CN101372752B - High temperature resistant alkaline water electrolytic cell barrier diaphragm and preparation thereof - Google Patents
High temperature resistant alkaline water electrolytic cell barrier diaphragm and preparation thereof Download PDFInfo
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- CN101372752B CN101372752B CN2007100591849A CN200710059184A CN101372752B CN 101372752 B CN101372752 B CN 101372752B CN 2007100591849 A CN2007100591849 A CN 2007100591849A CN 200710059184 A CN200710059184 A CN 200710059184A CN 101372752 B CN101372752 B CN 101372752B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a diaphragm for a high temperature resistance alkaline water electrolyser, which is a needle-punched non-woven polyphenyl thioether diaphragm. The method for preparing the diaphragm comprises the following steps: (1) fibrous material selecting: PPS fiber is selected to prepare non-woven base cloth; (2) web carding: the fibrous material is carded into a web by a carding machine by opening and mixing; (3) web lapping: a carded single-web is manufactured into a multi-layer fibrous web with required width and thickness by lapping the web by a lapping machine; (4) strengthening: reinforced materials of the lapped multi-layer fibrous web are fed into a needle machine to manufacture a non-woven cloth with certain strength by pre-needling and multiple main needling on frontside and back side; (5) post-treatment: sulfonating treatment is carried out on the non-woven cloth in 90 to 98 percent of H2SO4, and then is treated by 30 percent of potassium hydroxide solution. The preparation method has the advantages of simple process, clearness and definitude, easy industrialized implementation, convenient operation and low cost; furthermore, the preparation method has easyprocess control so as to ensure stable performance of the product and stable quality.
Description
Technical field
The present invention relates to a kind of water electrolyzer barrier film and preparation method thereof, particularly relate to a kind of high temperature resistant alkaline water electrolytic cell barrier diaphragm and preparation method thereof.
Background technology
Along with technology and expanding economy and Increase of population, make people increasing to the demand of the energy.Be the fossil oil of representative with oil, coal at present, use on the one hand and brought the serious environmental pollution, on the other hand because its non-renewable and limited reserves will bring serious energy dilemma.So the reproducible new forms of energy of development cleaning are more and more urgent.Hydrogen is with its cleanliness without any pollution, and is efficient, can store and advantage such as transportation, is regarded as optimal energy carrier.Hydrogen except that as the free of contamination energy, also is used in many fields such as electronics, military affairs, aerospace, chemical, metallurgy, building materials, meteorology and automobile as a kind of inflammable gas.
The method of making hydrogen is a lot, and wherein the water electrolysis hydrogen production technical development gets maturation the most, is widely used.
Go up direct current when two electrodes (negative electrode and anode) are logical respectively, and when immersing in the water, water will be decomposed and produce hydrogen and oxygen respectively at negative electrode and anode, this process is exactly a brine electrolysis, and such device then is a water electrolyzer.
Electrolyzer in the market can be divided into three kinds: alkaline electrolytic bath, proton exchange membrane electrolyser (PEM) and means of solid oxide electrolytic cell.Alkaline electrolytic bath is business-like the earliest cell technologies, though its efficient is minimum in three kinds of electrolyzers, since cheap, still be widely used at present, especially in extensive hydrogen manufacturing industry, the shortcoming of alkaline electrolytic bath is that efficient is lower and use asbestos as barrier film.
Barrier film all occupies very important position in any electrolyzer, it places between anode, the negative electrode, stops the mixing of anode side oxygen and cathode side hydrogen, to guarantee gas purity, to improve current efficiency and security.Its specific requirement is: in 100 ℃ to the weather resistance of 30% potassium hydroxide electrolyte, scale resistance, less ion by resistance, high electronics by resistance, by the high initial wettability of electrolytic solution and permanent wettability, higher resistance to air loss, thin thickness, high mechanical stability.
