CN102978654B - 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
- Publication number
- CN102978654B CN102978654B CN201210545793.6A CN201210545793A CN102978654B CN 102978654 B CN102978654 B CN 102978654B CN 201210545793 A CN201210545793 A CN 201210545793A CN 102978654 B CN102978654 B CN 102978654B
- Authority
- CN
- China
- Prior art keywords
- nanometer
- exchange membrane
- ion
- membrane
- ion exchange
- 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 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 low resistance high strength ionic exchange membrane 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
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 perfluorinated sulfonic acid 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, surface does not have functional inorganics to improve the conductivity of film yet simultaneously.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 current density natural circulation groove.
CN200910231445 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 certainly.This is continuous in the film due to sacrificial fiber and dense distribution, and 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 chlorine industry low resistance high strength ionic exchange membrane and preparation method thereof, the perfluorinated ion that this film strengthens containing multiple nano pore, screen cloth exchanges composite membrane, has better electro-chemical properties and physical strength simultaneously.
Terminological interpretation:
Nano material of the present invention all refers to that the diameter of filamentary material or the particle diameter of particle are nano level; Multiple nano pore refers to that as microscler and hollow ball shape, microscler duct diameter dimension is that nano level is called nano pore simultaneously containing at least two kinds of difform holes; The diameter of hollow ball shape hole is nano level, is called 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 made up of perfluorosulfonic acid ion exchange resin layer, perfluorinated carboxylic acid ion-exchange resin's layer, enhancing screen cloth and gas release coat; Wherein the perfluorinated sulfonic resin layer of thickness 80-150 micron and perfluorinated carboxylic acid resin's layer of thickness 8-12 micron form perfluorinated ion exchange resin basement membrane, and two outer surfaces of film all have the air release coating of 3-12 micron thickness; Fortifying fibre screen cloth is placed in perfluorinated sulfonic resin layer, also has nano pore and nanometer hole in perfluorinated sulfonic resin layer.
Described nano pore and nanometer hole are that the mixing nanometer expendable material contained in perfluorinated sulfonic resin in film preparation process decomposes or sacrifices the rear hole formed.Described mixing nanometer expendable material is the combination of nanometer sacrificial fiber and nano inorganic particle arbitrary proportion, wherein nanometer sacrificial fiber is selected from one of nanometer ethylene glycol terephthalate (PET) fiber, PA 66 (nylon66 fiber) fiber or combination, diameter 1-200 nanometer, length 1-30 micron; Nano inorganic particle is 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 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 0.9-1.00mmo1/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 0.88-1.05mmo1/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 0.9-1.00mmo1/g.
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 or propyl alcohol or Virahol, nano inorganic oxide optional ZnO, 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), gathers one or more in perfluoro propyl vinyl ether fiber, tetrafluoroethylene-perfluoro vinyl ether co-polymer fiber fluorocarbon polymer fiber.
According to the present invention, a kind of preparation method of chlorine industry low resistance high strength ionic exchange membrane, comprises step as follows:
A, the perfluorinated sulfonic resin adopting perfluorinated carboxylic acid resin, contain mixing nanometer expendable material, prepare perfluorinated ion exchange resin basement membrane by the technique of melting coextrusion or multi hot press compound;
Described mixing nanometer expendable material is the combination of nanometer sacrificial fiber and nano inorganic particle arbitrary proportion, wherein nanometer sacrificial fiber is selected from one of nanometer ethylene glycol terephthalate (PET) fiber, PA 66 (nylon66 fiber) fiber or combination, diameter 1-200 nanometer, length 1-30 micron; Nano inorganic particle is nano-carbonate powder, is preferably nano-calcium carbonate, 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 obtained basement membrane of step a, adopt continous vacuum recombining process fortifying fibre screen cloth is inserted indistinct close nanometer expendable material perfluorinated sulfonic resin layer surface or inner formation 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 hour make the transition; And the mixing nanometer expendable material point to take off in film, nanometer sacrificial fiber divide take off after in film, form nano pore, nano inorganic particle breakdown falls in film to be formed nanometer hole.
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 hour, take out.Namely chlorine industry low resistance high strength ionic exchange membrane of the present invention is obtained.
