CN111116979A - Recycling method of perfluorosulfonic acid proton exchange membrane, recycled product and application of recycled product - Google Patents
Recycling method of perfluorosulfonic acid proton exchange membrane, recycled product and application of recycled product Download PDFInfo
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- CN111116979A CN111116979A CN201911248857.4A CN201911248857A CN111116979A CN 111116979 A CN111116979 A CN 111116979A CN 201911248857 A CN201911248857 A CN 201911248857A CN 111116979 A CN111116979 A CN 111116979A
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- 239000012528 membrane Substances 0.000 title claims abstract description 97
- 238000004064 recycling Methods 0.000 title claims abstract description 64
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000001914 filtration Methods 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000007787 solid Substances 0.000 claims abstract description 68
- 239000003960 organic solvent Substances 0.000 claims abstract description 62
- 238000001035 drying Methods 0.000 claims abstract description 49
- 239000000706 filtrate Substances 0.000 claims abstract description 43
- 238000009835 boiling Methods 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 23
- 239000002738 chelating agent Substances 0.000 claims abstract description 15
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims description 60
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 46
- 239000002904 solvent Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 31
- 239000012153 distilled water Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 23
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 239000000446 fuel Substances 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 239000001433 sodium tartrate Substances 0.000 claims description 3
- 229960002167 sodium tartrate Drugs 0.000 claims description 3
- 235000011004 sodium tartrates Nutrition 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 3
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 28
- 238000011084 recovery Methods 0.000 description 37
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- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- HHKBNCKQWLHDDE-UHFFFAOYSA-N 2-aminoethanol;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid Chemical compound NCCO.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O HHKBNCKQWLHDDE-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 239000003054 catalyst Substances 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2225—Synthetic macromolecular compounds containing fluorine
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08J2300/102—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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
- Y02E60/50—Fuel cells
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The invention relates to a recycling method of a perfluorosulfonic acid proton exchange membrane, a recycled product and application thereof, wherein the recycling method comprises the following steps: (1) mixing a perfluorinated sulfonic acid proton exchange membrane, an organic solvent with a boiling point of 80-90 ℃ and water, filtering, collecting filtrate, and drying to obtain a first solid; (2) mixing the first solid, an organic solvent, water and a chelating agent, filtering, collecting filtrate, and drying to obtain a second solid; (3) and mixing the second solid, an organic solvent with a boiling point of 300-350 ℃ and water to obtain a perfluorinated sulfonic acid resin solution. The product obtained by the recycling method has high purity and yield, is environment-friendly, and has simple steps and low recycling cost.
Description
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to a method for recycling a perfluorinated sulfonic acid proton exchange membrane, a recycled product and application thereof.
Background
The cost of fuel cells is an impediment to their widespread adoption. The performance of the proton exchange membrane as an important component of the fuel cell has an important influence on the fuel cell, the cost of the proton exchange membrane accounts for 12% of the cost of the fuel cell stack, and the cost of the proton exchange membrane is further increased along with the reduction of the cost of the bipolar plate and other accessories of the fuel cell. Currently, most of the proton exchange membranes used are perfluorinated proton exchange membranes, and the major brands include Nafion series membranes of Dupont (Dupont), Dow membranes and Xus-B204 membranes of Dow chemical company (Dow), 3M perfluorosulfonic acid membranes, Alciplex, asahi glass company, Flemion, japan chlorine engineering company C series; ballard company BAM series membranes, belgium Solvay company Solvay series membranes; kerun, such as DF988, DF2801 and DF260 of Dong Yue group in Shandong province of China
The main components of the membrane are perfluorosulfonic acid (PSFA), and the difference mainly lies in the length of a side chain and the preparation process. With the explosion of the fuel cell industry, a great deal of leftover waste of proton exchange membranes is generated in laboratories, factories, and in use, and many Membrane Electrode Assembly (MEA) assemblies and proton exchange membranes in fuel cells also need to be disposed of. The traditional treatment method mostly adopts a landfill or incineration method. Because the perfluorosulfonic acid is structurally stable and is difficult to naturally degrade, landfill has adverse effects on the environment. The proton exchange membrane contains fluorine, and may cause environmental pollution after combustion. In the general recovery method, the added solvent is not well recycled, which causes secondary pollution to the environment,and the recovery purity is low, the impurities are more, and the proton exchange membrane cannot be used again.
