CN104018181B - Ionic conduction membrane for chlor-alkali industry and preparation method thereof - Google Patents
Ionic conduction membrane for chlor-alkali industry and preparation method thereof Download PDFInfo
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- CN104018181B CN104018181B CN201410251252.1A CN201410251252A CN104018181B CN 104018181 B CN104018181 B CN 104018181B CN 201410251252 A CN201410251252 A CN 201410251252A CN 104018181 B CN104018181 B CN 104018181B
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- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention belongs to the technical field of ionic membranes and particularly relates to a novel ionic conduction membrane for chlor-alkali industry. The membrane consists of a perfluorosulfonate ion-exchange resin based membrane, a porous reinforcing material and a surface layer formed by mixing microparticles of fluorine-containing resin and particles of an inorganic compound. The particles of the inorganic compound are selected from one or more of oxides, hydroxides and nitrides of group IV-A, group IV-B, group V-B, iron, cobalt, nickel, chromium, manganese or boron. The microparticles of fluorine-containing resin comprise one or more of microparticles of polytetrafluoroethylene, microparticles of PFA (Polyfluoroalkoxy), microparticles of polyfluorinated ethylene propylene, microparticles of polyfluorinated propyl vinyl ether or microparticles of polyvinylidene fluoride. The ionic conduction membrane for chlor-alkali industry can stably and efficiently treat alkali chloride solutions with wide concentration range and is suitable for operation in a zero polar distance electrolytic bath under a novel electric current density condition, so that the product purity is high. The invention further provides a preparation method of the ionic conduction membrane and the preparation method is simple and reasonable in process and easy for industrialized production.
Description
Technical field
The invention belongs to ionic membrane technical field, be specifically related to a kind of new ion conducting membranes for chlorine industry and preparation method thereof.
Background technology
In recent years, in ionic membrane method alkali-chloride produces, for realizing being electrolysed under conditions of concentration of lye height at high current density, low tank voltage, to reach the purpose improving productivity ratio with reducing power consumption, it it is critical only that shortening ionic membrane and interelectrode distance, to reduce its tank voltage, the electrolysis with ion-exchange film technique of narrow pole span type is made to reach practical.Continuous progress along with technology, zero polar distance electrolytic bath is widely used, but when interelectrode distance is reduced to less than 2mm, owing to film is close to negative electrode, and make the bubble hydrogen adhered on face be difficult to discharge, therefore on the face of negative electrode, gathering substantial amounts of bubble hydrogen.Bubble hinders current channel, makes the effectively electrolysis area of film reduce, causes CURRENT DISTRIBUTION on face uneven, and local polarisation effect substantially increases.Thus, making membrane resistance be increased dramatically with tank voltage on the contrary, its electrolytic power consumption significantly raises.
By the shortcoming overcoming bubble effect to be brought, make the bubble hydrogen of adhesion quickly discharge from the face that hydrophilic is little, develop the method for modifying of ionic membrane surface hydrophilic coating.Cover a kind of gas and the most porous porous type of liquid on film surface, without the non-electrode coating of electro catalytic activity after, make face hydrophilic substantially increase, anti-foaming ability significantly improves.The ionic membrane that hydrophilic coating is modified, can be close to electrode, greatly reduces tank voltage, is widely used in zero pole span type electrolysis with ion-exchange film technique at present.After hydrophilic coating modified technique needs by inorganic matter component and polymer agent mixture, being covered on ionic membrane surface by strike, particle implantation etc., patent CA2446448 and CA2444585 have carried out concrete introduction to coating process；Although this kind of method of modifying effect is notable, but technique is relative complex.Additionally, due to ionic membrane can experience alkaline stream in electrolysis running constantly wash away the continuous concussion caused with turbulent flow, the hydrophilic coating being attached to ionic membrane surface can gradually come off, and it is invalid that anti-foaming function is gradually decrease to.
Patent US 4502931 is mentioned and ionic membrane surface is used the method for ion etching carry out rough surfaceization modification, but the method is not only difficult to large area to be implemented, and anti-foaming ability is the highest, when anode-cathode distance is reduced to a certain degree, its groove pressure is still greater than 3.5V, and current efficiency is less than 90%.
Therefore, develop a kind of novel new ion conducting membranes for chlorine industry, its surface has permanently effective hydrophilic degassing function, and good anti-foaming effect can be persistently provided during state-of-the-art electrolysis bath and electrolysis process, reduce tank voltage, improve current efficiency, and power consumption can be reduced, have very important significance.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of new ion conducting membranes for chlorine industry, the alkali metal chloride solution of wide range of concentrations can be processed with stability and high efficiency for chlorine industry, it is suitable in zero polar distance electrolytic bath under novel high current densities running, there is the most excellent product purity index；The present invention also provides for its preparation method, technique advantages of simple, it is easy to industrialized production.
New ion conducting membranes for chlorine industry of the present invention, perfluorinated ion exchange resin basement membrane, porous reinforcing material and fluorine resin microparticle and inorganic compound particle the surface layer mixed forms.
