic resin that obtains of tetrafluoroethylene and the copolymerization of perfluor sulfonyl base vinyl ether, and exchange capacity is 0.9-1.05mmo1/g.Preferred tetrafluoroethylene and perfluor 3,6-dioxa-4-methyl-7-octene sulfonyl fluoride (CF further
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, adopt disclosed perfluorinated carboxylic acid resin's material at present, the polymkeric substance of preferably tetrafluoroethylene and the copolymerization of a small amount of perfluorocarboxylic acid ester vinyl ether, loading capacity is 0.9-1.05mmol/g.Preferred tetrafluoroethylene and perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters (CF further
2=CFOCF
2cF (CF
3) OCF
2cF
2cOOCH
3) polymkeric substance of copolymerization, 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), gathers one or more in perfluoro propyl vinyl ether fiber, tetrafluoroethylene-perfluoro vinyl ether co-polymer fiber fluorocarbon polymer fiber.
Above-mentioned air release coating is formed by the nano inorganic oxide-lower alcohol dispersion drying after ion exchange resin membrane surface containing perfluorinated sulfonic resin, wherein lower alcohol preferably ethanol, propyl alcohol or Virahol, nano inorganic oxide optional ZnO, TiO
2or ZrO
2, preferred nano inorganic oxide is ZrO
2.
Above-mentioned materials of the present invention is selected to be equally applicable in following preparation method.
The present invention also provides the preparation method of the chlorine industry fiber reinforcement ion-exchange membrane containing discontinuous nano pore.
A preparation method for chlorine industry fiber reinforcement ion-exchange membrane, comprises step as follows:
A, by nanometer sacrificial fiber material and perfluorinated sulfonic resin powder in mass ratio 1 ~ 20:100 fully mix after by melt extruding the perfluorinated sulfonic resin master batch obtained containing nanometer sacrificial fiber material; Nanometer sacrificial fiber material is wherein selected from nanometer trevira or nanometer polyamide fiber, diameter 1-200 nanometer, length 1 ~ 30 micron;
By perfluorinated carboxylic acid resin, the described perfluorinated sulfonic resin master batch containing nanometer sacrificial fiber material, prepare perfluorinated ion exchange resin basement membrane by the technique of melting coextrusion or multi hot press compound;
B, the surperficial or inner formation of perfluorinated sulfonic resin layer adopting continous vacuum recombining process fortifying fibre screen cloth to be inserted above-mentioned basement membrane strengthen ionic membrane;
C, step b gained strengthened ionic membrane and in the mixing solutions of KOH or the NaOH aqueous solution and organic solvent, at 90 DEG C of temperature, be hydrolyzed 6 ~ 12 hours make the transition; And point nanometer sacrificial fiber material taken off in film in perfluorinated sulfonic resin layer, form nano pore.
D, with containing massfraction 3 ~ 10wt% perfluorinated sulfonic resin, 5 ~ 15wt% nano inorganic oxide-lower alcohol dispersion liquid, double-face spray painting is carried out to the ionic membrane after transition, after dry, form air release coating;
E, spray complete film and be immersed in massfraction 0.2% ~ 2% aqueous sodium hydroxide solution, leave standstill aging 2 ~ 48 hours, namely obtain the chlorine industry fiber reinforcement ion-exchange membrane containing bar-shaped discontinuous nanochannel of the present invention.
In above-mentioned steps a, nanometer sacrificial fiber is 4 ~ 10:100 with perfluorinated sulfonic resin powder quality ratio; Nanometer sacrificial fiber material is wherein nanometer ethylene glycol terephthalate (PET) fiber or PA 66 (nylon66 fiber) fiber preferably, diameter 1-200 nanometer, length 1 ~ 30 micron;
In above-mentioned steps b, reinforcing fiber materials is selected from: tetrafluoroethylene (PTFE) fiber, perfluoroethylene-propylene fiber, Ion Exchange Fiber (CN101003588), gathers one or more in perfluoro propyl vinyl ether fiber, tetrafluoroethylene-perfluoro vinyl ether co-polymer fiber fluorocarbon polymer fiber.The specification of fortifying fibre screen cloth is by prior art.
