CN104018181A - Novel ionic conduction membrane for chlor-alkali industry and preparation method thereof - Google Patents
Novel ionic conduction membrane for chlor-alkali industry and preparation method thereof Download PDFInfo
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- CN104018181A CN104018181A CN201410251252.1A CN201410251252A CN104018181A CN 104018181 A CN104018181 A CN 104018181A CN 201410251252 A CN201410251252 A CN 201410251252A CN 104018181 A CN104018181 A CN 104018181A
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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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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 Novel ion conductive membranes for chlorine industry and preparation method thereof.
Background technology
In recent years, in ionic membrane method alkali-chloride is produced, for realize high current density, low bath voltage, with the high condition of concentration of lye under carry out electrolysis, boost productivity and the object that reduces power consumption to reach, its key is to shorten ionic membrane and interelectrode distance, to reduce its bath voltage, make the electrolysis with ion-exchange film technique of narrow pole span type reach practical.Along with the continuous progress of technology, zero polar distance electrolytic bath is used widely, but in the time that interelectrode distance is reduced to less than 2mm, because film and negative electrode are close to, and make the bubble hydrogen adhering on face be difficult to discharge, therefore gathered a large amount of bubble hydrogens on the face towards negative electrode.Bubble has hindered current channel, and effective electrolysis area of film is reduced, and causes distribution of current inequality on face, and local polarisation effect obviously increases.Thus, make on the contrary membrane resistance and bath voltage sharply increase, its electrolytic power consumption significantly raises.
The shortcoming of bringing for overcoming bubble effect discharges fast the bubble hydrogen adhering to from the little face of wetting ability, has developed the method for modifying of ionic membrane surface hydrophilic coating.All after porous multi-hole type, non-electrode coating without electro catalytic activity, face wetting ability is obviously increased at a kind of gas of film surface coverage and liquid, anti-latherability significantly improves.Ionic membrane after hydrophilic coating modification, can be close to electrode, greatly reduces bath voltage, is widely used at present zero pole span type electrolysis with ion-exchange film technique.Hydrophilic coating modified technique need to, by after inorganics component and polymer agent mixture, cover ionic membrane surface by strike, particle embedment method etc., and patent CA2446448 and CA2444585 have carried out concrete introduction to coating process; Although this kind of method of modifying effect is remarkable, technique relative complex.In addition, due to ionic membrane can experience alkaline stream in electrolysis operational process constantly wash away the continuous concussion causing with turbulent flow, the hydrophilic coating that is attached to ionic membrane surface can come off gradually, it is invalid that anti-foaming function is reduced to gradually.
Patent US 4502931 mentions and adopts the method for ion etching to carry out surface roughening modification on ionic membrane surface, but the method is not only difficult for big area to be implemented, and anti-latherability is not high, in the time that pole distance reduces to a certain degree, its groove is pressed and is still greater than 3.5V, and current efficiency is lower than 90%.
Therefore, develop a kind of novel Novel ion conductive membranes for chlorine industry, its surface has permanently effective hydrophilic degassed function, and can in state-of-the-art electrolyzer and electrolysis process process, continue the anti-foaming effect, reduction bath voltage, the raising current efficiency that provide good, and can reduce power consumption, have very important significance.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of Novel ion conductive membranes for chlorine industry, can process the alkali metal chloride solution of wide range of concentrations for chlorine industry stability and high efficiency, be adapted at moving in zero polar distance electrolytic bath under novel high current densities, there is very excellent product purity index; The present invention also provides its preparation method, and technique advantages of simple, is easy to suitability for industrialized production.
Novel ion conductive membranes for chlorine industry of the present invention, the upper layer being mixed by perfluorinated ion exchange resin basement membrane, porous strongthener and fluorine resin microparticle and inorganic compound particle forms.
Wherein: described perfluorinated ion exchange resin basement membrane is by forming taking perfluorinated sulfonic resin as main resin layer with taking perfluorinated carboxylic acid resin as main resin layer, taking perfluorinated sulfonic resin as main resin layer thickness is as 30-300 micron, preferably 50-150 micron, less taking perfluorinated sulfonic resin non diffusible ion content in main resin tunic, and to repulsive force hydroxy a little less than, thickness should not be excessively thin; Taking perfluorinated carboxylic acid resin as main resin layer thickness is as 2-30 micron, preferably 7-18 micron, taking perfluorinated carboxylic acid resin as main resin layer membrane resistance larger, thickness is unsuitable excessive.
That perfluorinated sulfonic resin taking mass ratio as 100:0.1-100:10 and perfluorinated carboxylic acid resin's blend or copolymerization form taking perfluorinated sulfonic resin as main resin layer; Its mass ratio is preferably 100:0.5-100:5.Perfluorinated carboxylic acid resin taking perfluorinated sulfonic resin existing on a small quantity in main resin layer but can play crucial transitional function, the gradient that sees through of water in film and ion is weakened, flux stability to ionic membrane plays a key effect, and can prevent peeling off between different retes simultaneously.