Wherein: described perfluorinated ion exchange resin basement membrane is made up of the resin bed based on perfluorinated sulfonic resin and the resin bed based on perfluorinated carboxylic acid resin, resin layer thickness based on perfluorinated sulfonic resin is for 30-300 micron, preferably 50-150 micron, in resin tunic based on perfluorinated sulfonic resin, fixed ion content is less, and more weak to repulsive force hydroxy, thickness should not be the thinnest；Resin layer thickness based on perfluorinated carboxylic acid resin is 2-30 micron, preferably 7-18 micron, and the resin bed membrane resistance based on perfluorinated carboxylic acid resin is relatively big, and thickness is unsuitable excessive.
Resin bed based on perfluorinated sulfonic resin is that the perfluorinated sulfonic resin with mass ratio as 100:0.1-100:10 and perfluorinated carboxylic acid resin are blended or copolymerization forms；Its mass ratio is preferably 100:0.5-100:5.The perfluorinated carboxylic acid resin's a small amount of existence in the resin bed based on perfluorinated sulfonic resin but can play the transitional function of key, make weakening through gradient of the water in film and ion, the flux stability of ionic membrane is played a key effect, the stripping of different film interlayer can be prevented simultaneously.
Resin bed based on perfluorinated carboxylic acid resin is that the perfluorinated carboxylic acid resin with mass ratio as 100:0.1-100:10 and perfluorinated sulfonic resin are blended or copolymerization forms, preferably 100:0.5-100:5.The perfluorinated sulfonic resin a small amount of existence in the resin bed based on perfluorinated carboxylic acid resin also can play the crucial transitional function described in epimere.
The exchange capacity of perfluorinated sulfonic resin is 0.8-1.5 mM/gram, preferably 0.9-1.1 mM/gram；The exchange capacity of perfluorinated carboxylic acid resin is 0.8-1.2 mM/gram, preferably 0.85-1.0 mM/gram.The exchange capacity of two kinds of resins to match, and difference should not be the biggest.
The surface layer thickness that fluorine resin microparticle and inorganic compound particle mix is between 20 nanometer-100 microns, preferably 200 nanometers-2 microns.In surface layer, fluorine resin microparticle is 1:100-100:1 with the mass ratio of inorganic compound particle.Surface layer is to be mixed with inorganic compound particle by fluorine resin microparticle; experiment shows; two kinds of granules are joined under suitable proportioning and mixed are applied to surface layer; while giving the chemical property that ion-conductive membranes is excellent; it is more suitable for the acid adding process of electrolytic process; and maloperation is added excessive acid there is toleration, improve whole conductive membranes anti-protonation ability under strongly acidic conditions.Wherein: the fluorine resin microparticle a kind of or the most several mixture in politef microparticle (PTFE), PFA microparticle, perfluoroethylene-propylene microparticle (FEP), poly-perfluoro propyl vinyl ether microparticle or Kynoar microparticle (PVDF).Fluorine resin microparticle be once pulverized in cryogenic pulverization device by resin granular material after, then be ground obtaining in cryogenic system, granule is provided with irregular apparent form, and the desorption bubbled for top layer has the effect of excellence.Fluorine resin microparticle particle size range in surface layer is between 20 nanometer-10 microns, preferably 50-300 nanometer.When particle diameter is too low, granule is easily reunited, plug ion passage；When particle diameter is too high, the microgranule projection formed on film surface is excessively obvious, easily departs under external force is swiped.
The inorganic compound particle a kind of or the most several mixture in IV-A race, IV-B race, V-B race, ferrum, cobalt, nickel, chromium, manganese or the oxide of boron element, hydroxide, nitride, preferably is selected from one or more in zirconium oxide, strontium oxide, stannum oxide, ferrum oxide, titanium oxide, silicon oxide, zirconium hydroxide or zirconium nitride.Inorganic compound particle particle size range in surface layer is between 20 nanometer-10 microns, preferably 20-300 nanometer.
Porous reinforcing material is politef non-woven fabrics, fiber intersection be overlap joint or merge, porous reinforcing material thickness between 1-200 micron, preferably 10-50 micron；To improve mechanical strength, prior art is used to prepare.Described politef non-woven fabrics porosity between 20-99%, preferably 50-85%.If porosity is too low, groove pressure otherwise can be caused to raise.
New ion conducting membranes for chlorine industry of the present invention, including following preparation process:
(1) by the way of screw-type extruder coextrusion, melt curtain coating and help fluorion exchanger resin basement membrane, again porous reinforcing material is immersed in fluorine carbon solvent, supersound process 1-2 hour, take out and be combined with perfluorinated ion exchange resin basement membrane more after drying, porous reinforcing material is introduced between film forming press-roller, under the effect of roll gap pressure, porous reinforcing material is pressed in perfluorinated ion exchange resin basement membrane, thus obtains perfluorinated ion-exchange membrane precursor.
(2) the perfluorinated ion-exchange membrane precursor prepared in step (1) is converted into there is the perfluorinated ion-exchange membrane of ion exchanging function.
(3) according to 1:1 weight ratio, water and ethanol being made into mixed liquor, add fluorine resin microparticle and inorganic compound particle mixture, in ball mill, homogenization processes, and forms dispersion liquid.
(4) dispersion liquid in (3) is attached to the perfluorinated ion-exchange membrane surface that step (2) obtains, forms finished product after drying.