Because the limitation of technology, at present domestic main hydrogen producer producer still adopts woven asbesto as barrier film, asbestos diaphragm is in excellent anti-corrosion performance below 90 ℃, in 30% the KOH solution, but its resistance is bigger,, when pressure increase easily dissolving and cause pollution to electrolytic solution too high when temperature; And asbestos have carinogenicity, can produce environment in the process of exploitation and processing use and pollute, and human body is worked the mischief.A lot of countries have proposed to forbid the use of asbestos in alkaline electrolytic bath.Therefore it is very urgent and necessary seeking new diaphragm material.
It is that the base cloth surface is coated with the barrier film of making hydrophilic modifying with sulfonation PPS with the PTFE fabric that italian patent 24836A/80 has introduced a kind of, this barrier film corrosion resistance nature is fine, but its production technique is comparatively complicated, need carry out roll compacting under High Temperature High Pressure, diaphragm size is subjected to certain limitation, and homogeneity is poor, and because its PTFE surface energy that adopts is very little, be difficult to bondedly, it and PPS material thermal expansion coefficient differ greatly, the easy layering so barrier film is heated.
U.S. Pat 4895634 adopts pure polyphenylene sulfide fibre to make woven cloth or nonwoven mat, and adopt means of different (sulfonation, phosphinylidyneization, phosphorylated) to carry out hydrophilic modifying, and claiming its membrane properties excellence according to patent, heatproof is corrosion-resistant, water-intake rate 300%, gas purity can reach 99.99%; But its membrane thicknesses is big (about 2mm), and its hydrophilic aftertreatment technology is complicated, and the time is grown (being about 2h), and its patent is not pointed out the barrier film complete processing.
At present, adopt needle-punched non-woven polyphenylene sulfide (PPS) barrier film, still belong to the first time at home, the associated viscera of its preparation method is not seen open yet.
Summary of the invention
In order to overcome existing membranous weak point, the invention provides a kind of high temperature resistant alkaline water electrolytic cell barrier diaphragm and preparation method thereof.
Technical scheme of the present invention is to realize like this.
A kind of high temperature resistant alkaline electrolytic bath barrier film is needle-punched non-woven polyphenylene sulfide (PPS) barrier film.
The membranous preparation method of a kind of high temperature resistant alkaline electrolytic bath, this method comprises:
(1) selection of fibrous material: select for use the PPS fiber to prepare the non-woven base cloth.Staple length is 20～80mm, and fiber number is 0.8～6.0dtex.
(2) carding: fibrous material is through shredding, mixing, carding machine carding.
(3) lapping: the multilayer fibre web of desired fabric width and thickness is made in the single net process lapping machine lapping after the combing.
(4) reinforce: the multilayer fibre web strongthener of completing is sent into needle loom,, make non-woven with certain brute force through pre-thorn and pros and cons multiple tracks master thorn.
(5) aftertreatment: hydrophilic treatment, with non-woven at 70～130 ℃, 90～98% H
2SO
4In carry out sulfonation and handled 20～40 minutes; Handle with 30% potassium hydroxide solution then.
Preparation method's technology of the present invention is simple, and clear and definite, and industrializing implementation is easy, and is simultaneously easy to operate, with low cost; Preparation method's technology controlling and process of the present invention is easy, therefore can guarantee that product performance are reliable, steady quality.
Utilize the prepared high temperature resistant alkaline water electrolytic cell barrier diaphragm excellent property of preparation method of the present invention, steady quality.Performance index such as the homogeneity of product, thickness, intensity, voidage, resistance to air loss, resistance, chemical resistant properties all meet the demands.The further barrier film of handling (sulfonation processing) production of process satisfies the service requirements of alkaline water electrolytic cell fully, and technical indicator meets or exceeds the technical requirements of China's building material industry standard (JC/T211-2000 barrier film woven asbesto standard).
Embodiment
The invention will be further described below in conjunction with embodiment.
A kind of high temperature resistant alkaline electrolytic bath barrier film is needle-punched non-woven polyphenylene sulfide (PPS) barrier film.