That perfluorinated carboxylic acid resin taking mass ratio as 100:0.1-100:10 and perfluorinated sulfonic resin blend or copolymerization form taking perfluorinated carboxylic acid resin as main resin layer, preferably 100:0.5-100:5.Perfluorinated sulfonic resin taking perfluorinated carboxylic acid resin existing on a small quantity in main resin layer also can play the crucial transitional function described in epimere.
The exchange capacity of perfluorinated sulfonic resin be 0.8-1.5 mmole/gram, preferably 0.9-1.1 mmole/gram; Perfluorinated carboxylic acid resin's exchange capacity be 0.8-1.2 mmole/gram, preferably 0.85-1.0 mmole/gram.The exchange capacity of two kinds of resins will match, and difference should not be too large.
The surface layer thickness that fluorine resin microparticle and inorganic compound particle mix is between 20 nanometer-100 micron, preferably 200 nanometer-2 micron.In upper layer, the mass ratio of fluorine resin microparticle and inorganic compound particle is 1:100-100:1.Upper layer is to be mixed by fluorine resin microparticle and inorganic compound particle; experiment shows; two kinds of particles are joined the mixed upper layer that is applied under suitable proportioning; in giving the chemical property of ion-conductive membranes excellence; more be adapted to the acid adding process of electrolytic process; and the excessive acid that adds to mishandle has tolerance, promote the anti-protonated ability of whole conductive membranes under strong acidic condition.Wherein: fluorine resin microparticle is selected from a kind of or any several mixture in tetrafluoroethylene microparticle (PTFE), PFA microparticle, perfluoroethylene-propylene microparticle (FEP), poly-perfluoro propyl vinyl ether microparticle or polyvinylidene difluoride (PVDF) microparticle (PVDF).Fluorine resin microparticle is after once being pulverized in cryogenic pulverization device by resin granular material, then in cryogenic unit, grinds and obtain, and particle all possesses irregular apparent pattern, has excellent effect for the desorption of top layer foaming.Fluorine resin microparticle particle size range in upper layer is between 20 nanometer-10 micron, preferably 50-300 nanometer.When particle diameter is too low, particle is easily reunited, plug ion passage; When particle diameter is too high, the particulate projection forming on film surface is too obvious, easily under external force scraping, departs from.
Inorganic compound particle is selected from a kind of in the oxide compound, oxyhydroxide, nitride of IV-A family, IV-B family, V-B family, iron, cobalt, nickel, chromium, manganese or boron or several mixtures, preferably one or more in autoxidation zirconium, strontium oxide, stannic oxide, ferric oxide, titanium oxide, silicon oxide, zirconium hydroxide or zirconium nitride arbitrarily.Inorganic compound particle particle size range in upper layer is between 20 nanometer-10 micron, preferably 20-300 nanometer.
Porous strongthener is tetrafluoroethylene non-woven fabrics, and fiber intersection is overlap joint or merges, porous strongthener thickness between 1-200 micron, preferably 10-50 micron; To improve physical strength, adopt prior art preparation.Described tetrafluoroethylene non-woven fabrics porosity between 20-99%, preferably 50-85%.If porosity is too low, otherwise can cause groove voltage rise high.
Novel ion conductive membranes for chlorine industry of the present invention, comprises following preparation process:
(1) help fluorion exchange resin basement membrane by the mode melting curtain coating of screw-type extruder coextrusion, again porous strongthener is immersed in fluorine carbon solvent, supersound process 1-2 hour, after taking-up is dry, carry out compound with perfluorinated ion exchange resin basement membrane again, between film forming press-roller, introduce porous strongthener, under the effect of roll gap pressure, porous strongthener is pressed in perfluorinated ion exchange resin basement membrane, thereby obtains perfluorinated ion-exchange membrane precursor.
(2) be the perfluorinated ion-exchange membrane with ion exchanging function by the perfluorinated ion-exchange membrane precursor conversion making in step (1).
(3) water and ethanol are made into mixed solution according to 1:1 weight ratio, add fluorine resin microparticle and inorganic compound particle mixture, homogenization processing in ball mill, forms dispersion liquid.
(4) dispersion liquid in (3) is attached to the perfluorinated ion-exchange membrane surface that step (2) obtains, forms after drying finished product.
Wherein: porous strongthener is immersed in supersound process 1-2 hour in fluorine carbon solvent by step (1), taking-up is carried out compound with perfluorinated ion exchange resin basement membrane after being dried again.Owing to being very difficult to the infiltration of tetrafluoroethylene non-woven fabrics, if without processing directly and basement membrane carries out compoundly, resin matrix cannot fill up the space of non-woven fabrics completely, thereby form the eakiness space of film body inside, not only easily deposit impurity, can also form space obstacle, increase resistance.After porous strongthener soaks 1-2 hour in fluorine carbon solvent, the infiltration of resin matrix is very easy, and the two can form well, combination closely, has not only increased mechanical strength, and because non-woven fabrics percentage of open area is high, very little on the impact of film body resistance.