Wherein: porous reinforcing material is immersed in supersound process 1-2 hour in fluorine carbon solvent by step (1), take out and be combined with perfluorinated ion exchange resin basement membrane more after drying.Owing to being the most difficult to the infiltration of politef non-woven fabrics, if being directly combined with basement membrane without processing, resin matrix cannot be fully filled with the space of non-woven fabrics, thus form the leakiness space within film body, not only easy depositing contaminants, moreover it is possible to form space obstacle, increase resistance.After porous reinforcing material soaks 1-2 hour in fluorine carbon solvent, the infiltration of resin matrix is very easy, the two can be formed good, combine closely, not only increase mechanical strength, and owing to non-woven fabrics percent opening is high, the impact on film body resistance be very little.
Fluorine carbon solvent described in step (1) is selected from: trifluorotrichloroethane (F 113) or trifluorotrichloroethane mix with other solvent；Other solvent is one or more in dehydrated alcohol, propanol, methanol, acetone, dichloromethane or aqueous surfactant solution.Surfactant is selected from commercial anionic, cationic, amphoteric or nonionic surfactant.
Step (2) be by step (1) prepare perfluorinated ion-exchange membrane precursor at a temperature of 10-200 DEG C, under the pressure of 20-100 ton, superpressure machine is used to carry out superpressure process with the speed of 1-50 m/min, after superpressure processes, perfluorinated ion-exchange membrane precursor be impregnated in the mixed aqueous solution of 15wt% dimethyl sulfoxide and 20wt% NaOH, be converted into the perfluorinated ion-exchange membrane with ion exchanging function.Wherein: superpressure processes the combination degree of compaction further increasing non-woven fabrics with basement membrane, superpressure processes the physical arrangement form improving non-woven fabrics and basement membrane the most to a certain extent simultaneously, it is detailed-oriented that the fibrillation of non-woven fabrics and the hot pressing of basement membrane cause crystalline texture, can be effectively improved ion transport effect.
In step (3) fluorine resin microparticle be once pulverized in cryogenic pulverization device by resin granular material after, then be ground obtaining in cryogenic system.The fluorine resin microparticle obtained possesses irregular apparent form, and the desorption bubbled for top layer has excellent effect.
Dispersion liquid in (3) is attached to the perfluorinated ion-exchange membrane surface that step (2) obtains by step (4), adhering mode is a variety of, including: spray, brush, roller coat, impregnate, transfer, the method, preferably spraying, roller coat such as spin coating.Technological operation is all by prior art.
In sum, the invention have the advantages that
(1) present invention instead of the inorganic oxide coating in existing product with the surface layer mixed by fluorine resin microparticle and inorganic compound particle; owing to resin microparticle is close with basement membrane material chemical constitution; there is the good compatibility and cementability; therefore can ensure that at the degasifying effect that the their entire life holding of ion-conductive membranes is good, and degasifying effect is much better than inorganic oxide coating.
(2) politef non-woven fabrics is combined with basement membrane after solvent processes, and have employed superpressure technique, while obtaining excellent chemical property and mechanical property, substantially increases the anti-impurity performance of ion-conductive membranes.
(3) the present invention is to provide and a kind of prepare chlorine and the ion-conductive membranes of sodium hydroxide/potassium hydroxide for electrolytic sodium chloride/potassium chloride, the introducing of politef non-woven fabrics improves the purity of product, purity of chlorine gas feeding >=99.5% that electrolysis obtains, hydrogen purity >=99.9%, salt content of soda≤5ppm.
(5) ion-conductive membranes of the present invention is suitable for the electrolysis of 30-35% concentration alkali, and prior art intermediate ion conductive membranes is typically suitable only for the electrolysis of 30-32% concentration alkali.
(6) ion-conductive membranes of the present invention can process the alkali metal chloride solution of wide range of concentrations with stability and high efficiency for chlorine industry, it is suitable in zero polar distance electrolytic bath under novel high current densities running, while improving product purity, tank voltage significantly reduces, higher than 5.5KA/m2Electric current density under, groove forces down in 2.75V.
(7) present invention is while giving the chemical property that ion-conductive membranes is excellent, is more suitable for the acid adding process of electrolytic process, and maloperation is added excessive acid has toleration, improves whole conductive membranes anti-protonation ability under strongly acidic conditions.
(8) present invention also provides for its preparation method, technique advantages of simple, it is easy to industrialized production.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
(1) perfluorinated carboxylic acid resin of the perfluorinated sulfonic resin and IEC=1.0mmol/g of choosing IEC=1.05mmol/g is combined into perfluorinated ion exchange resin basement membrane by the way of coextrusion is cast, in the resin bed based on perfluorinated sulfonic resin, perfluorinated sulfonic resin and perfluorinated carboxylic acid resin's mass ratio are 100:0.5, in the resin bed based on perfluorinated sulfonic resin, perfluorinated carboxylic acid resin and perfluorinated sulfonic resin mass ratio are 100:1, wherein the resin layer thickness based on perfluorinated sulfonic resin is 120 microns, and the resin layer thickness based on perfluorinated sulfonic resin is 10 microns.The trifluorotrichloroethane solvent again porous reinforcing material politef non-woven fabrics being immersed in ultrasonic processor processes 1.5 hours, wherein nonwoven thickness is 50 microns, porosity is 85%, take out and be combined with perfluorinated ion exchange resin basement membrane more after drying, porous reinforcing material is introduced between film forming press-roller, under the effect of roll gap pressure, porous reinforcing material is pressed in the middle of film body, thus forms perfluorinated ion-exchange membrane precursor.