In above-mentioned steps c, organic solvent is the one in ethanol, Virahol or dimethyl sulfoxide (DMSO) (DMSO).In mixing solutions, the mass percent concentration of KOH or NaOH is 12 ~ 28%, and the mass percent concentration containing organic solvent is 10 ~ 40%; In preferred mixing solutions, the mass percent concentration of KOH or NaOH is 15 ~ 20% further, and the mass percent concentration of organic solvent is 20 ~ 30%.
In above-mentioned steps d, nano inorganic oxide is ZrO preferably
2, the one of lower alcohol preferably in ethanol, propyl alcohol or Virahol.
In above-mentioned steps a, the described perfluorinated sulfonic resin layer thickness containing nanometer sacrificial fiber material is 80-150 micron, and perfluorinated carboxylic acid resin's layer thickness is 8-12 micron; The basement membrane total thickness of above-mentioned perfluorinated ion-exchange membrane controls between 90-160 micron, preferred 100-125 micron.
In above-mentioned steps d, air release coat-thickness is 3-12 micron.
Chlorine industry fiber reinforcement ion-exchange membrane prepared by the present invention contains discontinuous nano pore (or claiming passage or cavity), can be used on Membrane Used In Chlor-alkali Cell electrolyzer general at present.Present invention achieves and utilize nanometer sacrificial fiber material in film, manufacture discrete hollow tunnel, 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 be prepared by spinning, as polymeric spray electrostatic stretch spin processes, fabric of island-in-sea type polycomponent spin processes and singe screw polyblend method.The fiber of 0.001dtex (about 10nm) can be obtained by the singe screw method of polyblending.The present invention also obtains 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 combination of each processing parameter.
Advantage of the present invention is:
(1) the chlorine industry fiber reinforcement ion-exchange membrane containing discontinuous nano pore 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 containing discontinuous nano pore of the present invention, containing more nano pore, there is higher porosity in other words, decrease the transmission resistance of ion and water, thus reducing the bath voltage of film, chlorine industry electrolyzer uses this film can be more energy-conservation.
(3) of the present invention avoiding containing ion-exchange membrane preparation technology uses expensive band to weave the enhancing screen cloth of sacrificial fiber, and adopt nano-fiber material in conjunction with enhancing screen cloth cheap and easy to get, reduce manufacturing cost, avoid harsh weaving condition.
Accompanying drawing explanation
Fig. 1 is the cross section structure schematic diagram of the chlorine industry fiber reinforcement ion-exchange membrane containing discontinuous nano pore.Wherein, 1 is perfluorinated carboxylic acid resin's layer, and 2 is perfluorinated sulfonic resin layer, and 3 is discontinuous nano pore, and 4 is air release coating, and 5 is strengthen the fiber in screen cloth.
Embodiment
By the following examples the present invention is further described, but the present invention is not limited only to following examples.The raw material perfluorinated sulfonic resin selected in embodiment, perfluorinated carboxylic acid resin's powder and pellet all can be bought in market, 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 the powder that tetrafluoroethylene and the copolymerization of perfluor 3,6-dioxa-4-methyl-7-octene sulfonyl fluoride obtain.
(1) preparation of resin granular material
By diameter 20 ± 5 nanometer, long 10 ± 2 microns PET (nanometer sacrificial fiber material) and above-mentioned perfluorinated sulfonic resin powder in mass ratio 4:100 melt extrude the pellet that granulation obtains the perfluorinated sulfonic resin containing nanometer sacrificial fiber material after fully mixing.
The powder that tetrafluoroethylene and the copolymerization of perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters obtain, obtains the pellet of perfluorinated carboxylic acid resin 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, perfluorinated sulfonic resin pellet containing nanometer sacrificial fiber material, prepare perfluorinated ion exchange resin basement membrane by melting coextrusion processes; Perfluorinated sulfonic resin layer thickness containing nanometer sacrificial fiber material is 100 microns, and perfluorinated carboxylic acid resin's layer thickness is 10 microns.Then adopt continous vacuum recombining process PTFE to be strengthened screen cloth and insert formation enhancing ionic membrane in perfluorinated sulfonic resin layer inside in perfluorinated ion exchange resin basement membrane;
(3) transition of film and spraying
Step (2) gained is strengthened ionic membrane hydrolysis in the KOH water-ethanol solution (in mixing solutions KOH massfraction 20wt%, ethanol 30wt%) of 90 DEG C within 8 hours, carry out making the transition and remove the nanometer sacrificial fiber material in striping, form nano pore.With containing 3wt% perfluorinated sulfonic resin, 5wt% nanometer ZrO after dry
2-alcohol dispersion liquid carries out double-face spray painting to the ionic membrane after transition, forms air release coating after dry; Air release coat-thickness is 8 microns.Spraying complete film is immersed in massfraction 2% aqueous sodium hydroxide solution, leaves standstill the chlorine industry fiber reinforcement ion-exchange membrane namely obtained after aging 4 hours containing discontinuous nano pore.Structure as shown in Figure 1.