In above-mentioned steps a, mixing nanometer expendable material and perfluorinated sulfonic resin powder quality ratio are preferably 4 ~ 10:100, by melt extruding the perfluorinated sulfonic resin master batch obtained containing mixing nanometer expendable material after fully mixing.
In above-mentioned steps a, nano-carbonate is preferably nano-calcium carbonate, particle diameter 20-100 nanometer.
In above-mentioned steps a, the mass ratio of nanometer sacrificial fiber and nano inorganic particle is (1 ~ 99): (99 ~ 1), and preferably the mass ratio of nanometer sacrificial fiber and nano inorganic particle is (30 ~ 80) further: (70 ~ 20).
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 of 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, lower alcohol is ethanol, propyl alcohol or Virahol preferably.
In above-mentioned steps a, the described perfluorinated sulfonic resin layer thickness containing mixing nanometer expendable 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.
The low resistance high strength ionic exchange membrane of the discontinuous passage containing the various shape hole such as nano aperture and hole prepared by the present invention, 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, utilize nano inorganic particulate material in film, manufacture discrete spherically-shaped cavity, 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.0.001dtex(can be obtained by the singe screw method of polyblending and be about 10nm) fiber.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 low resistance high strength chlorine industry fiber reinforcement ion-exchange membrane containing various shape nano aperture 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 low resistance high strength chlorine industry fiber reinforcement ion-exchange membrane containing various shape nano aperture of the present invention, containing multiple nano pore and hole, there is higher porosity, decrease the transmission resistance of ion and water, thus reduce the bath voltage of film, Membrane Used In Chlor-alkali Cell electrolyzer use this film more energy-conservation.
(3) ion-exchange membrane preparation technology of the present invention avoids the enhancing screen cloth using expensive band braiding sacrificial fiber, and adopts nano-fiber material in conjunction with enhancing screen cloth cheap and easy to get, reduces manufacturing cost, avoids harsh weaving condition.
Accompanying drawing explanation
Fig. 1 is the cross section structure schematic diagram of ion-exchange membrane of the present invention.Wherein, 1 is perfluorinated carboxylic acid resin's layer, and 2 is perfluorinated sulfonic resin layer, and 3A is ball shaped nano hole, and 3B is rod-like nano duct, 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.
Perfluorinated carboxylic acid resin's loading capacity in the present embodiment is 0.93mmol/g, the powder that tetrafluoroethylene and the copolymerization of perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters obtain.
(1) preparation of resin granular material
The PET of cut-off footpath 20 ± 5 nanometer, length 10 ± 2 microns and the calcium carbonate of median size 25 nanometer in mass ratio 80:20 mix, and must mix nanometer expendable material.
By described mixing nanometer expendable material and above-mentioned perfluorinated sulfonic resin powder in mass ratio 4:100 melt extrude the pellet that granulation obtains containing the perfluorinated sulfonic resin mixing nanometer expendable material after fully mixing;
Separately get above-mentioned perfluorinated carboxylic acid resin obtains perfluorinated carboxylic acid resin pellet through melt extruding granulation.
(2) preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, containing the perfluorinated sulfonic resin pellet mixing nanometer expendable material, contained the perfluorinated ion exchange resin basement membrane of perfluorinated sulfonic resin layer and perfluorinated sulfonic resin layer by the preparation of melting coextrusion processes; Perfluorinated sulfonic resin layer thickness wherein containing mixing nanometer expendable material is 110 microns, and perfluorinated carboxylic acid resin's layer thickness is 10 microns.Then PTFE is strengthened the perfluorinated sulfonic resin layer inside formation enhancing ionic membrane that this basement membrane inserted by screen cloth by employing continous vacuum recombining process;
(3) transition of film and spraying
Step (2) gained is strengthened ionic membrane hydrolysis in the KOH water-ethanol solution (ethanol content 30wt%) of the massfraction 20% of 90 DEG C within 8 hours, carry out making the transition and remove the mixing nanometer expendable material in striping, form nano pore except after the PET in striping, geomery and the PET of nano pore adapt; Form nanometer hole except after the nano-calcium carbonate in 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
2alcohol dispersion liquid double-face spray painting is carried out to the ionic membrane after transition, form 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 and namely obtains ion-exchange membrane of the present invention after aging 4 hours.