(2) by perfluorinated ion-exchange membrane precursor prepared in step (1) at a temperature of 200 DEG C, under the pressure of 100 tons, superpressure machine is used to carry out superpressure process with the speed of 50 ms/min, after superpressure processes, perfluorinated ion-exchange membrane precursor is immersed at 85 DEG C in the mixed aqueous solution containing 15wt% dimethyl sulfoxide and 20wt% NaOH 80 minutes, is converted into the perfluorinated ion-exchange membrane possessing ion exchanging function.
(3) water and ethanol are made into mixed liquor according to the weight ratio of 1:1, add mean diameter be 300 nanometers, there is the fluorine resin microparticle of irregular polyhedrons pattern with the homogeneous mixture of the inorganic compound particle that mean diameter is 20 nanometers (fluorine resin microparticle be once pulverized in cryogenic pulverization device by resin granular material after, it is ground again obtaining in cryogenic system), in ball mill, homogenization processes, and forms the dispersion liquid that content is 15wt%；Wherein: fluorine resin microparticle PFA and inorganic compound particle zirconic mixing quality ratio are 1:100.
(4) method using spraying, is attached to the perfluorinated ion-exchange membrane both side surface that step (2) obtains by dispersion liquid, and surface layer thickness is 1 micron, forms finished product after drying.
Performance test:
The ion exchange membrane prepared is carried out in electrolysis bath the electrolysis test of sodium-chloride water solution, the sodium-chloride water solution of 300g/L is supplied anode chamber, water being supplied cathode chamber, it is ensured that the sodium chloride concentration discharged from anode chamber is 200g/L, the naoh concentration discharged from cathode chamber is 35%；Test temperature is 90 DEG C, and electric current density is 7.5kA/m2, through the electrolytic experiment of 23 days, average groove pressure was 2.76V, and average current efficiency is 99.7%.
Afterwards, adding inorganic matter Ca, Mg impurity 15ppb in supply sodium-chloride water solution, carry out the electrolytic experiment of 40 days under the same conditions as above, average groove pressure is stable at 2.77V, and average current efficiency is 99.7%.
Anode at electrolysis bath surveys the hydrochloric acid of add excess 17%, after causing the PH of light salt brine to reach 1.5, runs through emergency operation measure and recovers to be electrolysed to normal operating parameters, groove pressure after Wen Ding is 2.79V, current efficiency is 99.5%, the sustainable use of film, and property retention is good.
It is 1.1 Ω cm according to the surface resistance of standard SJ/T 10171.5 method test gained film-2, the abrasion loss using ASTM standard D 1044-99 test gained film is 2.7mg.
According to the electrolytic production examination criteria of standard, detection electrolytic production purity is respectively, purity of chlorine gas feeding 99.5%, hydrogen purity 99.9%, salt content of soda 3ppm.
Comparative example 1
Method preparation same as in Example 1 is used to possess the ion exchange membrane of ion exchanging function, prepare dispersion liquid the most after the same method, except that, it is 50 nano inorganic oxide granules that fluorine resin in dispersion liquid replaces with mean diameter with inorganic compound mixing microparticle, in ball mill, homogenization processes, and forms the dispersion liquid that content is 15wt%.Use the ion exchange membrane operating to be attached with inorganic oxide coating to both sides similarly to Example 1.
Carrying out the electrolysis test of sodium chloride solution under the same conditions as example 1, through the electrolytic experiment of 23 days, average groove pressure was 2.90V, and average current efficiency is 96.2%, and surface resistance is 2.3 Ω cm-2, the abrasion loss of film is 11mg.
Anode at electrolysis bath surveys the hydrochloric acid of add excess 17%, after causing the PH of light salt brine to reach 1.5, runs through emergency operation measure and recovers to be electrolysed to normal operating parameters, and the groove pressure after stablizing is 6.87V, and current efficiency is 70.5%, and film is thoroughly scrapped.
Comparative example 2
Method preparation same as in Example 1 is used to possess the ion exchange membrane of ion exchanging function, except that, porous reinforcing material was provided without fluorocarbon solvent immersion treatment with perfluorinated ion exchange resin basement membrane before carrying out being combined, and the most unused superpressure machine superpressure processes.Preparing fluorine resin and inorganic compound mixing microparticle dispersion liquid after the same method, in ball mill, homogenization processes, and forms the dispersion liquid that content is 15wt%.Operation similarly to Example 1 is used to obtain ion exchange membrane finished product.
Carrying out the electrolysis test of sodium chloride solution under the same conditions as example 1, through the electrolytic experiment of 23 days, average groove pressure was 2.83V, and average current efficiency is 99.0%, and surface resistance is 1.8 Ω cm-2.Afterwards, adding inorganic matter Ca, Mg impurity 15ppb in supply sodium-chloride water solution, carry out the electrolytic experiment of 40 days under the same conditions as above, average groove pressure is stable at 2.93V, and average current efficiency is 97.5%.Detection product purity is respectively, purity of chlorine gas feeding 98.5%, hydrogen purity 98.7%, salt content of soda 15ppm.