The described fluorine carbon solvent of step (1) is selected from: Freon 113 (F-113) or Freon 113 and other solvent; Other solvent is one or more in dehydrated alcohol, propyl alcohol, methyl alcohol, acetone, methylene dichloride or water phase surfactant mixture.Tensio-active agent is selected from commercial anionic, cationic, amphoteric or nonionic surface active agent.
Step (2) for by the perfluorinated ion-exchange membrane precursor making in step (1) at the temperature of 10-200 DEG C, under the pressure of 20-100 ton, use superpressure machine to carry out superpressure processing with the speed of 1-50 m/min, after superpressure is processed, perfluorinated ion-exchange membrane precursor be impregnated in the mixed aqueous solution of 15wt% dimethyl sulfoxide (DMSO) and 20wt% NaOH, be converted into the perfluorinated ion-exchange membrane with ion exchanging function.Wherein: superpressure is processed the combination degree of compactness that has further increased non-woven fabrics and basement membrane, superpressure is processed the physical structure form of also having improved to a certain extent non-woven fabrics and basement membrane simultaneously, it is detailed-oriented that the fibrillation of non-woven fabrics and the hot pressing of basement membrane cause crystalline texture, can effectively improve ion transport effect.
Fluorine resin microparticle is after once being pulverized in cryogenic pulverization device by resin granular material in step (3), then in cryogenic unit, grinds and obtain.The fluorine resin microparticle obtaining possesses irregular apparent pattern, and the desorption bubbling for top layer has excellent effect.
The 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, comprise: the methods such as spraying, brushing, roller coat, dipping, transfer printing, spin coating, preferably spraying, roller coat.Technological operation is all by prior art.
In sum, the present invention has the following advantages:
(1) the present invention uses the upper layer being mixed by fluorine resin microparticle and inorganic compound particle to substitute the inorganic oxide coating in currently available products; because resin microparticle is close with basement membrane material chemical structure; there is good consistency and cementability; therefore can ensure to keep good degasifying effect at the whole life period of ion-conductive membranes, and degasifying effect is much better than inorganic oxide coating.
(2) tetrafluoroethylene non-woven fabrics is compound with basement membrane after solvent treatment, and has adopted superpressure technique, in obtaining excellent chemical property and mechanical property, has greatly improved the anti-impurity performance of ion-conductive membranes.
(3) the present invention is to provide a kind of ion-conductive membranes of preparing chlorine and sodium hydroxide/potassium hydroxide for electrolytic sodium chloride/Repone K, the introducing of tetrafluoroethylene non-woven fabrics has improved the purity of product, purity of chlorine gas feeding >=99.5%, hydrogen purity >=99.9%, salt content of soda≤5ppm that electrolysis obtains.
(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 generally only suitable in the electrolysis of 30-32% concentration alkali.
(6) ion-conductive membranes of the present invention can be processed the alkali metal chloride solution of wide range of concentrations stability and high efficiency for chlorine industry, be adapted at moving in zero polar distance electrolytic bath under novel high current densities, in improving product purity, bath voltage significantly reduces, higher than 5.5KA/m
2current density under, groove forces down in 2.75V.
(7) the present invention, in giving the chemical property of ion-conductive membranes excellence, is more adapted to the acid adding process of electrolytic process, and the excessive acid that adds of mishandle is had to tolerance, has promoted the anti-protonated ability of whole conductive membranes under strong acidic condition.
(8) the present invention also provides its preparation method, and technique advantages of simple, is easy to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
(1) choose the perfluorinated sulfonic resin of IEC=1.05mmol/g and the perfluorinated carboxylic acid resin of IEC=1.0mmol/g is combined into perfluorinated ion exchange resin basement membrane by the mode of coextrusion curtain coating, taking perfluorinated sulfonic resin in main resin layer perfluorinated sulfonic resin and perfluorinated carboxylic acid resin's mass ratio as 100:0.5, taking perfluorinated sulfonic resin in main resin layer perfluorinated carboxylic acid resin and perfluorinated sulfonic resin mass ratio as 100:1, wherein taking perfluorinated sulfonic resin as main resin layer thickness is as 120 microns, taking perfluorinated sulfonic resin as main resin layer thickness is as 10 microns.Again porous strongthener tetrafluoroethylene non-woven fabrics is immersed in the Freon 113 solvent in ultrasonic processor and is processed 1.5 hours, wherein nonwoven thickness is 50 microns, porosity is 85%, after taking-up is dry, carry out compound with perfluorinated ion exchange resin basement membrane again, between film forming press-roller, introduce porous strongthener, under the effect of roll gap pressure, porous strongthener is pressed in the middle of film body, thereby forms perfluorinated ion-exchange membrane precursor.
(2) by the perfluorinated ion-exchange membrane precursor making in step (1) at the temperature of 200 DEG C, under the pressure of 100 tons, use superpressure machine to carry out superpressure processing with the speed of 50 ms/min, after superpressure is processed, perfluorinated ion-exchange membrane precursor is immersed in the mixed aqueous solution that contains 15wt% dimethyl sulfoxide (DMSO) and 20wt% NaOH at 85 DEG C to 80 minutes, is converted into the perfluorinated ion-exchange membrane that possesses ion exchanging function.