Ion-exchange membrane tensile strength prepared by the present embodiment is 31MPa, 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 3.11-3.13V, 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 nanometer expendable material is: the mixture of the calcium carbonate granule of diameter 20 ± 5 nanometer, the nylon66 fiber of long 10 ± 2 microns and median size 80 nanometer 30:70 in mass ratio.
By mixing nanometer expendable material 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, perfluorinated carboxylic acid resin's powder obtains the pellet of perfluorinated carboxylic acid resin through melt extruding granulation.
(2) preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, containing the perfluorinated sulfonic resin pellet mixing nanometer expendable material, by melt extruding the ion exchange resin basement membrane obtained respectively containing perfluorinated carboxylic acid resin's layer and perfluorinated sulfonic resin layer; Perfluorinated sulfonic resin layer thickness containing mixing nanometer expendable material is 115 microns, and perfluorinated carboxylic acid resin's layer thickness is 8 microns.
Then PTFE is strengthened the perfluorinated sulfonic resin layer inside formation enhancing ionic membrane that perfluorinated ion exchange resin basement membrane inserted by screen cloth by employing multi hot press compound again;
(3) transition of film and spraying
Step (2) gained is strengthened ionic membrane hydrolysis in the NaOH water-DMSO solution (DMSO containing 25%) of the massfraction 15% of 90 DEG C within 12 hours, to carry out making the transition and the mixing nanometer expendable material nylon 66 fiber removed in striping and calcium carbonate granule, form nano pore and hole.
(4) dry rear with containing massfraction 5% perfluorinated sulfonic resin and 12% nanometer ZrO
2virahol dispersion liquid double-face spray painting is carried out to the ionic membrane after transition, form 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 low resistance high strength chlorine industry fiber reinforcement ion-exchange membrane containing various shape nano aperture of the present invention after aging 36 hours.
Ionic membrane tensile strength prepared by the present embodiment is 35MPa, 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, zero pole span under test, 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), 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 33MPa, 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 3.10-3.12V, negative electrode alkali current efficiency 96.7%.
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.Air release coat-thickness is 4 microns.
Ionic membrane tensile strength prepared by the present embodiment is 32MPa, 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), the perfluorinated sulfonic resin loading capacity selected 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, 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 mixing expendable material and described perfluorinated sulfonic resin powder is 40:60.
Ionic membrane tensile strength prepared by the present embodiment is 23MPa, can 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), 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, 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 3.06-3.09V, negative electrode alkali current efficiency 97.5%.
Embodiment 8:
Step (1), step (2) are identical with embodiment 2 with step (3), unlike in step (1), mixing nanometer expendable material is the mixture of diameter 25 ± 5 nanometer, the long nylon66 fiber of 10 ± 2 microns and the calcium carbonate of median size 80 nanometer, mass ratio 50:50.
Ionic membrane tensile strength prepared by the present embodiment is 26MPa, 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 3.04-3.07V, negative electrode alkali current efficiency 97.4%.
Embodiment 9:
Step (1), step (2) are identical with embodiment 2 with step (3), and unlike in step (3), 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 25MPa, can 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 3.05-3.08V, negative electrode alkali current efficiency 97.2%.
Claims (9)
1. a preparation method for chlorine industry ion-exchange membrane, comprises step as follows:
A, the perfluorinated sulfonic resin adopting perfluorinated carboxylic acid resin, contain mixing nanometer expendable material, prepare perfluorinated ion exchange resin basement membrane by the technique of melting coextrusion or multi hot press compound;
Described mixing nanometer expendable material is the combination of nanometer sacrificial fiber and nano inorganic particle arbitrary proportion, wherein nanometer sacrificial fiber is selected from one of nanometer ethylene glycol terephthalate (PET) fiber, PA 66 (nylon66 fiber) fiber or combination, diameter 1-200 nanometer, length 1-30 micron; Nano inorganic particle is 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 obtained basement membrane of step a, adopt continous vacuum recombining process fortifying fibre screen cloth is inserted indistinct close nanometer expendable material perfluorinated sulfonic resin layer surface or inner formation 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 hour make the transition; And the mixing nanometer expendable material point to take off in film, nanometer sacrificial fiber divide take off after in film, form nano pore, nano inorganic particle breakdown falls in film to be formed nanometer hole;
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 hour, take out.