Embodiment 2
(1) perfluorinated carboxylic acid resin of the perfluorinated sulfonic resin and IEC=0.95mmol/g of choosing IEC=1.05mmol/g is combined into perfluorinated ion exchange resin basement membrane by the way of coextrusion is cast, in the resin bed based on perfluorinated sulfonic resin, perfluorinated sulfonic resin and perfluorinated carboxylic acid resin's mass ratio are 100:2, in the resin bed based on perfluorinated sulfonic resin, perfluorinated carboxylic acid resin and perfluorinated sulfonic resin mass ratio are 100:0.5, wherein the resin layer thickness based on perfluorinated sulfonic resin is 80 microns, and the resin layer thickness based on perfluorinated sulfonic resin is 15 microns.The trifluorotrichloroethane again porous reinforcing material politef non-woven fabrics being immersed in ultrasonic processor and dehydrated alcohol mixed solvent process 2 hours, wherein nonwoven thickness is 35 microns, porosity is 70%, take out and be combined with perfluorinated ion exchange resin basement membrane more after drying, porous reinforcing material is introduced between film forming press-roller, under the effect of roll gap pressure, porous reinforcing material is pressed in the middle of film body, thus forms perfluorinated ion-exchange membrane precursor.
(2) by perfluorinated ion-exchange membrane precursor prepared in step (1) at a temperature of 120 DEG C, under the pressure of 60 tons, superpressure machine is used to carry out superpressure process with the speed of 15 ms/min, after superpressure processes, perfluorinated ion-exchange membrane precursor is immersed at 85 DEG C in the mixed aqueous solution containing 15wt% dimethyl sulfoxide and 20wt% NaOH 80 minutes, is converted into the perfluorinated ion-exchange membrane possessing ion exchanging function.
(3) water and ethanol are made into mixed liquor according to the weight ratio of 1:1, add mean diameter be 200 nanometers, there is the fluorine resin microparticle of irregular polyhedrons pattern with the homogeneous mixture of the inorganic compound particle that mean diameter is 50 nanometers (fluorine resin microparticle and inorganic compound particle be all once pulverized in cryogenic pulverization device by resin granular material after, it is ground again obtaining in cryogenic system), in ball mill, homogenization processes, and forms the dispersion liquid that content is 15wt%.Wherein, fluorine resin microparticle FEP is 1:1 with the mixing quality ratio of inorganic compound particle silicon oxide.
(4) method using roller coat, is attached to the perfluorinated ion-exchange membrane both side surface that step (2) obtains by dispersion liquid, and surface layer thickness is about 900 nanometers, forms finished product after drying.
Performance test:
The ion exchange membrane prepared is carried out in electrolysis bath the electrolysis test of sodium-chloride water solution, the sodium-chloride water solution of 300g/L is supplied anode chamber, water being supplied cathode chamber, it is ensured that the sodium chloride concentration discharged from anode chamber is 200g/L, the naoh concentration discharged from cathode chamber is 34%；Test temperature is 90 DEG C, and electric current density is 7.5kA/m2, through the electrolytic experiment of 23 days, average groove pressure was 2.73V, and average current efficiency is 99.7%.
Afterwards, adding inorganic matter Ca, Mg impurity 15ppb in supply sodium-chloride water solution, carry out the electrolytic experiment of 40 days under the same conditions as above, average groove pressure is stable at 2.74V, and average current efficiency is 99.7%.
It is 1.0 Ω cm according to the surface resistance of standard SJ/T 10171.5 method test gained film-2, the abrasion loss using ASTM standard D 1044-99 test gained film is 2.7mg.
According to the electrolytic production examination criteria of standard, detection electrolytic production purity is respectively, purity of chlorine gas feeding 99.7%, hydrogen purity 99.8%, salt content of soda 3ppm.
Embodiment 3
(1) perfluorinated carboxylic acid resin of the perfluorinated sulfonic resin and IEC=0.95mmol/g of choosing IEC=1.1mmol/g is combined into perfluorinated ion exchange resin basement membrane by the way of coextrusion is cast, in the resin bed based on perfluorinated sulfonic resin, perfluorinated sulfonic resin and perfluorinated carboxylic acid resin's mass ratio are 100:3, in the resin bed based on perfluorinated sulfonic resin, perfluorinated carboxylic acid resin and perfluorinated sulfonic resin mass ratio are 100:2.5, wherein the resin layer thickness based on perfluorinated sulfonic resin is 150 microns, and the resin layer thickness based on perfluorinated sulfonic resin is 7 microns.The trifluorotrichloroethane again porous reinforcing material politef non-woven fabrics being immersed in ultrasonic processor and propanol solvent mixture process 2 hours, wherein nonwoven thickness is 10 microns, porosity is 60%, take out and be combined with perfluorinated ion exchange resin basement membrane more after drying, porous reinforcing material is introduced between film forming press-roller, under the effect of roll gap pressure, porous reinforcing material is pressed in the middle of film body, thus forms perfluorinated ion-exchange membrane precursor.
