CN104388978A - Micro-nano pore-containing chlorine-alkali ion membrane preparation method - Google Patents
Micro-nano pore-containing chlorine-alkali ion membrane preparation method Download PDFInfo
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Abstract
The present invention relates to a micro-nano pore-containing chlorine-alkali ion membrane preparation method, which comprises: adopting monovalent alkali metal chloride MCl ultra-fine powder as a sacrifice core material, adding to a perfluorosulfonic acid resin powder material, completely mixing, carrying out melting extrusion to obtain a MCl-containing perfluorosulfonic acid resin master batch, carrying out a melting co-extrusion or multi-layer hot pressing compounding process on the MCl-containing perfluorosulfonic acid resin master batch and the perfluorosulfonic acid resin to prepare a perfluorinated ion exchange resin base film, placing a reinforcing mesh cloth into the surface or the internal of the prepared perfluorinated ion exchange resin base film to form a reinforced ion membrane, carrying out hydrolysis transformation, carrying out double side spraying on the transformed ion membrane to form a gas release coating, and carrying out standing aging in a sodium hydroxide aqueous solution to obtain the finished product. The membrane can be used for the ion exchange membrane in the chlorine-alkali industry, especially for the 6-8 kA/m<2> ultra-high current density chlorine-alkali electrolysis process, and has the good mechanical property and the good electrochemical property.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole and preparation method thereof particularly.
Background technology
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.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.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 " sacrificial fiber ".So-called " sacrificial fiber ", 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 sacrificial fiber to be suitable for high electric 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 microns, the perfluorinated sulfonic resin rete of 90 ~ 120 microns, 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 front in 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.
Therefore, utilize superfine powdery material in film, manufacture discrete passage, become the effective ways addressed this problem.Superfine powder (also known as micro Nano material) comprises nano-particle material, submicron material and micro materials.Nano-particle material is also called ultrafine particle material, be made up of nanoparticle (nano particle), generally refer to the particle of size between 1nm ~ 100nm, it is the transitional region being in cluster and macro object boundary, from common about microcosmic and macroscopical viewpoint, such system is atypical microscopic system also atypical macrosystem both, and be a kind of typical Mesoscopic structure, it has surface effects, small-size effect and macro quanta tunnel effect.Usually, submicron material particle size diameter 100nm ~ 1.0 μm, micro materials particle size diameter 1.0 μm ~ 100 μm.On the other hand, in film, manufacture the optional autopolyester fiber of sacrifice core of discrete passage, tynex or carbonate (calcium).But, find through long-term research, due in ionic membrane containing sulfonic group, the existence of bivalent metal carbonate inevitably causes the ligand complex of divalent-metal ion and sulfonic acid group or chelating to adsorb in treating processes, formation Impurity deposition and have a strong impact on the performance of chlor-alkali film.In fact, chlorine industry is very strict to the requirement of salt solution impurity in producing, see Zhang Haichao, Xu Zhengliang.In salt solution, foreign ion is to the research [J] of ion-exchange membrane performance impact. Chinese chlor-alkali, 2013,12:5-8.Generally (calcium+magnesium) content of impurities does not allow more than 20ppb.Therefore, adopting carbonate to prepare chlor-alkali film as pore former must be prudent in dealing with to residual ion, prevents divalence and polyvalent metal ion from film, forming Impurity deposition.
Summary of the invention:
For the deficiency having now technology, the object of this invention is to provide a kind of preparation method of the chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole, the electro-chemical properties that prepared ion-exchange membrane has had simultaneously and physical strength.