(3) water and ethanol are made into mixed solution according to the weight ratio of 1:1, to add median size be 300 nanometers, have the fluorine resin microparticle of irregular polyhedrons pattern and median size is that (fluorine resin microparticle is after once being pulverized in cryogenic pulverization device by resin granular material for the uniform mixture of the inorganic compound particle of 20 nanometers, in cryogenic unit, grind again and to obtain), homogenization processing in ball mill, the dispersion liquid that formation content is 15wt%; Wherein: the zirconic mixing quality ratio of fluorine resin microparticle PFA and inorganic compound particle is 1:100.
(4) adopt the method spraying, dispersion liquid is attached to the perfluorinated ion-exchange membrane both side surface that step (2) obtains, surface layer thickness is 1 micron, forms after drying finished product.
Performance test:
The ion-exchange membrane preparing is carried out in electrolyzer to the electrolysis test of sodium chloride aqueous solution, the sodium chloride aqueous solution of 300g/L is supplied with to anolyte compartment, by water supply cathode compartment, ensure that the sodium chloride concentration of discharging from anolyte compartment is 200g/L, the naoh concentration of discharging from cathode compartment is 35%; Probe temperature is 90 DEG C, and current density is 7.5kA/m
2, through the electrolytic experiment of 23 days, average groove was pressed as 2.76V, and mean current efficiency is 99.7%.
Afterwards, add inorganics Ca, Mg impurity 15ppb to supplying with in sodium chloride aqueous solution, carry out the electrolytic experiment of 40 days under above-mentioned identical condition, average groove is pressed and is stabilized in 2.77V, and mean current efficiency is 99.7%.
Survey the hydrochloric acid that adds excessive 17% at the anode of electrolyzer, cause the PH of light salt brine to reach after 1.5, carry out electrolysis after returning to normal working parameter by emergency operation measure rapidly, groove after stable is pressed as 2.79V, current efficiency is 99.5%, the sustainable use of film, and property retention is good.
Surface resistance according to standard SJ/T 10171.5 method test gained films is 1.1 Ω cm
-2, adopting the abrasion loss of ASTM standard D 1044-99 test gained film is 2.7mg.
According to the electrolytic production examination criteria of standard, detect electrolytic production purity and be respectively, purity of chlorine gas feeding 99.5%, hydrogen purity 99.9%, salt content of soda 3ppm.
Comparative example 1
Adopt the method preparation identical with embodiment 1 to possess the ion-exchange membrane of ion exchanging function, prepare after the same method afterwards dispersion liquid, difference is, it is 50 nano inorganic oxide particles that fluorine resin in dispersion liquid and mineral compound mixing microparticle are replaced with to median size, homogenization processing in ball mill, the dispersion liquid that formation content is 15wt%.Adopt similarly to Example 1 operate to such an extent that be attached with the ion-exchange membrane of inorganic oxide coating to both sides.
Under the condition identical with embodiment 1, carry out the electrolysis test of sodium chloride solution, through the electrolytic experiment of 23 days, average groove was pressed as 2.90V, and mean current efficiency is 96.2%, and surface resistance is 2.3 Ω cm
-2, the abrasion loss of film is 11mg.
Survey the hydrochloric acid that adds excessive 17% at the anode of electrolyzer, cause the PH of light salt brine to reach after 1.5, carry out electrolysis after returning to normal working parameter rapidly by emergency operation measure, the groove after stable is pressed as 6.87V, current efficiency is 70.5%, and film is thoroughly scrapped.
Comparative example 2
Adopt the method preparation identical with embodiment 1 to possess the ion-exchange membrane of ion exchanging function, difference is, porous strongthener is carrying out before compound not adopting fluorocarbon solvent immersion treatment with perfluorinated ion exchange resin basement membrane, and does not also use afterwards the processing of superpressure machine superpressure.Prepare after the same method fluorine resin and mineral compound mixing microparticle dispersion liquid, homogenization processing in ball mill, the dispersion liquid that formation content is 15wt%.Adopt operation similarly to Example 1 to obtain ion-exchange membrane finished product.
Under the condition identical with embodiment 1, carry out the electrolysis test of sodium chloride solution, through the electrolytic experiment of 23 days, average groove was pressed as 2.83V, and mean current efficiency is 99.0%, and surface resistance is 1.8 Ω cm
-2.Afterwards, add inorganics Ca, Mg impurity 15ppb to supplying with in sodium chloride aqueous solution, carry out the electrolytic experiment of 40 days under above-mentioned identical condition, average groove is pressed and is stabilized in 2.93V, and mean current efficiency is 97.5%.Testing product purity is respectively, purity of chlorine gas feeding 98.5%, hydrogen purity 98.7%, salt content of soda 15ppm.