(2) by perfluorinated ion-exchange membrane precursor prepared in step (1) at a temperature of 80 DEG C, under the pressure of 60 tons, superpressure machine is used to carry out superpressure process with the speed of 1 m/min, after superpressure processes, perfluorinated ion-exchange membrane precursor is immersed at 85 DEG C in the mixed aqueous solution containing 15wt% dimethyl sulfoxide and 20wt% NaOH 80 minutes, is converted into the perfluorinated ion-exchange membrane possessing ion exchanging function.
(3) water and ethanol are made into mixed liquor according to the weight ratio of 1:1, add mean diameter be 150 nanometers, there is the fluorine resin microparticle of irregular polyhedrons pattern with the homogeneous mixture of the inorganic compound particle that mean diameter is 500 nanometers (fluorine resin microparticle be once pulverized in cryogenic pulverization device by resin granular material after, it is ground again obtaining in cryogenic system), in ball mill, homogenization processes, and forms the dispersion liquid that content is 15wt%.Wherein, fluorine resin microparticle PVDF is 1:50 with the mixing quality ratio of inorganic compound particle titanium oxide.
(4) using the method brushed, dispersion liquid is attached to the perfluorinated ion-exchange membrane both side surface that step (2) obtains, surface layer thickness is about 2 microns, forms finished product after drying.
Performance test:
The ion exchange membrane prepared is carried out in electrolysis bath the electrolysis test of sodium-chloride water solution, the sodium-chloride water solution of 300g/L is supplied anode chamber, water being supplied cathode chamber, it is ensured that the sodium chloride concentration discharged from anode chamber is 200g/L, the naoh concentration discharged from cathode chamber is 30%；Test temperature is 90 DEG C, and electric current density is 6.5kA/m2, through the electrolytic experiment of 23 days, average groove pressure was 2.75V, and average current efficiency is 99.8%.
Afterwards, adding inorganic matter Ca, Mg impurity 15ppb in supply sodium-chloride water solution, carry out the electrolytic experiment of 40 days under the same conditions as above, average groove pressure is stable at 2.75V, and average current efficiency is 99.8%.
It is 1.2 Ω cm according to the surface resistance of standard SJ/T 10171.5 method test gained film-2, the abrasion loss using ASTM standard D 1044-99 test gained film is 2.6mg.
According to the electrolytic production examination criteria of standard, detection electrolytic production purity is respectively, purity of chlorine gas feeding 99.8%, hydrogen purity 99.9%, salt content of soda 5ppm.
Embodiment 4
(1) perfluorinated carboxylic acid resin of the perfluorinated sulfonic resin and IEC=0.85mmol/g of choosing IEC=0.95mmol/g is combined into perfluorinated ion exchange resin basement membrane by the way of coextrusion is cast, in the resin bed based on perfluorinated sulfonic resin, perfluorinated sulfonic resin and perfluorinated carboxylic acid resin's mass ratio are 100:5, in the resin bed based on perfluorinated sulfonic resin, perfluorinated carboxylic acid resin and perfluorinated sulfonic resin mass ratio are 100:5, wherein the resin layer thickness based on perfluorinated sulfonic resin is 75 microns, and the resin layer thickness based on perfluorinated sulfonic resin is 15 microns.The trifluorotrichloroethane again porous reinforcing material politef non-woven fabrics being immersed in ultrasonic processor and methanol mixed solvent process 1 hour, wherein nonwoven thickness is 15 microns, porosity is 75%, take out and be combined with perfluorinated ion exchange resin basement membrane more after drying, porous reinforcing material is introduced between film forming press-roller, under the effect of roll gap pressure, porous reinforcing material is pressed in the middle of film body, thus forms perfluorinated ion-exchange membrane precursor.
(2) by perfluorinated ion-exchange membrane precursor prepared in step (1) at a temperature of 30 DEG C, under the pressure of 40 tons, superpressure machine is used to carry out superpressure process with the speed of 10 ms/min, after superpressure processes, perfluorinated ion-exchange membrane precursor is immersed at 85 DEG C in the mixed aqueous solution containing 15wt% dimethyl sulfoxide and 20wt% NaOH 80 minutes, is converted into the perfluorinated ion-exchange membrane possessing ion exchanging function.
(3) water and ethanol are made into mixed liquor according to the weight ratio of 1:1, add mean diameter be 50 nanometers, there is the fluorine resin microparticle of irregular polyhedrons pattern with the homogeneous mixture of the inorganic compound particle that mean diameter is 300 nanometers (fluorine resin microparticle be once pulverized in cryogenic pulverization device by resin granular material after, it is ground again obtaining in cryogenic system), in ball mill, homogenization processes, and forms the dispersion liquid that content is 15wt%.Wherein: fluorine resin microparticle PTFE is 100:1 with the mixing quality ratio of inorganic compound particle zirconium hydroxide.
(4) method using spraying, is attached to the perfluorinated ion-exchange membrane both side surface that step (2) obtains by dispersion liquid, and surface layer thickness is about 200 nanometers, forms finished product after drying.
