CN116607172A - Preparation method of special resin for alkaline water electrolysis cell diaphragm, product and application thereof - Google Patents
Preparation method of special resin for alkaline water electrolysis cell diaphragm, product and application thereof Download PDFInfo
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- CN116607172A CN116607172A CN202310558929.5A CN202310558929A CN116607172A CN 116607172 A CN116607172 A CN 116607172A CN 202310558929 A CN202310558929 A CN 202310558929A CN 116607172 A CN116607172 A CN 116607172A
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- alkaline water
- water electrolysis
- electrolysis cell
- sodium sulfide
- nano zirconia
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229920005989 resin Polymers 0.000 title claims abstract description 48
- 239000011347 resin Substances 0.000 title claims abstract description 48
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 41
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims description 20
- 230000018044 dehydration Effects 0.000 claims description 16
- 238000006297 dehydration reaction Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000004745 nonwoven fabric Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- 238000002074 melt spinning Methods 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 abstract description 43
- 229920000069 polyphenylene sulfide Polymers 0.000 abstract description 43
- 230000000694 effects Effects 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 210000004027 cell Anatomy 0.000 description 22
- 208000005156 Dehydration Diseases 0.000 description 15
- 239000000835 fiber Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000009987 spinning Methods 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000010425 asbestos Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229910052895 riebeckite Inorganic materials 0.000 description 7
- 239000004744 fabric Substances 0.000 description 5
- 238000006277 sulfonation reaction Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 210000000170 cell membrane Anatomy 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- RANCECPPZPIPNO-UHFFFAOYSA-N 2,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC=C1Cl RANCECPPZPIPNO-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFXZSGVZSSMCMB-UHFFFAOYSA-N 2,5-dichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(Cl)=CC=C1Cl LFXZSGVZSSMCMB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polyphenylene sulfate Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a preparation method of special resin for an alkaline water electrolysis cell diaphragm, which comprises the following steps: step one: putting N-methyl pyrrolidone and sodium sulfide aqueous solution into a polymerization kettle, heating and then dehydrating; step two: adding N-methyl pyrrolidone and p-dichlorobenzene into a polymerization kettle, continuously heating for polymerization, and finally performing a post-treatment procedure; the preparation method is also added with nano zirconia, wherein the nano zirconia can be added together with sodium sulfide aqueous solution in the first step, or can be added together with paradichlorobenzene in the second step. According to the preparation method disclosed by the invention, the nano zirconia is added in the preparation process of the resin, so that the nano zirconia is uniformly dispersed, and the hydrophilic modification effect on the polyphenylene sulfide is improved; the further proposal is that the third monomer with special substituent groups is added in the polymerization stage while the nano zirconia is added, and the aim of obviously improving the hydrophilicity of the polyphenylene sulfide is achieved by utilizing the synergy of the nano zirconia and the third monomer.
Description
Technical Field
The invention relates to the technical field of diaphragms, in particular to a preparation method of a special resin for an alkaline water electrolysis cell diaphragm, a product and application thereof.
Background
The hydrogen energy is widely concerned worldwide as an efficient and clean secondary energy source, and the H is produced in a large scale and at low cost 2 Is to develop and utilize H 2 One of the important links of energy sources. The hydrogen production by water electrolysis has the advantages of relatively simple operation, relatively mature technology and H production 2 High purity and no pollution in the hydrogen production process, and is used for realizing large-scale production of H 2 Is an important means of (a). Currently, domestic alkaline water electrolysis is dominant in the water electrolysis industry.
In general, an alkaline electrolyzer is charged with an electrolyte (typically 20 to 30wt% aqueous potassium hydroxide solution) and water is decomposed by direct current to produce H at the cathode 2 Anode producing O 2 H that the diaphragm will produce 2 、O 2 The strict isolation allows free movement of ions in the circuit within the cell. The quality of the diaphragm is directly related to H 2 、O 2 And thus becomes a thermoelectric for research. The requirements for the separator include:
1) Can be wetted by electrolyte, so that ions in the solution can smoothly pass through;
2) The air tightness is good, and the safe operation of the electrolytic tank and the purity of the outlet gas are not affected;
3) Has enough mechanical strength;
4) The electrolyte is not corroded by alkali liquor, so that the chemical stability is strong;
5) Low price and is suitable for industrial use.