Embodiment 2
(1) choose the perfluorinated sulfonic resin of IEC=1.05mmol/g and the perfluorinated carboxylic acid resin of IEC=0.95mmol/g is combined into perfluorinated ion exchange resin basement membrane by the mode of coextrusion curtain coating, taking perfluorinated sulfonic resin in main resin layer perfluorinated sulfonic resin and perfluorinated carboxylic acid resin's mass ratio as 100:2, taking perfluorinated sulfonic resin in main resin layer perfluorinated carboxylic acid resin and perfluorinated sulfonic resin mass ratio as 100:0.5, wherein taking perfluorinated sulfonic resin as main resin layer thickness is as 80 microns, taking perfluorinated sulfonic resin as main resin layer thickness is as 15 microns.Again porous strongthener tetrafluoroethylene non-woven fabrics is immersed in Freon 113 in ultrasonic processor and dehydrated alcohol mixed solvent and processes 2 hours, wherein nonwoven thickness is 35 microns, porosity is 70%, after taking-up is dry, carry out compound with perfluorinated ion exchange resin basement membrane again, between film forming press-roller, introduce porous strongthener, under the effect of roll gap pressure, porous strongthener is pressed in the middle of film body, thereby forms perfluorinated ion-exchange membrane precursor.
(2) by the perfluorinated ion-exchange membrane precursor making in step (1) at the temperature of 120 DEG C, under the pressure of 60 tons, use superpressure machine to carry out superpressure processing with the speed of 15 ms/min, after superpressure is processed, perfluorinated ion-exchange membrane precursor is immersed in the mixed aqueous solution that contains 15wt% dimethyl sulfoxide (DMSO) and 20wt% NaOH at 85 DEG C to 80 minutes, is converted into the perfluorinated ion-exchange membrane that possesses ion exchanging function.
(3) water and ethanol are made into mixed solution according to the weight ratio of 1:1, to add median size be 200 nanometers, have the fluorine resin microparticle of irregular polyhedrons pattern and median size is that (fluorine resin microparticle and inorganic compound particle are all after once being pulverized in cryogenic pulverization device by resin granular material for the uniform mixture of the inorganic compound particle of 50 nanometers, in cryogenic unit, grind again and to obtain), homogenization processing in ball mill, the dispersion liquid that formation content is 15wt%.Wherein, the mixing quality ratio of fluorine resin microparticle FEP and inorganic compound particle silicon oxide is 1:1.
(4) method of employing roller coat, is attached to by dispersion liquid the perfluorinated ion-exchange membrane both side surface that step (2) obtains, and surface layer thickness is about 900 nanometers, forms after drying finished product.
Performance test:
The ion-exchange membrane preparing is carried out in electrolyzer to the electrolysis test of sodium chloride aqueous solution, the sodium chloride aqueous solution of 300g/L is supplied with to anolyte compartment, by water supply cathode compartment, ensure that the sodium chloride concentration of discharging from anolyte compartment is 200g/L, the naoh concentration of discharging from cathode compartment is 34%; Probe temperature is 90 DEG C, and current density is 7.5kA/m
2, through the electrolytic experiment of 23 days, average groove was pressed as 2.73V, and mean current efficiency is 99.7%.
Afterwards, add inorganics Ca, Mg impurity 15ppb to supplying with in sodium chloride aqueous solution, carry out the electrolytic experiment of 40 days under above-mentioned identical condition, average groove is pressed and is stabilized in 2.74V, and mean current efficiency is 99.7%.
Surface resistance according to standard SJ/T 10171.5 method test gained films is 1.0 Ω cm
-2, adopting the abrasion loss of ASTM standard D 1044-99 test gained film is 2.7mg.
According to the electrolytic production examination criteria of standard, detect electrolytic production purity and be respectively, purity of chlorine gas feeding 99.7%, hydrogen purity 99.8%, salt content of soda 3ppm.
Embodiment 3
(1) choose the perfluorinated sulfonic resin of IEC=1.1mmol/g and the perfluorinated carboxylic acid resin of IEC=0.95mmol/g is combined into perfluorinated ion exchange resin basement membrane by the mode of coextrusion curtain coating, taking perfluorinated sulfonic resin in main resin layer perfluorinated sulfonic resin and perfluorinated carboxylic acid resin's mass ratio as 100:3, taking perfluorinated sulfonic resin in main resin layer perfluorinated carboxylic acid resin and perfluorinated sulfonic resin mass ratio as 100:2.5, wherein taking perfluorinated sulfonic resin as main resin layer thickness is as 150 microns, taking perfluorinated sulfonic resin as main resin layer thickness is as 7 microns.Again porous strongthener tetrafluoroethylene non-woven fabrics is immersed in Freon 113 in ultrasonic processor and propyl alcohol mixed solvent and processes 2 hours, wherein nonwoven thickness is 10 microns, porosity is 60%, after taking-up is dry, carry out compound with perfluorinated ion exchange resin basement membrane again, between film forming press-roller, introduce porous strongthener, under the effect of roll gap pressure, porous strongthener is pressed in the middle of film body, thereby forms perfluorinated ion-exchange membrane precursor.