Disadvantageously, the PPS fiber that is applied to alkaline electrolysis hydrogen manufacturing diaphragm for electrolytic cell material is hydrophobic, can not satisfy the important need of and good wettability quick by electrolytic solution, yet bad wettability will cause the gathering of bubble in the operational process, hinder ionic and pass through, increased resistance, the final energy consumption that increases electrolyzer, so, must carry out hydrophilic treatment to barrier film.
The preparation method of high temperature resistant alkaline water electrolytic cell barrier diaphragm of the present invention mainly comprises five steps: the selection of (1) fibrous material; (2) shredding of fiber, mixing, combing, one-tenth net; (3) lapping: the multilayer fibre web of desired fabric width and thickness is made in the single net process lapping machine lapping after the combing; (4) pinprick reinforcement; (5) hydrophilic aftertreatment.According to prior art, the technical issues that need to address mainly contain two: the membranous one-tenth mesh reinforcement technique of non-woven, barrier film aftertreatment technology are selected and processing parameter setting.
Preparation method of the present invention requires selected fibrous material must have anti-highly basic under the high temperature, good in oxidation resistance, and the intensity height possesses the characteristic of good hydrophilic property simultaneously.Experimental study shows, polyetheretherketonefiber fiber 50% alkali lye boil for a long time for 100 ℃ boil the back do not have weightless, no loss of strength, and be beneficial to carrying out smoothly of sulfonation reaction, be easy to the grafting sulfonic acid group, the present invention selects polyphenylene sulfide fibre for use, staple length is 20～80mm, and fiber number is 0.8～6.0dtex.
The problem that emphasis of the present invention solves is membranous one-tenth mesh reinforcement technique of non-woven and hydrophilic treatment process.As the alkaline electrolytic bath barrier film, require material to have certain intensity, porosity, thin thickness and have preferably wetting ability to have less resistance to reduce equipment energy consumption to guarantee it.Be limited to pinprick reinforcement technology, product thickness can not be too small, and the too small meeting of thickness produces considerable influence to the intensity of material, and the present invention tries hard to make its thickness minimum under the situation that guarantees product strength as far as possible.Because the research of domestic p-poly-phenyl thioether fiber is very few, the present invention adopts the sulfonated method that it is handled, and constantly carries out technology and explores, and finally finds out best process for sulfonation parameter.
Preparation method of the present invention does not address part and is applicable to prior art.
Utilize preparation method of the present invention can make alkaline electrolytic bath barrier film of the present invention.Compare with the test of China building material industry standard JC211 asbestos diaphragm, the performance requriements of product of the present invention all satisfies the service requirements of alkaline electrolytic bath.Product specific targets of the present invention are as shown in table 1.
Table 1 product of the present invention and JC211 asbestos diaphragm test rating contrast table
| Index parameter | Product of the present invention | The JC211 asbestos diaphragm |
| Grammes per square metre g/m 2Tensile strength (vertically) N/50mm ventilation property m 3/(m 2Min) thickness mm water-intake rate hygrometric state resistance to air loss mmH 2O cell voltage V current density A/m 2Energy consumption kwh/m 3H 2Film cost RMB/m 2 | Below 500 more than 1000 more than 8 below 1.5 more than 310% below 2801.8 more than 4000 below 4.3 below 200 | 4 ± 0.5200%300 above 2.020004.8300 more than 1.95 more than 4000 ± 502500 |
Annotate: the tensile strength of product of the present invention can satisfy service requirements, the tensile strength numerical value surplus of JC211 asbestos diaphragm.
Provide specific embodiments of the invention below:
Select PPS fiber production alkaline electrolytic bath barrier film for use.
Example one: staple length is 40mm, and fiber number is 1.1dtex.
(1) carding: fibrous material is through shredding, mixing, carding machine carding and lapping.