For a long time, the main raw material of the alkaline electrolytic cell diaphragm is asbestos, and the asbestos diaphragm has the advantages of good hydrophilic performance, easy ion passing and the like; however, the swelling and chemical instability of the asbestos diaphragm itself lead to the defect of serious swelling in specific operating environments, especially under high current load, leading to a shortened service life; moreover, due to the limitation of the asbestos material, the temperature of the electrolyte can only be controlled below 90 ℃, and when the temperature of the electrolyte exceeds 90 ℃, the corrosion of the asbestos diaphragm is aggravated, so that the pollution to the electrolyte is caused, and the service life of the electrolyte is influenced. In view of the above, the development of a novel diaphragm material capable of replacing an asbestos diaphragm has become an important topic in the industry.
Polyphenylene Sulfide (PPS) materials have the advantage of being chemically stable, and resistant to severe water electrolysis conditions of high temperatures and strong alkali, thereby becoming a popular choice for replacing asbestos diaphragms. However, PPS is highly hydrophobic and requires treatment such as grafting, oxidation, sulfonation, and plasma to form a hydrophilic surface.
In the Chinese patent document with the publication number of CN101372752A, a high-temperature-resistant alkaline water electrolysis cell diaphragm and a preparation method thereof are disclosed, wherein a polyphenylene sulfide diaphragm is prepared by a needle punching non-woven fabric technology, and then the PPS non-woven fabric is subjected to sulfonation treatment and neutralization by sequentially using 90-98% concentrated sulfuric acid and 30% potassium hydroxide solution so as to improve the hydrophilicity of the non-woven fabric. Although the water absorption rate of the product prepared by adopting the technical scheme is up to more than 310%, the production process is extremely not environment-friendly, not only is strong corrosive raw materials such as strong acid, strong alkali and the like adopted, but also has great production danger, needs to consume a large amount of water resources in the cleaning process of post-treatment, has longer cleaning time, and is complex in process operation and not suitable for industrial production. And meanwhile, fiber embrittlement exists after sulfonation treatment, so that the service life of the diaphragm is shortened.
As another example, in chinese patent document with application publication No. CN 104746202A, a membrane fabric for a water electrolysis cell and a production method thereof are disclosed, wherein polyphenylene sulfide fibers are spun through a cotton spinning process of blowing-carding-drawing-roving-spinning-winding-doubling-twisting-heat setting, and then the obtained polyphenylene sulfide yarns are woven through a loom to obtain a high-density woven fabric; finally, hydrophilic processing is carried out by plasma treatment, so that hydrophilic groups are generated on the surface of the fabric. However, the plasma treatment adopted in the technical scheme can only generate hydrophilic groups on the surface of the fiber in nanometer level depth, and meanwhile, the change of the surface property has a certain effectiveness, and the obtained hydrophilic groups gradually decrease along with the extension of time, so that the loss of hydrophilicity is caused, and the degree of hydrophilic wettability of the material is limited in improvement. Moreover, the process equipment investment is high, and the method is not suitable for large-scale industrial production.
Then, as disclosed in Chinese patent document with application publication number of CN 113862821A, a polyphenylene sulfate fiber fabric type alkaline water electrolysis diaphragm and a preparation method thereof are disclosed, wherein zirconia inorganic nano particles and polyphenylene sulfide resin are mixed and granulated, zirconia modified polyphenylene sulfide fibers are obtained through melt spinning, and then the fibers are spun and woven into cloth, and then through a water needling process, the polyphenylene sulfide fiber fabric type alkaline water electrolysis diaphragm is obtained. In the technical scheme, only the nano zirconia and the polyphenylene sulfide are simply blended and modified, and the problem of agglomeration of the nano material is known, so that the method is difficult to disperse the zirconia in nano scale, and the hydrophilic modification effect of the zirconia on the polyphenylene sulfide is further affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a preparation method of resin special for an alkaline water electrolysis cell diaphragm, wherein nano zirconia is added in the preparation process of the resin, so that the nano zirconia is uniformly dispersed, and the hydrophilic modification effect of polyphenylene sulfide is improved; the further proposal is that the third monomer with special substituent groups is added in the polymerization stage while the nano zirconia is added, and the aim of obviously improving the hydrophilicity of the polyphenylene sulfide is achieved by utilizing the synergy of the nano zirconia and the third monomer.