(2) by the perfluorinated ion-exchange membrane precursor making in step (1) at the temperature of 80 DEG C, under the pressure of 60 tons, use superpressure machine to carry out superpressure processing with the speed of 1 m/min, after superpressure is processed, perfluorinated ion-exchange membrane precursor is immersed in the mixed aqueous solution that contains 15wt% dimethyl sulfoxide (DMSO) and 20wt% NaOH at 85 DEG C to 80 minutes, is converted into the perfluorinated ion-exchange membrane that possesses ion exchanging function.
(3) water and ethanol are made into mixed solution according to the weight ratio of 1:1, to add median size be 150 nanometers, have the fluorine resin microparticle of irregular polyhedrons pattern and median size is that (fluorine resin microparticle is after once being pulverized in cryogenic pulverization device by resin granular material for the uniform mixture of the inorganic compound particle of 500 nanometers, in cryogenic unit, grind again and to obtain), homogenization processing in ball mill, the dispersion liquid that formation content is 15wt%.Wherein, the mixing quality ratio of fluorine resin microparticle PVDF and inorganic compound particle titanium oxide is 1:50.
(4) adopt the method for brushing, 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 after drying finished product.
Performance test:
The ion-exchange membrane preparing is carried out in electrolyzer to the electrolysis test of sodium chloride aqueous solution, the sodium chloride aqueous solution of 300g/L is supplied with to anolyte compartment, by water supply cathode compartment, ensure that the sodium chloride concentration of discharging from anolyte compartment is 200g/L, the naoh concentration of discharging from cathode compartment is 30%; Probe temperature is 90 DEG C, and current density is 6.5kA/m
2, through the electrolytic experiment of 23 days, average groove was pressed as 2.75V, and mean current efficiency is 99.8%.
Afterwards, add inorganics Ca, Mg impurity 15ppb to supplying with in sodium chloride aqueous solution, carry out the electrolytic experiment of 40 days under above-mentioned identical condition, average groove is pressed and is stabilized in 2.75V, and mean current efficiency is 99.8%.
Surface resistance according to standard SJ/T 10171.5 method test gained films is 1.2 Ω cm
-2, adopting the abrasion loss of ASTM standard D 1044-99 test gained film is 2.6mg.
According to the electrolytic production examination criteria of standard, detect electrolytic production purity and be respectively, purity of chlorine gas feeding 99.8%, hydrogen purity 99.9%, salt content of soda 5ppm.
Embodiment 4
(1) choose the perfluorinated sulfonic resin of IEC=0.95mmol/g and the perfluorinated carboxylic acid resin of IEC=0.85mmol/g is combined into perfluorinated ion exchange resin basement membrane by the mode of coextrusion curtain coating, taking perfluorinated sulfonic resin in main resin layer perfluorinated sulfonic resin and perfluorinated carboxylic acid resin's mass ratio as 100:5, taking perfluorinated sulfonic resin in main resin layer perfluorinated carboxylic acid resin and perfluorinated sulfonic resin mass ratio as 100:5, wherein taking perfluorinated sulfonic resin as main resin layer thickness is as 75 microns, taking perfluorinated sulfonic resin as main resin layer thickness is as 15 microns.Again porous strongthener tetrafluoroethylene non-woven fabrics is immersed in Freon 113 in ultrasonic processor and methanol mixed solvent and processes 1 hour, wherein nonwoven thickness is 15 microns, porosity is 75%, after taking-up is dry, carry out compound with perfluorinated ion exchange resin basement membrane again, between film forming press-roller, introduce porous strongthener, under the effect of roll gap pressure, porous strongthener is pressed in the middle of film body, thereby forms perfluorinated ion-exchange membrane precursor.
(2) by the perfluorinated ion-exchange membrane precursor making in step (1) at the temperature of 30 DEG C, under the pressure of 40 tons, use superpressure machine to carry out superpressure processing with the speed of 10 ms/min, after superpressure is processed, perfluorinated ion-exchange membrane precursor is immersed in the mixed aqueous solution that contains 15wt% dimethyl sulfoxide (DMSO) and 20wt% NaOH at 85 DEG C to 80 minutes, is converted into the perfluorinated ion-exchange membrane that possesses ion exchanging function.
(3) water and ethanol are made into mixed solution according to the weight ratio of 1:1, to add median size be 50 nanometers, have the fluorine resin microparticle of irregular polyhedrons pattern and median size is that (fluorine resin microparticle is after once being pulverized in cryogenic pulverization device by resin granular material for the uniform mixture of the inorganic compound particle of 300 nanometers, in cryogenic unit, grind again and to obtain), homogenization processing in ball mill, the dispersion liquid that formation content is 15wt%.Wherein: the mixing quality ratio of fluorine resin microparticle PTFE and inorganic compound particle zirconium hydroxide is 100:1.
(4) adopt the method spraying, dispersion liquid is attached to the perfluorinated ion-exchange membrane both side surface that step (2) obtains, surface layer thickness is about 200 nanometers, forms after drying finished product.