Performance test:
The ion exchange membrane prepared is carried out in electrolysis bath the electrolysis test of sodium-chloride water solution, the sodium-chloride water solution of 300g/L is supplied anode chamber, water being supplied cathode chamber, it is ensured that the sodium chloride concentration discharged from anode chamber is 200g/L, the naoh concentration discharged from cathode chamber is 31%；Test temperature is 90 DEG C, and electric current density is 6.5kA/m2, through the electrolytic experiment of 23 days, average groove pressure was 2.71V, and average current efficiency is 99.7%.
Afterwards, adding inorganic matter Ca, Mg impurity 15ppb in supply sodium-chloride water solution, carry out the electrolytic experiment of 40 days under the same conditions as above, average groove pressure is stable at 2.71V, and average current efficiency is 99.7%.
It is 1.2 Ω cm according to the surface resistance of standard SJ/T 10171.5 method test gained film-2, the abrasion loss using ASTM standard D 1044-99 test gained film is 2.7mg.
According to the electrolytic production examination criteria of standard, detection electrolytic production purity is respectively, purity of chlorine gas feeding 99.8%, hydrogen purity 100%, salt content of soda 3ppm.
Embodiment 5
(1) perfluorinated carboxylic acid resin of the perfluorinated sulfonic resin and IEC=0.85mmol/g of choosing IEC=0.9mmol/g is combined into perfluorinated ion exchange resin basement membrane by the way of coextrusion is cast, in the resin bed based on perfluorinated sulfonic resin, perfluorinated sulfonic resin and perfluorinated carboxylic acid resin's mass ratio are 100:5.5, in the resin bed based on perfluorinated sulfonic resin, perfluorinated carboxylic acid resin and perfluorinated sulfonic resin mass ratio are 100:5, wherein the resin layer thickness based on perfluorinated sulfonic resin is 50 microns, and the resin layer thickness based on perfluorinated sulfonic resin is 18 microns.The trifluorotrichloroethane again porous reinforcing material politef non-woven fabrics being immersed in ultrasonic processor and acetone mixed solvent process 1.5 hours, wherein nonwoven thickness is 10 microns, porosity is 85%, take out and be combined with perfluorinated ion exchange resin basement membrane more after drying, porous reinforcing material is introduced between film forming press-roller, under the effect of roll gap pressure, porous reinforcing material is pressed in the middle of film body, thus forms perfluorinated ion-exchange membrane precursor.
(2) by perfluorinated ion-exchange membrane precursor prepared in step (1) at a temperature of 10 DEG C, under the pressure of 20 tons, superpressure machine is used to carry out superpressure process with the speed of 50 ms/min, after superpressure processes, perfluorinated ion-exchange membrane precursor is immersed at 85 DEG C in the mixed aqueous solution containing 15wt% dimethyl sulfoxide and 20wt% NaOH 80 minutes, is converted into the perfluorinated ion-exchange membrane possessing ion exchanging function.
(3) water and ethanol are made into mixed liquor according to the weight ratio of 1:1, add mean diameter be 200 nanometers, there is the fluorine resin microparticle of irregular polyhedrons pattern with the homogeneous mixture of the inorganic compound particle that mean diameter is 50 nanometers (fluorine resin microparticle be once pulverize in cryogenic pulverization device after, it is ground again obtaining in cryogenic system), in ball mill, homogenization processes, and forms the dispersion liquid that content is 15wt%.Wherein, fluorine resin microparticle PFA is 50:1 with the mixing quality ratio of inorganic compound particle stannum oxide.
(4) method using spraying, is attached to the perfluorinated ion-exchange membrane both side surface that step (2) obtains by dispersion liquid, and surface layer thickness is about 1 micron, forms finished product after drying.
Performance test:
The ion exchange membrane prepared is carried out in electrolysis bath the electrolysis test of sodium-chloride water solution, the sodium-chloride water solution of 300g/L is supplied anode chamber, water being supplied cathode chamber, it is ensured that the sodium chloride concentration discharged from anode chamber is 200g/L, the naoh concentration discharged from cathode chamber is 32%；Test temperature is 90 DEG C, and electric current density is 5.5kA/m2, through the electrolytic experiment of 23 days, average groove pressure was 2.70V, and average current efficiency is 99.7%.
Afterwards, adding inorganic matter Ca, Mg impurity 15ppb in supply sodium-chloride water solution, carry out the electrolytic experiment of 40 days under the same conditions as above, average groove pressure is stable at 2.71V, and average current efficiency is 99.7%.
It is 1.1 Ω cm according to the surface resistance of standard SJ/T 10171.5 method test gained film-2, the abrasion loss using ASTM standard D 1044-99 test gained film is 2.7mg.
According to the electrolytic production examination criteria of standard, detection electrolytic production purity is respectively, purity of chlorine gas feeding 99.8%, hydrogen purity 99.9%, salt content of soda 3ppm.
Claims (10)
1. the ion-conductive membranes for chlorine industry, it is characterised in that: the surface layer mixed by perfluorinated ion exchange resin basement membrane, porous reinforcing material and fluorine resin microparticle and inorganic compound particle forms；
Described perfluorinated ion exchange resin basement membrane is made up of the resin bed based on perfluorinated sulfonic resin and the resin bed based on perfluorinated carboxylic acid resin, resin bed based on perfluorinated sulfonic resin is that perfluorinated sulfonic resin and perfluorinated carboxylic acid resin are blended or copolymerization forms, and the resin bed based on perfluorinated carboxylic acid resin is perfluorinated carboxylic acid resin and perfluorinated sulfonic resin is blended or copolymerization forms.