The specific technical scheme is as follows:
the preparation method of the resin special for the alkaline water electrolysis cell diaphragm comprises the following steps:
step one: putting N-methyl pyrrolidone and sodium sulfide aqueous solution into a polymerization kettle, heating and then dehydrating;
step two: adding N-methyl pyrrolidone and p-dichlorobenzene into a polymerization kettle, continuously heating for polymerization, and finally obtaining the resin special for the alkaline water electrolysis cell diaphragm through a post-treatment procedure;
the preparation method is also added with nano zirconia, wherein the nano zirconia can be added together with sodium sulfide aqueous solution in the first step, or can be added together with paradichlorobenzene in the second step.
According to the preparation method disclosed by the invention, the nano zirconia is added in the polymerization stage of the PPS resin, so that the nano zirconia is uniformly dispersed, and the hydrophilic modification effect on the polyphenylene sulfide is improved. Experiments show that compared with the method without adding nano zirconia or the method that nano zirconia is added in a blending mode after the preparation of PPS resin is completed, the effect of hydrophilic modification on polyphenylene sulfide is inferior to that of the invention. Experiments also find that the addition of nano zirconia can obviously reduce the average grain diameter of the prepared PPS resin, improve the crystallization temperature of the PPS resin, ensure that the crystallization temperature is higher, and are easier to process and form in the spinning process, thereby being convenient for processing.
Preferably, a third monomer is further added in the second step of the preparation method disclosed by the invention;
the third monomer is selected from monosubstituted paradichlorobenzene, and the substituent is selected from one or more of sulfonic acid group, hydroxyl group, carboxylic acid group, aldehyde group and phosphate group;
experiments show that the addition of the third monomer can further reduce the average particle size of the prepared PPS resin and improve the crystallization temperature of the PPS resin; and the hydrophilicity of the finally prepared PPS-based alkaline water electrolysis cell diaphragm can be obviously improved through the synergistic addition of the third monomer and the nano zirconia.
Preferably, the molar ratio of the added nano zirconia to the sodium sulfide is 0.05-3.00: 100, wherein the average grain diameter of the nano zirconia is 1-100 nm.
Further preferably, the molar ratio of the nano zirconia to the sodium sulfide is 0.5-3.0: 100, wherein the average grain diameter of the nano zirconia is 50-100 nm.
Preferably:
the molar ratio of the third monomer to the sodium sulfide in the first step is 0.01-0.5: 1, a step of;
the ratio of the sum of the moles of paradichlorobenzene and the moles of the third monomer to the moles of sodium sulfide in the step one is 0.8 to 1.3.
Further preferably, the substituent in the third monomer is selected from one or more of a sulfonic acid group, a hydroxyl group, a carboxylic acid group, and a phosphoric acid group;
the molar ratio of the third monomer to the sodium sulfide in the first step is 0.05-0.1: 1, a step of;
the ratio of the sum of the moles of paradichlorobenzene and the moles of the third monomer to the moles of sodium sulfide in the step one is 1.0 to 1.2.
Still more preferably:
the molar ratio of the nanometer zirconia to the sodium sulfide is 0.5:100, wherein the average grain diameter of the nano zirconia is 50nm;
the substituent in the third monomer is selected from sulfonic acid groups and/or hydroxyl groups;
the molar ratio of the third monomer to sodium sulfide in the first step is 0.1:1, a step of;
the ratio of the sum of the moles of p-dichlorobenzene and the moles of the third monomer to the moles of sodium sulfide in step one was 1.1.