Technical scheme of the present invention is as follows:
Containing a preparation method for the chlorine industry fiber reinforcement ion-exchange membrane of micro-nano hole, comprise step as follows:
(1) with the superfine powder of monovalent base metal chloride MCl for sacrificing core, MCl superfine powder is added in perfluorinated sulfonic resin powder, fully after mixing by melt extruding the perfluorinated sulfonic resin master batch containing MCl obtained;
Wherein, in the quality of perfluorinated sulfonic resin powder, described MCl superfine powder accounting is 1 ~ 45wt%;
Described MCl superfine powder is selected from the sodium-chlor of particle diameter 10nm ~ 50 μm, Repone K, the powder granule of lithium chloride or hollow structure powder;
(2) by the perfluorinated sulfonic resin containing MCl obtained for step (1) and perfluorinated carboxylic acid resin, perfluorinated ion exchange resin basement membrane is made by the technique of melting co-extrusion or multi hot press compound;
(3) employing continous vacuum rotary drum recombining process, inserts the obtained ion exchange fluoro resin membrane surface of step (2) or inner formation enhancing ionic membrane by strengthening screen cloth;
(4) the hydrolyzed solution hydrolysis enhancing ionic membrane that step (3) is obtained being placed in 90 DEG C makes the transition for 3 ~ 12 hours;
(5) with the lower alcohol dispersion liquid containing massfraction 3 ~ 10% perfluorinated sulfonic resin, 5 ~ 15% nano-oxides, double-face spray painting is carried out to the ionic membrane after transition, after dry, form air release coating;
(6) step (5) being sprayed complete film is immersed in massfraction 0.2% ~ 2% aqueous sodium hydroxide solution, leaves standstill aging 2 ~ 24 hours, namely obtains the chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole of the present invention.
The multilayer complex films be made up of perfluorosulfonic acid ion exchange resin layer, perfluorinated carboxylic acid ion-exchange resin's layer, enhancing screen cloth and gas release coat containing the chlorine industry fiber reinforcement ion-exchange membrane of micro-nano hole of the present invention.
Preferred according to the present invention, in step (1), described MCl superfine powder is particle diameter 20nm ~ 20 μm sodium chloride particles; Preferably, in the quality of perfluorinated sulfonic resin powder, described MCl superfine powder accounting is 5 ~ 18%.
Preferably, in step (1), described perfluorinated sulfonic resin exchange capacity is 0.9 ~ 1.20mmo1/g.In step (2), described perfluorinated carboxylic acid resin's loading capacity is 0.9 ~ 1.15mmo1/g.
Preferred according to the present invention, making the basement membrane total thickness of perfluorinated ion-exchange membrane described in step (2) between 90-190 micron, wherein, is 6-12:1 containing the perfluorinated sulfonic resin of MCl and the Thickness Ratio of perfluorinated carboxylic acid resin's layer, preferred 9-11:1.
Further preferably, the basement membrane total thickness 100-135 micron of perfluorinated ion-exchange membrane is made described in step (2); Wherein, the perfluorinated sulfonic resin thickness containing MCl is 92 ~ 120 microns, and perfluorinated carboxylic acid resin's layer thickness is 8 ~ 15 microns.
Preferred according to the present invention, in step (4), described hydrolyzed solution is the mixing solutions of the aqueous solution of KOH or NaOH of massfraction 15% ~ 25% and organic solvent 95:5 ~ 60:40 by volume; Described organic solvent is the one in ethanol, Virahol or dimethyl sulfoxide (DMSO) (DMSO).
Preferred according to the present invention, in step (5), described nano-oxide is selected from zirconium white (ZrO
2) nano powder, titanium dioxide (TiO
2) nano powder or aluminum oxide (Al
2o
3) one in nano powder or combination, described lower alcohol is ethanol, propyl alcohol or Virahol.Air release coat-thickness is 5 ~ 10 microns.Perfluorinated sulfonic resin described in step (5) is identical with the perfluorinated sulfonic resin of step (1).
The raw material used in the method for the invention described above is prior art, and perfluorinated sulfonic resin is the perfluorinated sulfonic resin that obtains of tetrafluoroethylene and the copolymerization of perfluor sulfonyl base vinyl ether preferably.Such as: perfluor 3,6-dioxa-4-methyl-7-octene sulfonyl fluoride, structural formula is: CF
2=CFOCF
2cF (CF
3) OCF
2cF
2sO
2f; Exchange capacity is 0.9 ~ 1.20mmo1/g.Perfluorinated carboxylic acid resin, adopts 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, such as: perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters, structural formula is: CF
2=CFOCF
2cF (CF
3) OCF
2cF
2cOOCH
3; Loading capacity is 0.9 ~ 1.15mmo1/g.