Ionic membrane tensile strength prepared by the present embodiment is 32MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density under, negative electrode NaOH solution quality 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 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
By diameter 20 ± 5 nanometer, long 15 ± 5 microns nylon 66 fiber and above-mentioned perfluorinated sulfonic resin powder in mass ratio 10:100 melt extrude the pellet that granulation obtains the perfluorinated sulfonic resin containing nano-fiber material after fully mixing.The logical embodiment 1 of pellet preparation of perfluorinated carboxylic acid resin.
(2) preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, perfluorinated sulfonic resin pellet containing nano-fiber material, by melt extruding the perfluorinated ion exchange resin basement membrane obtained respectively containing perfluorinated carboxylic acid ion-exchange resin's film and perfluorosulfonic acid ion exchange resin membrane; Perfluorinated sulfonic resin layer thickness containing nanometer sacrificial fiber material is 95 microns, and perfluorinated carboxylic acid resin's layer thickness is 8 microns.Then adopt multi hot press compound again PTFE to be strengthened screen cloth and insert perfluorinated sulfonic resin layer inside formation enhancing ionic membrane;
(3) transition of film and spraying
Step (2) gained is strengthened ionic membrane hydrolysis in the NaOH water-DMSO solution (mixing solutions NaOH massfraction 15wt%, ethanol 25wt%) of 90 DEG C within 12 hours, carry out making the transition and remove the nanometer sacrificial fiber material in striping, form nanochannel.With containing massfraction 5% perfluorinated sulfonic resin, 12% nanometer ZrO after dry
2-Virahol dispersion liquid carries out double-face spray painting to the ionic membrane after transition, forms air release coating after dry; Air release coat-thickness is 6 microns.Spraying complete film is immersed in massfraction 0.2% aqueous sodium hydroxide solution, leaves standstill and namely obtains the chlorine industry fiber reinforcement ion-exchange membrane containing discontinuous nano pore of the present invention after aging 36 hours.
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 4.5kA/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 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), are 50 ± 5 nanometers, length 20 ± 2 microns unlike the diameter of PET in step (1).
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 4.5kA/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 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), unlike in step (3), with containing massfraction 9% perfluorinated sulfonic resin, 8wt% nanometer ZrO
2-alcohol dispersion liquid carries out double-face spray painting to dried ionic membrane transition.
Ionic membrane tensile strength prepared by the present embodiment is 30MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density under, negative electrode NaOH solution 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 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 unlike in step (1), selection perfluorinated sulfonic resin loading capacity is 0.91mmol/g, perfluorinated carboxylic acid resin's loading capacity is 0.99mmol/g.
Ionic membrane tensile strength prepared by the present embodiment is 25MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density under, negative electrode NaOH solution massfraction 32%, anode enter groove salt solution NaCl concentration 305g/L, go out the condition of groove salt solution NaCl concentration 210g/L, groove temperature 86 DEG C, activated cathode, 1mm pole span under 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 unlike in step (1), the mass ratio of PET and described perfluorinated sulfonic resin powder is 20:100.
Ionic membrane tensile strength prepared by the present embodiment is 23MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density under, negative electrode NaOH solution massfraction 32%, anode enter groove salt solution NaCl concentration 305g/L, go out the condition of groove salt solution NaCl concentration 210g/L, groove temperature 86 DEG C, activated cathode, 1mm pole span under 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 unlike in step (1), selection perfluorinated sulfonic resin loading capacity is 0.93mmol/g, perfluorinated carboxylic acid resin's loading capacity is 1.03mmol/g.