With the continuous preference of the raw materials and the technological parameters, the hydrophilicity of the finally prepared PPS-based alkaline water electrolysis cell diaphragm is continuously improved.
In the first step:
the mass concentration of the sodium sulfide aqueous solution is 20-80%; preferably 35wt%.
The molar ratio of the N-methyl pyrrolidone to the sodium sulfide is 1.0-5.0: 1, preferably 2.0:1.
in the first step, the temperature rising rate is 1-10 ℃/min, and the dehydration procedure is carried out after the temperature rises to 150-210 ℃;
in the second step, the polymerization is carried out after the temperature is raised to 240-280 ℃, the temperature raising rate is 1-20 ℃/min, and the polymerization time is 1-8 h;
the post-treatment includes a washing treatment and a drying treatment.
The washing treatment sequentially comprises acetone washing and pure water washing;
the molar ratio of the acetone to the sodium sulfide in the step one is 1-50: 1, the washing times are 1 to 6 times, and the washing temperature is 10 to 40 ℃;
the pure water is washed, and the molar ratio of the pure water to the sodium sulfide in the step one is 1-100: 1, the washing times are 1-10 times, and the washing temperature is 50-200 ℃;
the temperature of the drying treatment is 80-180 ℃ and the time is 1-12 h.
Preferably:
the nano zirconia is added together with the sodium sulfide aqueous solution in the first step; experiments show that the nano zirconia is added in the dehydration stage, which is more beneficial to reducing the average particle size of the prepared PPS resin and improving the crystallization temperature of the PPS resin; however, the effect is different at a lower nano zirconia addition amount, and is more remarkable at a higher addition amount.
The invention also discloses the resin special for the alkaline water electrolysis cell diaphragm prepared by the method.
The invention also discloses a preparation method of the alkaline water electrolysis cell diaphragm, which is prepared by taking the resin special for the alkaline water electrolysis cell diaphragm prepared by the method as a raw material and performing a melt spinning process and a needle punching non-woven fabric process.
The alkaline water electrolytic cell membrane prepared by the invention has excellent hydrophilicity, the water absorption rate can reach 285% at the highest, and the wicking height can reach 421mm at the highest.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method disclosed by the invention, the nano zirconia is added in the polymerization stage of the PPS resin, so that the nano zirconia is uniformly dispersed, and the hydrophilic modification effect on the polyphenylene sulfide is improved; the preparation method can also obviously reduce the average grain diameter of the prepared PPS resin and improve the crystallization temperature of the PPS resin.
The invention also discloses a preferable preparation method, wherein a third monomer with a special substituent group is added in the polymerization stage, and the third monomer is cooperated with the addition of nano zirconia, so that the average particle size of the prepared PPS resin is further reduced, and the crystallization temperature of the PPS resin is increased; the hydrophilicity of the finally prepared PPS-based alkaline water electrolysis cell diaphragm is improved more remarkably.
Detailed Description
The present invention will be described in further detail with reference to examples and comparative examples, but embodiments of the present invention are not limited thereto.
Example 1
Step one: n-methylpyrrolidone (NMP), an aqueous solution of sodium sulfide (35 wt%) and nano zirconia (d50=50 nm) were charged into a polymerizer, wherein sodium sulfide was 100mol, NMP was 200mol, and the molar ratio of nano zirconia to sodium sulfide was 0.5:100; after heating, carrying out a dehydration procedure, wherein the dehydration heating rate is 5 ℃/min, the dehydration end point temperature is 180 ℃, and no bubbles are generated in the absorption liquid within 1min from the dehydration to the air duct outlet of the dehydration kettle;
step two: NMP, paradichlorobenzene and a third monomer of 2-hydroxy-1, 4 dichlorobenzene are added into a polymerization kettle, the molar ratio of paradichlorobenzene to sodium sulfide added in the first step is 1.05,2-hydroxy-1, 4 dichlorobenzene to sodium sulfide added in the first step is 0.05, the NMP is 300mol, polymerization is carried out after further heating, the heating rate of the polymerization is 5 ℃/min, the heat preservation temperature of the polymerization stage is 240 ℃, and the polymerization duration is 4 hours.