2. the preparation method of ion-exchange membrane as claimed in claim 1, it is characterized in that in step a, mixing nanometer expendable material is 4 ~ 10:100 with perfluorinated sulfonic resin powder quality ratio, fully obtains containing the perfluorinated sulfonic resin master batch mixing nanometer expendable material by melt extruding after mixing.
3. the preparation method of ion-exchange membrane as claimed in claim 1, it is characterized in that in step a, nano-carbonate is nano-calcium carbonate, particle diameter 20-100 nanometer.
4. the preparation method of ion-exchange membrane as claimed in claim 1, it is characterized in that in above-mentioned steps a, the mass ratio of nanometer sacrificial fiber and nano inorganic particle is (1 ~ 99): (99 ~ 1).
5. the preparation method of ion-exchange membrane as claimed in claim 1, it is characterized in that in above-mentioned steps a, the mass ratio of nanometer sacrificial fiber and nano inorganic particle is (30 ~ 80): (70 ~ 20).
6. the preparation method of ion-exchange membrane as claimed in claim 1, it is characterized in that in step c, organic solvent is ethanol, Virahol or dimethyl sulfoxide (DMSO).
7. the preparation method of ion-exchange membrane as claimed in claim 1, it is characterized in that in step c, in mixing solutions, the mass percent concentration of KOH or NaOH is 12 ~ 28%, and the mass percent concentration of organic solvent is 10 ~ 40%.
8. the preparation method of 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.
9. the preparation method of ion-exchange membrane as claimed in claim 1, is characterized in that in step a, and the described perfluorinated sulfonic resin layer thickness containing mixing nanometer expendable material is 80-150 micron, and perfluorinated carboxylic acid resin's layer thickness is 8-12 micron; In steps d, air release coat-thickness is 3-12 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210545793.6A CN102978654B (en) | 2012-12-14 | 2012-12-14 | Low-resistance and high-strength ion exchange membrane for chlor-alkali industry and preparation method of low-resistance and high-strength ion exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210545793.6A CN102978654B (en) | 2012-12-14 | 2012-12-14 | Low-resistance and high-strength ion exchange membrane for chlor-alkali industry and preparation method of low-resistance and high-strength ion exchange membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102978654A CN102978654A (en) | 2013-03-20 |
| CN102978654B true CN102978654B (en) | 2015-03-18 |
Family
ID=47852985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210545793.6A Active CN102978654B (en) | 2012-12-14 | 2012-12-14 | Low-resistance and high-strength ion exchange membrane for chlor-alkali industry and preparation method of low-resistance and high-strength ion exchange membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102978654B (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN104018180B (en) * | 2014-06-06 | 2016-10-05 | 山东东岳高分子材料有限公司 | Zero pole span amberplex and preparation method thereof |
| US20170198404A1 (en) * | 2014-06-06 | 2017-07-13 | Shandong Dongye Polymer Material Co., Ltd. | Ion-conducting membrane used in chlor-alkali industry 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 |
| CN103993329B (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 |
| CN104018181B (en) * | 2014-06-06 | 2017-01-11 | 山东东岳高分子材料有限公司 | Ionic conduction membrane for chlor-alkali industry and preparation method thereof |
| JP6434732B2 (en) * | 2014-07-24 | 2018-12-05 | 株式会社アストム | Production method of ion exchange membrane |
| 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 |
| WO2017043590A1 (en) * | 2015-09-08 | 2017-03-16 | 旭硝子株式会社 | Production method for ion exchange membrane for alkali chloride electrolysis and production method for alkali chloride electrolysis device |
| 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 |
| CA3018495C (en) * | 2017-01-27 | 2021-01-19 | Asahi Kasei Kabushiki Kaisha | Ion exchange membrane and electrolyzer |
| 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 |
| CN111020629A (en) * | 2019-12-31 | 2020-04-17 | 山东东岳未来氢能材料有限公司 | Perfluorocarboxylic acid ion exchange membrane with bubble-dispelling function and preparation method thereof |