(2) reinforce: the multilayer fibre web of completing is sent into needle loom,, make non-woven with certain brute force through pre-thorn and pros and cons multiple tracks master thorn.
(3) hydrophilic aftertreatment: with non-woven at 70 ℃, 98% H
2SO
4In carry out sulfonation and handled 40 minutes; Handle with 30% potassium hydroxide solution then.
Example two: staple length is 50mm, and fiber number is 1.1dtex.
(1) carding: fibrous material is through shredding, mixing, carding machine carding and lapping.
(2) reinforce: the multilayer fibre web of completing is sent into needle loom,, make non-woven with certain brute force through pre-thorn and pros and cons multiple tracks master thorn.
(3) hydrophilic aftertreatment: with non-woven at 80 ℃, 95% H
2SO
4In carry out sulfonation and handled 30 minutes; Handle with 30% potassium hydroxide solution then.
Example three: staple length is 60mm, and fiber number is 3.0dtex.
(1) carding: fibrous material is through shredding, mixing, carding machine carding and lapping.
(2) reinforce: the multilayer fibre web of completing is sent into needle loom,, make non-woven with certain brute force through pre-thorn and pros and cons multiple tracks master thorn.
(3) hydrophilic aftertreatment: with non-woven at 90 ℃, 90% H
2SO
4In carry out sulfonation and handled 30 minutes; Handle with 30% potassium hydroxide solution then.
Example four: staple length is 50mm, and fiber number is 2.2dtex.
(1) carding: fibrous material is through shredding, mixing, carding machine carding and lapping.
(2) reinforce: the multilayer fibre web of completing is sent into needle loom,, make non-woven with certain brute force through pre-thorn and pros and cons multiple tracks master thorn.
(3) hydrophilic aftertreatment: with non-woven at 130 ℃, 98% H
2SO
4In carry out sulfonation and handled 20 minutes; Handle with 30% potassium hydroxide solution then.
Example five: staple length is 70mm, and fiber number is 4.4dtex.
(1) carding: fibrous material is through shredding, mixing, carding machine carding and lapping.
(2) reinforce: the multilayer fibre web of completing is sent into needle loom,, make non-woven with certain brute force through pre-thorn and pros and cons multiple tracks master thorn.
(3) hydrophilic aftertreatment: with non-woven at 100 ℃, 98% H
2SO
4In carry out sulfonation and handled 20 minutes; Handle with 30% potassium hydroxide solution then.
Example six: staple length is 38mm, and fiber number is 1.5dtex.
(1) carding: fibrous material is through shredding, mixing, carding machine carding and lapping.
(2) reinforce: the multilayer fibre web of completing is sent into needle loom,, make non-woven with certain brute force through pre-thorn and pros and cons multiple tracks master thorn.
(3) hydrophilic aftertreatment: with non-woven at 80 ℃, 98% H
2SO
4In carry out sulfonation and handled 20 minutes; Handle with 30% potassium hydroxide solution then.