Ionic membrane tensile strength prepared by the present embodiment is 29MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density under, negative electrode NaOH solution quality 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 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), unlike in step (1), by the nylon 66 fiber of diameter 5-30 nanometer, long 5-20 micron and described perfluorinated sulfonic resin powder in mass ratio 16:100 melt extrude the pellet that granulation obtains the perfluorinated sulfonic resin containing nano-fiber material after fully mixing.
Ionic membrane tensile strength prepared by the present embodiment is 24MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density under, negative electrode NaOH solution quality 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 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 unlike in step (3), selection perfluorinated sulfonic resin loading capacity is 0.93mmol/g, perfluorinated carboxylic acid resin's loading capacity is 1.03mmol/g.
Ionic membrane tensile strength prepared by the present embodiment is 26MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density under, negative electrode NaOH solution quality 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 3.09-3.13V, negative electrode alkali current efficiency 97.4%.
Claims (7)
1. a chlorine industry preparation method for fiber reinforcement ion-exchange membrane, comprises step as follows:
A, by nanometer sacrificial fiber material and perfluorinated sulfonic resin powder in mass ratio 1 ~ 20:100 fully mix after by melt extruding the perfluorinated sulfonic resin master batch obtained containing nanometer sacrificial fiber material; Nanometer sacrificial fiber material is wherein selected from nanometer trevira or nanometer polyamide fiber, diameter 1-200 nanometer, length 1 ~ 30 micron;
By perfluorinated carboxylic acid resin, the described perfluorinated sulfonic resin master batch containing nanometer sacrificial fiber material, prepare perfluorinated ion exchange resin basement membrane by the technique of melting coextrusion or multi hot press compound;
B, the surperficial or inner formation of perfluorinated sulfonic resin layer adopting continous vacuum recombining process fortifying fibre screen cloth to be inserted above-mentioned basement membrane strengthen ionic membrane;
C, step b gained strengthened ionic membrane and in the mixing solutions of KOH or the NaOH aqueous solution and organic solvent, at 90 DEG C of temperature, be hydrolyzed 6 ~ 12 hours make the transition; And point nanometer sacrificial fiber material taken off in film in perfluorinated sulfonic resin layer, form nano pore;
D, with the lower alcohol dispersion liquid containing massfraction 3 ~ 10wt% perfluorinated sulfonic resin and 5 ~ 15wt% nano inorganic oxide, double-face spray painting is carried out to the ionic membrane after transition, after dry, form air release coating;
E, spray complete film and be immersed in massfraction 0.2% ~ 2% aqueous sodium hydroxide solution, leave standstill aging 2 ~ 48 hours, to obtain final product.
2. the preparation method of ion-exchange membrane as claimed in claim 1, it is characterized in that in step a, nanometer sacrificial fiber is 4 ~ 10:100 with perfluorinated sulfonic resin powder quality ratio.
3. the chlorine industry as claimed in claim 1 preparation method of fiber reinforcement ion-exchange membrane, it is characterized in that in step a, nanometer sacrificial fiber material is nanometer ethylene glycol terephthalate (PET) fiber or PA 66 (nylon66 fiber) fiber, diameter 1-200 nanometer, length 1 ~ 30 micron.
4. the chlorine industry as claimed in claim 1 preparation method of fiber reinforcement ion-exchange membrane, it is characterized in that, in step b, reinforcing fiber materials is selected from: one or more in tetrafluoroethylene (PTFE) fiber, perfluoroethylene-propylene fiber, poly-perfluoro propyl vinyl ether fiber, tetrafluoroethylene-perfluoro vinyl ether co-polymer fiber fluorocarbon polymer fiber.
5. the chlorine industry preparation method of fiber reinforcement ion-exchange membrane as claimed in claim 1, is characterized in that in step c, organic solvent is ethanol, Virahol or dimethyl sulfoxide (DMSO).
6. the chlorine industry preparation method of fiber reinforcement ion-exchange membrane as claimed in claim 1, it is characterized in that the mass percent concentration of KOH or NaOH in the mixing solutions in step c is 12 ~ 28%, the mass percent concentration of organic solvent is 10 ~ 40%.