Step three: respectively and continuously washing the product obtained in the step two with acetone for 2 times, wherein the washing temperature is 30 ℃, and the molar ratio of resin to acetone is 50:1 each time; and respectively and continuously washing with pure water for 5 times, wherein the washing temperature is 80 ℃, the molar ratio of the resin to the pure water is 100:1 each time, and finally drying at 120 ℃ for 6 hours to obtain the resin special for the alkaline water electrolytic cell diaphragm.
Comparative example 1
The preparation process was substantially the same as in example 1, except that nano zirconia was not added in the dehydration process of step one.
Comparative example 2
The preparation process is substantially the same as in example 1, except that:
the nano zirconia is not added in the dehydration procedure of the first step;
the third monomer is not added in the polymerization step of the second step.
Example 2
The preparation process was substantially the same as in example 1, except that the third monomer added in the polymerization step of step two was replaced with equimolar 2-sulfo-1, 4-dichlorobenzene.
Example 3
The preparation process was substantially the same as in example 1, except that the third monomer added in the polymerization step of step two was replaced with equimolar 2-carboxylate-1, 4-dichlorobenzene.
Example 4
The preparation process was substantially the same as in example 1, except that the third monomer added in the polymerization step of step two was replaced with equimolar 2-aldehyde-1, 4-dichlorobenzene.
Example 5
The preparation process was substantially the same as in example 1, except that the third monomer added in the polymerization step of step two was replaced with equimolar 2-phosphate-1, 4-dichlorobenzene.
Example 6
The preparation process was substantially the same as in example 1, except that in the polymerization step of the second step, the molar ratio of p-dichlorobenzene to sodium sulfide added in the first step was 1.0:1, 2-hydroxy-1, 4-dichlorobenzene to sodium sulfide added in the first step was 0.1:1.
Example 7
The preparation process was substantially the same as in example 2, except that the molar ratio of nano zirconia to sodium sulfide added in the dehydration step one was replaced with 0.05:100.
Example 8
The preparation process was substantially the same as in example 2, except that the molar ratio of nano zirconia to sodium sulfide added in the dehydration step one was replaced with 1.5:100.
Example 9
The preparation process was substantially the same as in example 2, except that the molar ratio of nano zirconia to sodium sulfide added in the dehydration step one was replaced with 3.0:100.
Example 10
The preparation process was essentially the same as in example 9, except that the nano zirconia was not added in the dehydration step of step one, but was added simultaneously with the third monomer in step two, the molar ratio of added nano zirconia to sodium sulfide in step one was still 3.0:100.
Example 11
The preparation process was substantially the same as in example 2, except that the average particle size of the nano zirconia added in the dehydration step one was replaced with d50=100 nm, respectively.
Example 12
The preparation process was substantially the same as in example 1, except that the third monomer was not added in the polymerization process of step two.
Example 13
The preparation process is substantially the same as in example 1, except that the nano zirconia is not added in the dehydration step of step one, but is added simultaneously with the third monomer in step two, and the molar ratio of the added nano zirconia to sodium sulfide in step one is still 0.5:100.
The average particle diameter and crystallization temperature data of the resins prepared in each example and comparative example are given in table 1 below.
TABLE 1
| Numbering device | Average particle diameter a /μm | Crystallization temperature b /℃ |
| Example 1 | 430 | 225 |
| Comparative example 1 | 1300 | 198 |
| Comparative example 2 | 1500 | 193 |
| Example 2 | 440 | 225 |
| Example 3 | 445 | 225 |
| Example 4 | 490 | 223 |
| Example 5 | 460 | 224 |
| Example 6 | 405 | 226 |
| Example 7 | 1100 | 204 |
| Example 8 | 550 | 222 |
| Example 9 | 650 | 219 |
| Example 10 | 670 | 218 |
| Example 11 | 560 | 221 |
| Example 12 | 520 | 222 |
| Example 13 | 480 | 224 |
a. The average particle diameter is obtained by sieving
b. The crystallization temperature is obtained by DSC test, specifically, the temperature is raised to 380 ℃ from normal temperature at 5 ℃/min, the temperature is kept for 5min, and then the temperature is lowered to normal temperature at a cooling speed of 5 ℃/min.