Ion-conductive membranes for chlorine industry the most according to claim 1, it is characterised in that: the resin layer thickness based on perfluorinated sulfonic resin is 30-300 micron, and the resin layer thickness based on perfluorinated carboxylic acid resin is for 2-30 micron；Resin bed based on perfluorinated sulfonic resin is that the perfluorinated sulfonic resin with mass ratio as 100:0.1-100:10 and perfluorinated carboxylic acid resin are blended or copolymerization forms；Resin bed based on perfluorinated carboxylic acid resin is that the perfluorinated carboxylic acid resin with mass ratio as 100:0.1-100:10 and perfluorinated sulfonic resin are blended or copolymerization forms.
Ion-conductive membranes for chlorine industry the most according to claim 2, it is characterised in that: the exchange capacity of perfluorinated sulfonic resin is 0.8-1.5 mM/gram, and the exchange capacity of perfluorinated carboxylic acid resin is 0.8-1.2 mM/gram.
Ion-conductive membranes for chlorine industry the most according to claim 1; it is characterized in that: the surface layer thickness that fluorine resin microparticle and inorganic compound particle mix is between 20 nanometer-100 microns, in surface layer, fluorine resin microparticle is 1:100-100:1 with the mass ratio of inorganic compound particle.
Ion-conductive membranes for chlorine industry the most according to claim 1, it is characterised in that: the inorganic compound particle a kind of or the most several mixture in IV-A race, IV-B race, V-B race, ferrum, cobalt, nickel, chromium, manganese or the oxide of boron element, hydroxide, nitride.
Ion-conductive membranes for chlorine industry the most according to claim 1, it is characterised in that: the fluorine resin microparticle a kind of or the most several mixture in politef microparticle, PFA microparticle, perfluoroethylene-propylene microparticle, poly-perfluoro propyl vinyl ether microparticle or Kynoar microparticle.
7. according to the ion-conductive membranes for chlorine industry described in claim 1,5 or 6, it is characterised in that: the fluorine resin microparticle in surface layer, particle size range is between 20 nanometer-10 microns；Inorganic compound particle particle size range in surface layer is between 20 nanometer-10 microns.
Ion-conductive membranes for chlorine industry the most according to claim 1, it is characterised in that: porous reinforcing material is politef non-woven fabrics, and fiber intersection is overlap joint or merges, and porous reinforcing material thickness is between 1-200 micron；Politef non-woven fabrics porosity is between 20-99%.
9. the preparation method of the ion-conductive membranes for chlorine industry described in a claim 1, it is characterised in that: comprise the following steps:
(1) by the way of screw-type extruder coextrusion, melt curtain coating and help fluorion exchanger resin basement membrane, again porous reinforcing material is immersed in fluorine carbon solvent, supersound process 1-2 hour, take out and be combined with perfluorinated ion exchange resin basement membrane more after drying, porous reinforcing material is introduced between film forming press-roller, under the effect of roll gap pressure, porous reinforcing material is pressed in perfluorinated ion exchange resin basement membrane, thus obtains perfluorinated ion-exchange membrane precursor；
(2) the perfluorinated ion-exchange membrane precursor prepared in step (1) is converted into there is the perfluorinated ion-exchange membrane of ion exchanging function；
(3) according to 1:1 weight ratio, water and ethanol being made into mixed liquor, add fluorine resin microparticle and inorganic compound particle mixture, in ball mill, homogenization processes, and forms dispersion liquid；
(4) dispersion liquid in (3) is attached to the perfluorinated ion-exchange membrane surface that step (2) obtains, forms finished product after drying.
The preparation method of the ion-conductive membranes for chlorine industry the most according to claim 9, it is characterized in that: in step (3) fluorine resin microparticle be once pulverized in cryogenic pulverization device by resin granular material after, then be ground obtaining in cryogenic system.
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| CN201410251252.1A CN104018181B (en) | 2014-06-06 | 2014-06-06 | Ionic conduction membrane for chlor-alkali industry and preparation method thereof |
| PCT/CN2014/000656 WO2015184572A1 (en) | 2014-06-06 | 2014-07-07 | Novel ion-conducting membrane used in chlor-alkali industry and preparation method therefor |
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| CN109968574B (en) * | 2019-05-16 | 2024-02-06 | 江苏科润膜材料有限公司 | Steel belt casting device for producing enhanced perfluorinated ion exchange membrane and membrane manufacturing 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 |
| 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 |
| 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 |
| 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 |
| CN111074295B (en) * | 2019-12-31 | 2021-07-16 | 山东东岳高分子材料有限公司 | Novel 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 |
| CN113061251B (en) * | 2021-03-22 | 2022-11-29 | 河北科技大学 | A kind of modified polyimide and its preparation method and application |
| KR20230152725A (en) | 2021-03-29 | 2023-11-03 | 저지앙 하이프루프 뉴 에너지 컴퍼니 리미티드 | Special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane, composite membrane electrode, special highly reinforced fluorine-containing chlor-alkali cell membrane, special release membrane, and method for manufacturing the same. |
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| 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 |
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