Performance test:
The ion-exchange membrane preparing is carried out in electrolyzer to the electrolysis test of sodium chloride aqueous solution, the sodium chloride aqueous solution of 300g/L is supplied with to anolyte compartment, by water supply cathode compartment, ensure that the sodium chloride concentration of discharging from anolyte compartment is 200g/L, the naoh concentration of discharging from cathode compartment is 31%; Probe temperature is 90 DEG C, and current density is 6.5kA/m
2, through the electrolytic experiment of 23 days, average groove was pressed as 2.71V, and mean current efficiency is 99.7%.
Afterwards, add inorganics Ca, Mg impurity 15ppb to supplying with in sodium chloride aqueous solution, carry out the electrolytic experiment of 40 days under above-mentioned identical condition, average groove is pressed and is stabilized in 2.71V, and mean current efficiency is 99.7%.
Surface resistance according to standard SJ/T 10171.5 method test gained films is 1.2 Ω cm
-2, adopting the abrasion loss of ASTM standard D 1044-99 test gained film is 2.7mg.
According to the electrolytic production examination criteria of standard, detect electrolytic production purity and be respectively, purity of chlorine gas feeding 99.8%, hydrogen purity 100%, salt content of soda 3ppm.
Embodiment 5
(1) choose the perfluorinated sulfonic resin of IEC=0.9mmol/g and the perfluorinated carboxylic acid resin of IEC=0.85mmol/g is combined into perfluorinated ion exchange resin basement membrane by the mode of coextrusion curtain coating, taking perfluorinated sulfonic resin in main resin layer perfluorinated sulfonic resin and perfluorinated carboxylic acid resin's mass ratio as 100:5.5, taking perfluorinated sulfonic resin in main resin layer perfluorinated carboxylic acid resin and perfluorinated sulfonic resin mass ratio as 100:5, wherein taking perfluorinated sulfonic resin as main resin layer thickness is as 50 microns, taking perfluorinated sulfonic resin as main resin layer thickness is as 18 microns.Again porous strongthener tetrafluoroethylene non-woven fabrics is immersed in Freon 113 in ultrasonic processor and acetone mixed solvent and processes 1.5 hours, wherein nonwoven thickness is 10 microns, porosity is 85%, after taking-up is dry, carry out compound with perfluorinated ion exchange resin basement membrane again, between film forming press-roller, introduce porous strongthener, under the effect of roll gap pressure, porous strongthener is pressed in the middle of film body, thereby forms perfluorinated ion-exchange membrane precursor.
(2) by the perfluorinated ion-exchange membrane precursor making in step (1) at the temperature of 10 DEG C, under the pressure of 20 tons, use superpressure machine to carry out superpressure processing with the speed of 50 ms/min, after superpressure is processed, perfluorinated ion-exchange membrane precursor is immersed in the mixed aqueous solution that contains 15wt% dimethyl sulfoxide (DMSO) and 20wt% NaOH at 85 DEG C to 80 minutes, is converted into the perfluorinated ion-exchange membrane that possesses ion exchanging function.
(3) water and ethanol are made into mixed solution according to the weight ratio of 1:1, to add median size be 200 nanometers, have the fluorine resin microparticle of irregular polyhedrons pattern and median size is that (fluorine resin microparticle is after once pulverizing in cryogenic pulverization device for the uniform mixture of the inorganic compound particle of 50 nanometers, in cryogenic unit, grind again and to obtain), homogenization processing in ball mill, the dispersion liquid that formation content is 15wt%.Wherein, the mixing quality ratio of fluorine resin microparticle PFA and inorganic compound particle stannic oxide is 50:1.
(4) adopt the method spraying, dispersion liquid is attached to the perfluorinated ion-exchange membrane both side surface that step (2) obtains, surface layer thickness is about 1 micron, forms after drying finished product.
Performance test:
The ion-exchange membrane preparing is carried out in electrolyzer to the electrolysis test of sodium chloride aqueous solution, the sodium chloride aqueous solution of 300g/L is supplied with to anolyte compartment, by water supply cathode compartment, ensure that the sodium chloride concentration of discharging from anolyte compartment is 200g/L, the naoh concentration of discharging from cathode compartment is 32%; Probe temperature is 90 DEG C, and current density is 5.5kA/m
2, through the electrolytic experiment of 23 days, average groove was pressed as 2.70V, and mean current efficiency is 99.7%.
Afterwards, add inorganics Ca, Mg impurity 15ppb to supplying with in sodium chloride aqueous solution, carry out the electrolytic experiment of 40 days under above-mentioned identical condition, average groove is pressed and is stabilized in 2.71V, and mean current efficiency is 99.7%.
Surface resistance according to standard SJ/T 10171.5 method test gained films is 1.1 Ω cm
-2, adopting the abrasion loss of ASTM standard D 1044-99 test gained film is 2.7mg.
According to the electrolytic production examination criteria of standard, detect electrolytic production purity and be respectively, purity of chlorine gas feeding 99.8%, hydrogen purity 99.9%, salt content of soda 3ppm.