Performance test:
the resins prepared in each example and each comparative example are respectively melted and blended by a double screw extruder, extruded and granulated, dried for 12 hours under vacuum at 100 ℃, and then prepared into an alkaline water electrolytic cell diaphragm by combining a conventional spinning process with a conventional needle-punched non-woven fabric process, and the specific process flow is as follows:
the spinning process comprises the following steps: granulating, drying, spinning, winding, bundling, drafting, heat setting, crimping and cutting. Wherein the spinning temperature is 340 ℃, the circular blowing speed is 0.9m/min, the circular blowing temperature is 25 ℃, and the tension heat setting temperature is 245 ℃.
The process for needling non-woven fabrics comprises the following steps: bale opener, coarse opening, cotton mixing bin, fine opening, carding, lapping, needling and cutting. Wherein the main cylinder speed is 600m/min, and the needling density is 1000 needles/cm 2 Gram weight 550g/m 2 The needling rolling speed is 5m/min.
The alkaline water electrolysis cell diaphragms prepared by adopting the resin raw materials of examples 1-13 through spinning and needling processes are numbered as samples 1-13 in sequence; the alkaline water electrolysis cell diaphragms prepared by adopting the resin raw materials of comparative examples 1-2 through spinning and needling processes are numbered as samples 14-15 in sequence.
The resin prepared in comparative example 2 was mechanically blended with nano zirconia (average particle size 50 nm), wherein nano zirconia accounts for 3% of the mass of the resin, melt blended and extruded to pelletize by a twin screw extruder, vacuum dried at 100 ℃ for 12 hours, and then prepared into an alkaline water electrolytic cell membrane, numbered sample 16, by combining the conventional spinning process with the conventional needle punched non-woven fabric process.
The resin prepared in comparative example 2 was melt-extruded by a twin screw extruder to be pelletized, vacuum-dried at 100℃for 12 hours, and then polyphenylene sulfide fiber was prepared as in the above spinning process and subjected to the following surface treatment:
and (3) sulfonating the polyphenylene sulfide fiber in 540g/L sulfuric acid and 320g/L chromic acid at 80 ℃ for 10min, and then sequentially washing the sulfonated polyphenylene sulfide fiber with water at normal temperature, washing with hot water at 50 ℃, reducing and washing with water with ultrasonic waves, and drying to obtain the hydrophilic polyphenylene sulfide fiber.
And then the alkaline water electrolysis cell diaphragm is prepared by adopting the conventional needle punched non-woven fabric process, and the number of the alkaline water electrolysis cell diaphragm is sample 17.
Mechanically blending the resin prepared in comparative example 2 with nano zirconia (average particle size of 50 nm), wherein the nano zirconia accounts for 3% of the mass of the resin, melt blending and extrusion granulating by a double screw extruder, vacuum drying at 100 ℃ for 12 hours, preparing polyphenylene sulfide fiber according to the spinning process, and carrying out the following surface treatment:
and (3) carrying out sulfonation treatment on the polyphenylene sulfide fiber in 540g/L sulfuric acid and 320g/L chromic acid at the treatment temperature of 80 ℃ for 10min, and then sequentially carrying out normal-temperature water washing, hot water washing at 50 ℃, reduction washing, ultrasonic water washing and drying on the polyphenylene sulfide fiber subjected to the sulfonation treatment to obtain the hydrophilic polyphenylene sulfide fiber.
The alkaline water electrolysis cell membrane, sample 18, was then prepared using the conventional needle punched non-woven process described above.
All alkaline water electrolysis cell separators prepared as described above were tested separately and the test data are shown in table 2 below.
TABLE 2
The applicant states that the present invention is illustrated by the above examples as a detailed method of the present invention, but the present invention is not limited to the above detailed method.