7. the chlorine industry preparation method of fiber reinforcement ion-exchange membrane as claimed in claim 1, it is characterized in that in steps d, nano inorganic oxide is ZrO
2, lower alcohol is ethanol, propyl alcohol or Virahol.
Priority Applications (1)
| 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 |
Applications Claiming Priority (1)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103031566A CN103031566A (en) | 2013-04-10 |
| CN103031566B true CN103031566B (en) | 2015-03-18 |
Family
ID=48018951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210540972.0A Active CN103031566B (en) | 2012-12-14 | 2012-12-14 | Fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nano-pore canal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103031566B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103556179B (en) * | 2013-11-04 | 2016-04-06 | 山东东岳高分子材料有限公司 | High current density perfluorinated ion-exchange membrane of carbon nano-tube modification and preparation method thereof |
| 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 |
| CN103540951B (en) * | 2013-11-04 | 2016-08-17 | 山东东岳高分子材料有限公司 | A kind of ion exchange membrane for oxygen cathode electrolysis and preparation method thereof |
| CN104018179B (en) * | 2014-06-06 | 2017-01-04 | 山东东岳高分子材料有限公司 | Ion-conductive membranes and preparation method thereof |
| GB2531808A (en) | 2014-11-03 | 2016-05-04 | Short Brothers Plc | Methods and precursors for manufacturing a perforated composite part |
| WO2016117170A1 (en) * | 2015-01-21 | 2016-07-28 | 株式会社 東芝 | Porous diaphragm, production method therefor, electrode unit for producing hypochlorous acid water, and hypochlorous-acid-water production device using same |
| 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 |
| CN110699706B (en) * | 2019-11-27 | 2021-05-28 | 山东东岳高分子材料有限公司 | Fluoride ion exchange membrane for alkali chloride electrolysis |
| CN111074296B (en) * | 2019-12-31 | 2021-07-09 | 山东东岳高分子材料有限公司 | Air bubble dispersing coating with ion conduction function and preparation method thereof |
| 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 |
| CN111188060B (en) * | 2019-12-31 | 2021-08-10 | 山东东岳高分子材料有限公司 | Diaphragm of reinforced low-resistance chlor-alkali electrolytic cell and preparation method thereof |
| CN111188064B (en) * | 2019-12-31 | 2021-07-09 | 山东东岳高分子材料有限公司 | Enhanced perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4297196A (en) * | 1980-03-17 | 1981-10-27 | Hooker Chemicals & Plastics Corp. | Stable low voltage microporous diaphragm for electrolytic cells |
| US4437951A (en) * | 1981-12-15 | 1984-03-20 | E. I. Du Pont De Nemours & Co. | Membrane, electrochemical cell, and electrolysis process |
| CN87104168A (en) * | 1986-06-13 | 1987-12-23 | 旭硝子株式会社 | Be used for electrolytic ion-exchange membrane |
| CN1062382A (en) * | 1990-09-27 | 1992-07-01 | 旭硝子株式会社 | Fluorine-containing cationic exchange membrane and the application in electrolysis thereof |
| CN1624202A (en) * | 2003-12-05 | 2005-06-08 | 山东东岳高分子材料有限公司 | Perfluoro ion exchange solvation reinfercing film and its preparation method |
| CN101220168A (en) * | 2007-12-24 | 2008-07-16 | 南京航空航天大学 | Poriferous full fluorine ion switching membrane, its manufacturing method and use |
| CN101768758A (en) * | 2009-12-07 | 2010-07-07 | 山东东岳神舟新材料有限公司 | Cation permeation composite membrane for electrolysis |
-
2012
- 2012-12-14 CN CN201210540972.0A patent/CN103031566B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4297196A (en) * | 1980-03-17 | 1981-10-27 | Hooker Chemicals & Plastics Corp. | Stable low voltage microporous diaphragm for electrolytic cells |
| US4437951A (en) * | 1981-12-15 | 1984-03-20 | E. I. Du Pont De Nemours & Co. | Membrane, electrochemical cell, and electrolysis process |
| CN87104168A (en) * | 1986-06-13 | 1987-12-23 | 旭硝子株式会社 | Be used for electrolytic ion-exchange membrane |
| CN1062382A (en) * | 1990-09-27 | 1992-07-01 | 旭硝子株式会社 | Fluorine-containing cationic exchange membrane and the application in electrolysis thereof |
| CN1624202A (en) * | 2003-12-05 | 2005-06-08 | 山东东岳高分子材料有限公司 | Perfluoro ion exchange solvation reinfercing film and its preparation method |