Claims (1)
1. the preparation method of a high temperature resistant alkaline water electrolytic cell barrier diaphragm, described barrier film is a needle-punched non-woven polyphenylene sulfide barrier film, it is characterized in that:
This membranous preparation method may further comprise the steps:
(1) selection of fibrous material: select for use the PPS fiber to prepare the non-woven base cloth, staple length is 20～80mm, and fiber number is 0.8～6.0dtex;
(2) carding: fibrous material is through shredding, mixing, carding machine carding;
(3) lapping: the multilayer fibre web of desired fabric width and thickness is made in the single net process lapping machine lapping after the combing;
(4) reinforce: the multilayer fibre web strongthener of completing is sent into needle loom,, make non-woven with certain brute force through pre-thorn and pros and cons multiple tracks master thorn;
(5) aftertreatment: hydrophilic treatment, with non-woven at 70～130 ℃, 90～98% H
2SO
4In carry out sulfonation and handled 20～40 minutes; Handle with 30% potassium hydroxide solution then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100591849A CN101372752B (en) | 2007-08-21 | 2007-08-21 | High temperature resistant alkaline water electrolytic cell barrier diaphragm and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100591849A CN101372752B (en) | 2007-08-21 | 2007-08-21 | High temperature resistant alkaline water electrolytic cell barrier diaphragm and preparation thereof |
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| Publication Number | Publication Date |
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| CN101372752A CN101372752A (en) | 2009-02-25 |
| CN101372752B true CN101372752B (en) | 2010-12-08 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103938337A (en) | 2013-01-18 | 2014-07-23 | 东丽纤维研究所（中国）有限公司 | Diaphragm cloth for water electrolyser and method for producing diaphragm cloth |
| WO2016162417A1 (en) * | 2015-04-08 | 2016-10-13 | Stojadinovic Jelena | Woven or nonwoven web |
| CN106148992A (en) * | 2015-04-20 | 2016-11-23 | 李坚 | Ionic membrane catalysis method or electrodialysis catalysis method water hydrogen manufacturing and application thereof |
| CN106480573A (en) * | 2015-08-24 | 2017-03-08 | 东丽纤维研究所（中国）有限公司 | A kind of high-performance polyphenylene sulfide fiber tectosome and its production method and purposes |
| EP3447177B1 (en) * | 2016-04-18 | 2023-10-25 | Toray Industries, Inc. | Polyphenylene sulfide woven fabric for water electrolyser and manufacturing method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539082A (en) * | 1983-06-11 | 1985-09-03 | Bayer Aktiengesellschaft | Woven diaphragm for aqueous electrolytes |
| US4707228A (en) * | 1986-06-06 | 1987-11-17 | Treadwell Corporation | Diaphragm for electrolytic and electrochemical cells |
| US4895634A (en) * | 1987-06-22 | 1990-01-23 | Fratelli Testori S.P.A. | Porous separatory member entirely made of polyphenylene sulfide for the electrolysis of water |
| CN1747199A (en) * | 2005-07-26 | 2006-03-15 | 天津工业大学 | Production of nickel-hydrogen diaphragm and products thereof |
| CN1752294A (en) * | 2005-08-23 | 2006-03-29 | 陈维军 | High-efficient diaphragm and mfg. method |
| CN1861870A (en) * | 2006-06-22 | 2006-11-15 | 时准 | High performance fibre nonwoven fabric and mfg. method thereof |
-
2007
- 2007-08-21 CN CN2007100591849A patent/CN101372752B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539082A (en) * | 1983-06-11 | 1985-09-03 | Bayer Aktiengesellschaft | Woven diaphragm for aqueous electrolytes |
| US4707228A (en) * | 1986-06-06 | 1987-11-17 | Treadwell Corporation | Diaphragm for electrolytic and electrochemical cells |
| US4895634A (en) * | 1987-06-22 | 1990-01-23 | Fratelli Testori S.P.A. | Porous separatory member entirely made of polyphenylene sulfide for the electrolysis of water |
| CN1747199A (en) * | 2005-07-26 | 2006-03-15 | 天津工业大学 | Production of nickel-hydrogen diaphragm and products thereof |
| CN1752294A (en) * | 2005-08-23 | 2006-03-29 | 陈维军 | High-efficient diaphragm and mfg. method |
| CN1861870A (en) * | 2006-06-22 | 2006-11-15 | 时准 | High performance fibre nonwoven fabric and mfg. method thereof |
Non-Patent Citations (2)
| Title |
|---|
| V. M. ROSA等."NEW MATERIALS FOR WATER ELECTROLYSIS DIAPHRAGMS".Int. J. Hydrogen EnergyVol. 20 No. 9.1995,Vol. 20(No. 9),697-700. * |
| V.M.ROSA等."NEWMATERIALSFORWATERELECTROLYSISDIAPHRAGMS".Int.J.HydrogenEnergyVol.20No.9.1995 Vol. 20(No. 9) |
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