One or more in the Ion Exchange Fiber that described fortifying fibre is selected from tetrafluoroethylene (PTFE) fiber, prepared by perfluoroethylene-propylene fiber, CN101003588, poly-perfluoro propyl vinyl ether fiber, tetrafluoroethylene-perfluoro vinyl ether co-polymer fiber fluorocarbon polymer fiber.
Chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole of the present invention, may be used for, on Membrane Used In Chlor-alkali Cell electrolyzer general at present, being particularly useful for superhigh-current-density (6 ~ 10kA/m
2even higher) chloric alkali electrolysis technique.
Feature of the present invention: the present invention selects the powder granule of the villaumite sodium-chlor of monovalent metal, Repone K, lithium chloride or hollow structure powder to do to sacrifice core; sodium-chlor, Repone K, lithium chloride except have good water-soluble except; its superfine powder also has excellent high high-temp stability simultaneously; therefore can keep solid shape in the course of processing, corresponding micro-nano hole can be left upon dissolution.And there is not any reaction in the material such as sulfonic acid, carboxylic acid in the villaumite of monovalent metal and film, can meet the requirement of chlorine industry to foreign ion in salt solution.By step (4) ion exchange resin conversion become and sacrifice core in the process of the ion-exchange membrane with ion exchanging function and also decompose.
The invention has the beneficial effects as follows:
1, the chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole 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 micro-nano hole of the present invention, containing more micro-nano hole, there is higher porosity in other words, decrease the transmission resistance of ion and water, thus reduce the bath voltage of film, this means can be more energy-conservation with this film, may be used for superhigh-current-density (6 ~ 10kA/m
2even higher) electrolysis process.
3, the chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole of the present invention, its preparation technology avoids the enhancing screen cloth using expensive band sacrificial fiber, and adopt inorganic nano material in conjunction with enhancing screen cloth cheap and easy to get, greatly reduce manufacturing cost, avoid harsh weaving condition.
4, the chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole of the present invention, solubilized superfine powder used has higher melt temperature (sodium-chlor fusing point 801 DEG C), its micro-nano structure can not be destroyed in film process, is conducive to the stability maintaining micro-nano hole.
5, the chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole of the present invention, solubilized superfine powder used has good solubility energy, dissolution rate at normal temperatures and pressures in the aqueous solution is fast, avoids chemical decomposition process, can not pollute film itself simultaneously.
6, the chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole of the present invention, its preparation technology adopts inorganic micro-nano salt material soluble in water, has both simplified manufacturing course and has again reduced production cost.
Accompanying drawing explanation
Fig. 1 is the cross section structure schematic diagram of the chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole prepared by the present invention.Wherein, 1 is perfluorinated carboxylic acid resin's layer, and 2 is perfluorinated sulfonic resin layer, and 3 is micro-nano hole, 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.
Embodiment 1:
A. the preparation of resin granular material
Perfluorinated sulfonic resin is the powder that tetrafluoroethylene and the copolymerization of perfluor 3-oxa--4-butylene sulfonic acid fluoride obtain, loading capacity is 0.99mmol/g, the sodium chloride particle of median size 60nm (can be prepared by literature method: Zhang Li, Cheng Humin, Ma Jiming. the preparation [J] of NaCl nanoparticle in Nonaqueous reverse microemulsions. Acta PhySico-Chimica Sinica, 2002,18 (01): 79-81.) with above-mentioned perfluorinated sulfonic resin powder in mass ratio 9:100 melt extrude the pellet of perfluorinated sulfonic resin that granulation obtains containing nanometer sodium chloride particle after fully mixing.
Adopt the powder that tetrafluoroethylene and the copolymerization of perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters obtain, obtain the pellet of perfluorinated carboxylic acid resin through melt extruding granulation, loading capacity is 0.95mmol/g.
B. the preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, perfluorinated sulfonic resin pellet containing nanometer sodium chloride particle, prepare perfluorinated ion exchange resin basement membrane by melting coextrusion processes; Then adopt continous vacuum rotary drum recombining process PTFE to be strengthened screen cloth and insert perfluorinated ion exchange resin basement membrane inner perfluorinated sulfonic resin side formation enhancing ionic membrane;
The basement membrane total thickness of perfluorinated ion-exchange membrane is at 120 microns.Wherein, be 110 microns containing nanometer sodium chloride particle perfluorinated sulfonic resin thickness, perfluorinated carboxylic acid resin's layer thickness is 10 microns.PTFE strengthens screen cloth and accounts for perfluorinated sulfonic resin mass ratio 1%.