Claims (10)
1. for a Novel ion conductive membranes for chlorine industry, it is characterized in that: the upper layer being mixed by perfluorinated ion exchange resin basement membrane, porous strongthener and fluorine resin microparticle and inorganic compound particle forms.
2. the Novel ion conductive membranes for chlorine industry according to claim 1, it is characterized in that: described perfluorinated ion exchange resin basement membrane is by forming taking perfluorinated sulfonic resin as main resin layer with taking perfluorinated carboxylic acid resin as main resin layer, taking perfluorinated sulfonic resin as main resin layer thickness is as 30-300 micron, taking perfluorinated carboxylic acid resin as main resin layer thickness is as 2-30 micron; That perfluorinated sulfonic resin taking mass ratio as 100:0.1-100:10 and perfluorinated carboxylic acid resin's blend or copolymerization form taking perfluorinated sulfonic resin as main resin layer; That perfluorinated carboxylic acid resin taking mass ratio as 100:0.1-100:10 and perfluorinated sulfonic resin blend or copolymerization form taking perfluorinated carboxylic acid resin as main resin layer.
3. the Novel ion conductive membranes for chlorine industry according to claim 2, is characterized in that: the exchange capacity of perfluorinated sulfonic resin be 0.8-1.5 mmole/gram, perfluorinated carboxylic acid resin's exchange capacity be 0.8-1.2 mmole/gram.
4. the Novel ion conductive membranes for chlorine industry according to claim 1; it is characterized in that: the surface layer thickness that fluorine resin microparticle and inorganic compound particle mix is that between 20 nanometer-100 micron, in upper layer, the mass ratio of fluorine resin microparticle and inorganic compound particle is 1:100-100:1.
5. the Novel ion conductive membranes for chlorine industry according to claim 1, is characterized in that: inorganic compound particle is selected from a kind of in the oxide compound, oxyhydroxide, nitride of IV-A family, IV-B family, V-B family, iron, cobalt, nickel, chromium, manganese or boron or several mixture arbitrarily.
6. the Novel ion conductive membranes for chlorine industry according to claim 1, is characterized in that: fluorine resin microparticle is selected from a kind of or any several mixture in tetrafluoroethylene microparticle, PFA microparticle, perfluoroethylene-propylene microparticle, poly-perfluoro propyl vinyl ether microparticle or polyvinylidene difluoride (PVDF) microparticle.
7. according to the Novel ion conductive membranes for chlorine industry described in claim 1,5 or 6, it is characterized in that: the fluorine resin microparticle in upper layer, particle size range is between 20 nanometer-10 micron; Inorganic compound particle particle size range in upper layer is between 20 nanometer-10 micron.
8. the Novel ion conductive membranes for chlorine industry according to claim 1, is characterized in that: porous strongthener is tetrafluoroethylene non-woven fabrics, and fiber intersection is overlap or merge, and porous strongthener thickness is between 1-200 micron; Tetrafluoroethylene non-woven fabrics porosity is between 20-99%.
9. a preparation method for the Novel ion conductive membranes for chlorine industry claimed in claim 1, is characterized in that: comprise the following steps:
(1) help fluorion exchange resin basement membrane by the mode melting curtain coating of screw-type extruder coextrusion, again porous strongthener is immersed in fluorine carbon solvent, supersound process 1-2 hour, after taking-up is dry, carry out compound with perfluorinated ion exchange resin basement membrane again, between film forming press-roller, introduce porous strongthener, under the effect of roll gap pressure, porous strongthener is pressed in perfluorinated ion exchange resin basement membrane, thereby obtains perfluorinated ion-exchange membrane precursor;
(2) be the perfluorinated ion-exchange membrane with ion exchanging function by the perfluorinated ion-exchange membrane precursor conversion making in step (1);
(3) water and ethanol are made into mixed solution according to 1:1 weight ratio, add fluorine resin microparticle and inorganic compound particle mixture, homogenization processing in ball mill, forms dispersion liquid;
(4) dispersion liquid in (3) is attached to the perfluorinated ion-exchange membrane surface that step (2) obtains, forms after drying finished product.
10. the preparation method of the Novel ion conductive membranes for chlorine industry according to claim 9, it is characterized in that: fluorine resin microparticle is after once being pulverized in cryogenic pulverization device by resin granular material in step (3), then in cryogenic unit, grind and obtain.
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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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| CN111020630A (en) * | 2019-12-31 | 2020-04-17 | 山东东岳未来氢能材料有限公司 | Ultrathin perfluorocarboxylic acid ion exchange membrane with bubble-dispelling function and preparation method thereof |
| CN111074295A (en) * | 2019-12-31 | 2020-04-28 | 山东东岳未来氢能材料有限公司 | Novel low-resistance ion conduction membrane for chlor-alkali industry and preparation method thereof |
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| WO2015184572A1 (en) | 2015-12-10 |
| CN104018181B (en) | 2017-01-11 |
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