Claims (10)
1. The preparation method of the resin special for the alkaline water electrolysis cell diaphragm is characterized by comprising the following steps of:
step one: putting N-methyl pyrrolidone and sodium sulfide aqueous solution into a polymerization kettle, heating and then dehydrating;
step two: adding N-methyl pyrrolidone and p-dichlorobenzene into a polymerization kettle, continuously heating for polymerization, and finally obtaining the resin special for the alkaline water electrolysis cell diaphragm through a post-treatment procedure;
the preparation method is also added with nano zirconia, wherein the nano zirconia can be added together with sodium sulfide aqueous solution in the first step, or can be added together with paradichlorobenzene in the second step.
2. The method for producing a resin for alkaline water electrolysis cell separator according to claim 1, wherein in the first step:
the mass concentration of the sodium sulfide aqueous solution is 20-80%;
the molar ratio of the N-methyl pyrrolidone to the sodium sulfide is 1.0-5.0: 1.
3. the method for preparing the resin special for the alkaline water electrolysis cell diaphragm, according to claim 1, wherein the molar ratio of the added nano zirconia to the sodium sulfide is 0.05-3.00: 100;
the average grain diameter of the nano zirconia is 1-100 nm.
4. The method for producing a resin for alkaline water electrolysis cell separators according to claim 1, wherein the nano zirconia is added together with an aqueous sodium sulfide solution in the first step.
5. The method for producing a resin for alkaline water electrolysis cell separator according to claim 1, wherein a third monomer is further added in the second step;
the third monomer is selected from monosubstituted paradichlorobenzene, and the substituent is selected from one or more of sulfonic acid group, hydroxyl group, carboxylic acid group, aldehyde group and phosphate group;
the molar ratio of the third monomer to the sodium sulfide in the first step is 0.01-0.5: 1, a step of;
the ratio of the sum of the mole numbers of paradichlorobenzene and the third monomer to the mole number of sodium sulfide in the step one is 0.8-1.3: 1.
6. the method for preparing the resin special for the alkaline water electrolysis cell diaphragm, which is characterized by comprising the following steps of:
the substituent is selected from one or more of sulfonic acid group, hydroxyl group, carboxylic acid group and phosphoric acid group;
the molar ratio of the third monomer to the sodium sulfide in the first step is 0.05-0.1: 1, a step of;
the ratio of the sum of the mole numbers of paradichlorobenzene and the third monomer to the mole number of sodium sulfide in the step one is 1.0 to 1.2:1.
7. the method for preparing the resin special for the alkaline water electrolysis cell diaphragm, which is characterized in that:
the molar ratio of the added nano zirconia to the sodium sulfide is 0.5-3.0: 100;
the average grain diameter of the nano zirconia is 50-100 nm.
8. The method for preparing the resin special for the alkaline water electrolysis cell diaphragm, according to claim 1, is characterized in that:
in the first step, the temperature rising rate is 1-10 ℃/min, and the dehydration procedure is carried out after the temperature rises to 150-210 ℃;
in the second step, the polymerization is carried out after the temperature is raised to 240-280 ℃, the temperature raising rate is 1-20 ℃/min, and the polymerization time is 1-8 h;
the post-treatment includes a washing treatment and a drying treatment.
9. A resin specially used for alkaline water electrolysis cell diaphragms prepared by the method according to any one of claims 1 to 8.
10. The preparation method of the alkaline water electrolysis cell diaphragm is characterized in that the resin special for the alkaline water electrolysis cell diaphragm is adopted as a raw material, and is prepared through a melt spinning process and a needle punching non-woven fabric process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117512692A (en) * | 2023-11-17 | 2024-02-06 | 武汉理工大学 | Coating type alkaline water electrolysis hydrogen production diaphragm |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117512692A (en) * | 2023-11-17 | 2024-02-06 | 武汉理工大学 | Coating type alkaline water electrolysis hydrogen production diaphragm |
| CN117512692B (en) * | 2023-11-17 | 2024-05-03 | 武汉理工大学 | Coating type alkaline water electrolysis hydrogen production diaphragm |
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