C. transition of film and surface treatment
Above gained enhancing ionic membrane is hydrolyzed in the massfraction 25%KOH aqueous solution-Virahol (85:15 volume ratio) solution of 90 DEG C and within 6 hours, makes the transition.With containing massfraction 5% perfluorinated sulfonic resin, 12wt%ZrO
2the alcohol dispersion liquid of nano powder carries out double-face spray painting to dried ionic membrane transition, forms air release coating (coat-thickness about 8 microns) after dry; 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 micro-nano hole of the present invention after aging 24 hours.
Ionic membrane tensile strength prepared by the present embodiment is 42MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 5.5kA/m
2current density under, negative electrode NaOH solution quality enters groove salt solution NaCl concentration 305g/L than concentration 32%, anode, go out the condition of groove salt solution NaCl concentration 210g/L, groove temperature 85 ~ 87 DEG C, activated cathode, 1mm pole span under test, bath voltage is 2.91 ~ 2.93V, current efficiency 97.8%.
Embodiment 2:
(1) preparation of resin granular material
Perfluorinated sulfonic resin is tetrafluoroethylene, R 1216 and perfluor 3, the powder that the copolymerization of 6-dioxa-4-methyl-7-octene sulfonyl fluoride obtains, loading capacity is 1.06mmol/g, melt extrudes pellet that granulation obtain perfluorinated sulfonic resin containing solubilized superfine powder after fully being mixed by the Repone K powder (solubilized superfine powder) of particle diameter 100nm ~ 10 μm with above-mentioned perfluorinated sulfonic resin powder (mass ratio 15:100).Adopt the powder that tetrafluoroethylene and the copolymerization of perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters obtain, loading capacity is 0.97mmol/g, obtains the pellet of perfluorinated carboxylic acid resin through melt extruding granulation.
(2) preparation of film and enhancing
Adopting the perfluorinated sulfonic resin pellet of above-mentioned perfluorinated carboxylic acid resin's pellet, described chloride containing potassium powder, obtaining perfluorocarboxylic acid and perfluorosulfonic acid ion exchange resin membrane respectively by melt extruding; Then adopt multi hot press compound again PTFE to be strengthened screen cloth and insert perfluorinated ion exchange resin basement membrane inside formation enhancing ionic membrane;
The basement membrane total thickness of perfluorinated ion-exchange membrane is at 105 microns.Wherein, be 96 microns containing nanometer sodium chloride particle perfluorinated sulfonic resin thickness, perfluorinated carboxylic acid resin's layer thickness is 9 microns.PTFE strengthens screen cloth and accounts for perfluorinated sulfonic resin mass ratio 0.5%.
(3) transition of film and surface treatment
The hydrolysis in the massfraction 15%KOH aqueous solution-DMSO mixing solutions (volume ratio 80:20) of 90 DEG C of step (2) gained ionic membrane is made the transition for 12 hours.With containing massfraction 5% perfluorinated sulfonic resin, 9% nanometer ZrO
2virahol dispersion liquid double-face spray painting is carried out to dried ionic membrane transition, form air release coating (coat-thickness about 12 microns) after dry; Spraying complete film is immersed in 2% potassium hydroxide aqueous solution, leaves standstill and namely obtains the chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole of the present invention after aging 4 hours.
Ionic membrane tensile strength prepared by the present embodiment is 41MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 6.5kA/m
2current density under, negative electrode KOH solution quality enters groove salt solution KCl concentration 300g/L than concentration 32%, anode, go out the condition of groove salt solution KCl concentration 202g/L, groove temperature 85 ~ 87 DEG C, activated cathode, zero pole span under test, bath voltage is 2.97 ~ 3.00V, current efficiency 97.9%.
Embodiment 3:
Step (1), step (2) are identical with embodiment 1 with step (3), the hollow structure sodium-chlor powder being 100nm ~ 10 μm unlike the median size of solubilized superfine powder in step (1) (can be prepared by literature method: Tao Yuhong etc., the superfine sodium chloride powder preparation of hollow structure and surface analysis, inorganic chemicals industry, 2010,42 (7): 31 ~ 33).