| CN111074298B (en) * | 2019-12-31 | 2021-11-05 | 山东东岳高分子材料有限公司 | Perfluorosulfonic acid ion exchange membrane for chloride electrolysis and preparation method thereof |
| CN111020630B (en) * | 2019-12-31 | 2021-07-13 | 山东东岳高分子材料有限公司 | Ultrathin perfluorocarboxylic acid ion exchange membrane with bubble-dispelling function and preparation method thereof |
| CN111118542B (en) * | 2019-12-31 | 2021-07-09 | 山东东岳高分子材料有限公司 | Ultrathin perfluorocarboxylic acid ion exchange membrane with rough coating and preparation method thereof |
| CN111074299B (en) * | 2019-12-31 | 2021-07-13 | 山东东岳高分子材料有限公司 | Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali metal chloride electrolysis 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 |
| CN111101152B (en) * | 2019-12-31 | 2021-07-09 | 山东东岳高分子材料有限公司 | Perfluorocarboxylic acid ion exchange membrane with rough coating and preparation method thereof |
| CN111188051A (en) * | 2019-12-31 | 2020-05-22 | 山东东岳未来氢能材料有限公司 | Novel ultra-thin low-resistance ion conduction membrane for chlor-alkali industry and preparation method thereof |
| CN111118541B (en) * | 2019-12-31 | 2021-07-09 | 山东东岳高分子材料有限公司 | Ultrathin low-resistance chlor-alkali perfluorinated ion exchange membrane 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 |
| 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 |
| 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 |
| CN112481658A (en) * | 2020-11-26 | 2021-03-12 | 山东东岳高分子材料有限公司 | Enhanced chlor-alkali ion conduction membrane containing hollowed-out tunnel and preparation method thereof |
| CN112606255B (en) * | 2020-11-30 | 2023-03-24 | 山东东岳未来氢能材料股份有限公司 | Processing method of ion exchange resin applied to catalysis field |
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 CN201210545793.6A patent/CN102978654B/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 |
|---|---|
| CN102978654A (en) | 2013-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| 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 | |
| CN103031566B (en) | Fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nano-pore canal and preparation method thereof | |
| 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 | |
| KR102112648B1 (en) | Polymer electrolyte membrane | |
| CN101768758B (en) | Cation permeation composite membrane for electrolysis | |
| CN105355949B (en) | A kind of preparation method of micro nanometer fiber compound proton exchange membrane | |
| CN104388978A (en) | Micro-nano pore-containing chlorine-alkali ion membrane preparation method | |
| CN104018181B (en) | Ionic conduction membrane for chlor-alkali industry and preparation method thereof | |
| US20170198405A1 (en) | Zero polar distance ion exchange membrane and preparation method thereof | |
| CN103540951B (en) | A kind of ion exchange membrane for oxygen cathode electrolysis and preparation method thereof | |
| CN103515640B (en) | A kind of carbon nanofiber-reinforcedproton proton exchange membrane and preparation method thereof | |
| CN103993329A (en) | Ion-conducting membrane and preparation method thereof | |
| CN103556178B (en) | For the ion-exchange membrane and preparation method thereof of superhigh-current-density oxygen cathode electrolysis | |
| CN110699706B (en) | Fluoride ion exchange membrane for alkali chloride electrolysis | |
| Goo et al. | Polyamide-coated Nafion composite membranes with reduced hydrogen crossover produced via interfacial polymerization | |
| JP6150616B2 (en) | Polymer electrolyte composition and polymer electrolyte membrane | |
| JP2005041956A (en) | Coagulation forming process and manufacturing apparatus for porous membrane | |
| TW202032840A (en) | Gas diffusion electrode, method for manufacturing gas diffusion electrode, membrane electrode assembly, and fuel cell | |
| 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 | |
| CN111921567A (en) | Enhanced perfluorinated sulfonic acid ion exchange membrane 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 | |
| KR102018538B1 (en) | A Separator for Zn-Br Redox Flow Battery, Manufacturing method thereof and A Zn-Br Redox Flow Battery containing the same |
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: 20180403 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 Tangshan, Shandong, Huantai Town, Zibo Patentee before: Shandong Dongyue Polymer Material Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200429 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. |