| CN101220168A (en) * | 2007-12-24 | 2008-07-16 | 南京航空航天大学 | Poriferous full fluorine ion switching membrane, its manufacturing method and use |
| CN101768758A (en) * | 2009-12-07 | 2010-07-07 | 山东东岳神舟新材料有限公司 | Cation permeation composite membrane for electrolysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103031566A (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103031566B (en) | Fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nano-pore canal and preparation method thereof | |
| CN102978654B (en) | Low-resistance and high-strength ion exchange membrane for chlor-alkali industry and preparation method of low-resistance and high-strength ion exchange membrane | |
| CN103014757B (en) | Hole-containing fiber reinforced ion exchange membrane for chlor-alkali industry and preparation method thereof | |
| CN103556179B (en) | High current density perfluorinated ion-exchange membrane of carbon nano-tube modification and preparation method thereof | |
| CN101773788B (en) | Fluorine-containing ion exchange membrane with reinforced sacrificial fiber mesh cloth | |
| CN101768758B (en) | Cation permeation composite membrane for electrolysis | |
| CN104388978A (en) | Micro-nano pore-containing chlorine-alkali ion membrane preparation method | |
| CN103540951B (en) | A kind of ion exchange membrane for oxygen cathode electrolysis and preparation method thereof | |
| EP3527697B1 (en) | Diaphragm for electrolyzing alkaline water, and device for electrolyzing alkaline water | |
| CN104018180A (en) | Zero-polar-distance ion exchange membrane and preparation method thereof | |
| CN103515640B (en) | A kind of carbon nanofiber-reinforcedproton proton exchange membrane and preparation method thereof | |
| CN104018181B (en) | Ionic conduction membrane for chlor-alkali industry and preparation method thereof | |
| EP3348674A1 (en) | Production method for ion exchange membrane for alkali chloride electrolysis and production method for alkali chloride electrolysis device | |
| CN103556178B (en) | For the ion-exchange membrane and preparation method thereof of superhigh-current-density oxygen cathode electrolysis | |
| CN103464009B (en) | Ethylene-tetrafluoroethylene (ETFE) copolymer porous membrane and preparation method thereof | |
| CN111188065A (en) | Enhanced perfluorinated sulfonic acid ion exchange membrane for chloride electrolysis and preparation method thereof | |
| CN101811359A (en) | Preparation method and equipment of unequal-width multilayer composite ionic membrane | |
| EP3348675B1 (en) | Production method for ion exchange membrane for alkali chloride electrolysis and production method for alkali chloride electrolysis apparatus | |
| CN104134812B (en) | Fiber-net-reinforced polymer electrolyte membrane and preparation method thereof | |
| CN110699706A (en) | Fluoride ion exchange membrane for alkali chloride electrolysis | |
| CN111921567A (en) | Enhanced perfluorinated sulfonic acid ion exchange membrane and preparation method thereof | |
| CN112323095B (en) | High-strength low-cell-pressure perfluorinated ion exchange membrane for chlor-alkali industry and preparation method thereof | |
| CN112481658A (en) | Enhanced chlor-alkali ion conduction membrane containing hollowed-out tunnel and preparation method thereof | |
| CN114959794B (en) | Diaphragm for electrolytically producing chemicals | |
| CN112430831B (en) | Ion exchange membrane suitable for zero-polar-distance electrolytic cell and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180404 Address after: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park Patentee after: Shandong Dongyue future hydrogen energy materials Co., Ltd. Address before: 256401 Shandong Dongyue high molecular material Co., Ltd., Tangshan Town, Huantai County, Zibo City, Shandong Province Patentee before: Shandong Dongyue Polymer Material Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200507 Address after: 256401 Tangshan Town, Huantai County, Zibo, Shandong Patentee after: SHANDONG DONGYUE POLYMER MATERIAL Co.,Ltd. Address before: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park Patentee before: Shandong Dongyue future hydrogen energy materials Co.,Ltd. |