Ionic membrane tensile strength prepared by the present embodiment is 39MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 7.5kA/m
2current density under, negative electrode NaOH solution quality enters groove salt solution NaCl concentration 305g/L than concentration 32%, anode, go out the condition of groove salt solution NaCl concentration 203g/L, groove temperature 85 ~ 87 DEG C, activated cathode, 1mm pole span under test, bath voltage is 3.13 ~ 3.16V, current efficiency 96.8%.
Embodiment 4:
As described in Example 1, unlike, described sodium-chlor nano particle and perfluorinated sulfonic resin powder in mass ratio 20:100 melt extrude the pellet that granulation obtains the perfluorinated sulfonic resin containing solubilized superfine powder after fully mixing.
Ionic membrane tensile strength prepared by the present embodiment is 43MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 7.0kA/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 3.15 ~ 3.18V, current efficiency 96.9%.
Embodiment 5:
As described in Example 2, unlike, solubilized superfine powder used be the Repone K powder of particle diameter 100nm ~ 1 μm.
Ionic membrane tensile strength prepared by the present embodiment is 45MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 7.8kA/m
2current density under, negative electrode KOH solution quality enters groove salt solution KCl concentration 305g/L than concentration 32%, anode, go out the condition of groove salt solution KCl concentration 205g/L, groove temperature 85 ~ 87 DEG C, activated cathode, zero pole span under test, bath voltage is 3.09 ~ 3.12V, current efficiency 97.7%.
Embodiment 6:
As described in Example 2, unlike, by the potassium chloride particle of particle diameter 100nm ~ 20 μm and described perfluorinated sulfonic resin powder in mass ratio 18:100 melt extrude the pellet that granulation obtains the perfluorinated sulfonic resin containing solubilized superfine powder after fully mixing.
Ionic membrane tensile strength prepared by the present embodiment is 44MPa, may be used for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 8.5kA/m
2current density under, negative electrode NaOH solution quality enters groove salt solution NaCl concentration 305g/L than concentration 32%, anode, go out the condition of groove salt solution NaCl concentration 205g/L, groove temperature 85 ~ 87 DEG C, activated cathode, zero pole span under test, bath voltage is 3.23 ~ 3.25V, current efficiency 97.7%.
Claims (10)
1., containing a chlorine industry preparation method for fiber reinforcement ion-exchange membrane for micro-nano hole, comprise step as follows:
(1) with the superfine powder of monovalent base metal chloride MCl for sacrificing core, MCl superfine powder is added in perfluorinated sulfonic resin powder, fully after mixing by melt extruding the perfluorinated sulfonic resin master batch containing MCl obtained;
Wherein, in the quality of perfluorinated sulfonic resin powder, described MCl superfine powder accounting is 1 ~ 45wt%;
Described MCl superfine powder is selected from the sodium-chlor of particle diameter 10nm ~ 50 μm, Repone K, the powder granule of lithium chloride or hollow structure powder;
(2) by the perfluorinated sulfonic resin containing MCl obtained for step (1) and perfluorinated carboxylic acid resin, perfluorinated ion exchange resin basement membrane is made by the technique of melting co-extrusion or multi hot press compound;
(3) employing continous vacuum rotary drum recombining process, inserts the obtained ion exchange fluoro resin membrane surface of step (2) or inner formation enhancing ionic membrane by strengthening screen cloth;
(4) the hydrolyzed solution hydrolysis enhancing ionic membrane that step (3) is obtained being placed in 90 DEG C makes the transition for 3 ~ 12 hours;
(5) with the lower alcohol dispersion liquid containing massfraction 3 ~ 10% perfluorinated sulfonic resin, 5 ~ 15% nano-oxides, double-face spray painting is carried out to the ionic membrane after transition, after dry, form air release coating;
(6) step (5) being sprayed complete film is immersed in massfraction 0.2% ~ 2% aqueous sodium hydroxide solution, leaves standstill aging 2 ~ 24 hours, namely obtains the chlorine industry fiber reinforcement ion-exchange membrane containing micro-nano hole of the present invention.
2. the chlorine industry preparation method of fiber reinforcement ion-exchange membrane containing micro-nano hole as claimed in claim 1, it is characterized in that in step (1), described MCl superfine powder is particle diameter 20nm ~ 20 μm sodium chloride particles.
3. the chlorine industry preparation method of fiber reinforcement ion-exchange membrane containing micro-nano hole as claimed in claim 1, it is characterized in that in step (1), in the quality of perfluorinated sulfonic resin powder, described MCl superfine powder accounting is 5 ~ 18%.
4. the chlorine industry preparation method of fiber reinforcement ion-exchange membrane containing micro-nano hole as claimed in claim 1, is characterized in that, in step (1), described perfluorinated sulfonic resin exchange capacity is 0.9 ~ 1.20mmo1/g; In step (2), described perfluorinated carboxylic acid resin's loading capacity is 0.9 ~ 1.15mmo1/g.
5. the preparation method of chlorine industry with fiber reinforcement ion-exchange membrane containing micro-nano hole as claimed in claim 1, it is characterized in that in step (2), the described basement membrane total thickness making perfluorinated ion-exchange membrane is between 90-190 micron, wherein, be 6-12:1 containing the perfluorinated sulfonic resin of MCl and the Thickness Ratio of perfluorinated carboxylic acid resin's layer.
6. the chlorine industry preparation method of fiber reinforcement ion-exchange membrane containing micro-nano hole as claimed in claim 1, is characterized in that in step (2), described in make perfluorinated ion-exchange membrane basement membrane total thickness be 100-135 micron.Wherein, the perfluorinated sulfonic resin thickness containing MCl is 92 ~ 120 microns, and perfluorinated carboxylic acid resin's layer thickness is 8 ~ 15 microns.
7. the preparation method of chlorine industry with fiber reinforcement ion-exchange membrane containing micro-nano hole as claimed in claim 1, it is characterized in that in step (4), described hydrolyzed solution is the mixing solutions of the aqueous solution of KOH or NaOH of massfraction 15% ~ 25% and organic solvent 95:5 ~ 60:40 by volume; Described organic solvent is the one in ethanol, Virahol or dimethyl sulfoxide (DMSO) (DMSO).
8. the preparation method of chlorine industry with fiber reinforcement ion-exchange membrane containing micro-nano hole as claimed in claim 1, it is characterized in that in step (5), described nano-oxide is selected from one in zirconia nano-powder, titanic oxide nano or alumina nano powder or combination.
9. the chlorine industry preparation method of fiber reinforcement ion-exchange membrane containing micro-nano hole as claimed in claim 1, is characterized in that, in step (5), described lower alcohol is ethanol, propyl alcohol or Virahol.
10. the chlorine industry preparation method of fiber reinforcement ion-exchange membrane containing micro-nano hole as claimed in claim 1, is characterized in that, in step (5), air release coat-thickness is 5 ~ 10 microns.
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| CN111188060A (en) * | 2019-12-31 | 2020-05-22 | 山东东岳未来氢能材料有限公司 | Diaphragm of reinforced low-resistance chlor-alkali electrolytic cell and preparation method thereof |
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| CN112323095A (en) * | 2020-09-24 | 2021-02-05 | 山东东岳高分子材料有限公司 | High-strength low-cell-pressure perfluorinated ion exchange membrane for chlor-alkali industry and preparation method thereof |
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| CN110923748A (en) * | 2019-11-27 | 2020-03-27 | 山东东岳高分子材料有限公司 | Ion exchange membrane with cross-linked structure on surface for alkali metal electrolysis and preparation method thereof |
| CN110923748B (en) * | 2019-11-27 | 2021-05-28 | 山东东岳高分子材料有限公司 | Ion exchange membrane with cross-linked structure on surface for alkali metal electrolysis and preparation method thereof |
| CN111188060A (en) * | 2019-12-31 | 2020-05-22 | 山东东岳未来氢能材料有限公司 | Diaphragm of reinforced low-resistance chlor-alkali electrolytic cell 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 |
| 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 |
| CN112323095A (en) * | 2020-09-24 | 2021-02-05 | 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 |
| CN112430831A (en) * | 2020-09-24 | 2021-03-02 | 山东东岳高分子材料有限公司 | Ion exchange membrane suitable for zero-polar-distance electrolytic cell 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 |
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