CN110066421A discloses a method for recovering perfluorosulfonic acid resin of waste membranes, which comprises the steps of physically cleaning, then carrying out chemical treatment and/or biological treatment on the raw materials after the physical cleaning, treating the raw materials in one or more of an organic solvent, an acidic solution, an alkaline solution, a redox solution and a microbial flora, cleaning the raw materials with pure water, drying and crushing the raw materials for later use; dissolving the raw materials after chemical treatment and/or biological treatment in a solvent, adding additives according to the requirement for component adjustment, and filtering to obtain a resin solution. The method provided by the invention needs acid solution, alkaline solution, redox solution, microbial flora and the like, is complex to operate and has higher recycling cost.
CN107431229A discloses a recycling method comprising immersing a component containing perfluorosulfonic acid ionomer in a solvent containing aliphatic diol, and heating. The use of the recovered perfluorosulfonic acid ionomer is disclosed. Among them, the perfluorosulfonic acid ionomer component suitable for use may also contain a catalyst. The treatment of the parts also requires chopping or shredding. The product obtained by the method has low purity.
CN109088080A discloses a proton exchange membrane fuel cell. The method comprises the steps of disassembling the proton exchange membrane fuel cell, dissolving the perfluorosulfonic acid membrane and regenerating a casting membrane, oxidizing, complexing and purifying and refining platinum to finally obtain the bipolar plate, the regenerated perfluorosulfonic acid membrane and a platinum ingot. Wherein the treatment of the perfluorosulfonic acid membrane comprises solvent dissolution, vacuum defoaming, membrane casting and the like. The perfluorosulfonic acid resin obtained by the method has low recovery rate and purity.
Therefore, the development of a recycling method of a perfluorosulfonic acid proton exchange membrane which is environment-friendly, simple in steps, low in cost, high in recovery rate and high in product purity is urgently needed in the field.
Disclosure of Invention
In view of the defects of the prior art, one of the purposes of the present invention is to provide a method for recycling a perfluorosulfonic acid proton exchange membrane. The product obtained by the recycling method has high purity and yield, is environment-friendly, and has simple steps and low recycling cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a recycling method of a perfluorosulfonic acid proton exchange membrane, which is characterized by comprising the following steps:
(1) mixing a perfluorosulfonic acid proton exchange membrane, an organic solvent with a boiling point of 80-90 ℃ (such as 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃ and the like) and water, filtering, collecting filtrate, and drying to obtain a first solid;
(2) mixing the first solid, an organic solvent, water and a chelating agent, filtering, collecting filtrate, and drying to obtain a second solid;
(3) mixing the second solid, an organic solvent having a boiling point of 300 to 350 ℃ (for example, 305 ℃, 310 ℃, 315 ℃, 320 ℃, 325 ℃, 330 ℃, 335 ℃, 340 ℃, 345 ℃ and the like) and water to obtain a perfluorosulfonic acid resin solution.
The invention provides a recycling method of a perfluorinated sulfonic acid proton exchange membrane, which comprises the steps of firstly dissolving the perfluorinated sulfonic acid proton exchange membrane in a low-boiling-point (80-90 ℃) organic solvent for primary treatment, then dissolving the perfluorinated sulfonic acid proton exchange membrane in the organic solvent for secondary treatment under the action of a chelating agent, further removing metal ions, and finally dissolving the perfluorinated sulfonic acid proton exchange membrane in a high-boiling-point (300-350 ℃) organic solvent to obtain a perfluorinated sulfonic acid resin solution, wherein the three specific dissolving operations are matched with two filtering operations, so that the treatment steps are optimized, the perfluorinated sulfonic acid resin solution with higher purity and higher recovery rate can be obtained, the purity is 90-99%, and the recovery rate is 90-99%;
the recycling method provided by the invention does not produce polluting substances, is environment-friendly, is simple to operate and has low cost.
The perfluorinated sulfonic acid proton exchange membrane can be derived from a directly discarded commercially-available proton exchange membrane, and a support membrane of the perfluorinated sulfonic acid proton exchange membrane is removed; or from a membrane electrode assembly, and the assembly is split into a perfluorosulfonic acid proton exchange membrane (with a spray catalyst) and a gas diffusion layer.
Preferably, in the step (1), the organic solvent of the organic solvent with the boiling point of 80-90 ℃ comprises any one or a combination of at least two of methanol, ethanol, propanol, isopropanol and n-butanol.
Preferably, in the step (1), the volume ratio of the organic solvent with the boiling point of 80-90 ℃ to water is (1-4: 1), such as 1.1:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, and the like.
Preferably, in step (1), after the mixing, heating and stirring are performed.
Preferably, in the step (1), the stirring temperature is 40 to 80 ℃, for example, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ and the like.
Preferably, in the step (1), the stirring time is 2-10 h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h and the like.
Preferably, in the step (1), a filter screen is used for the filtration, and the mesh number of the filter screen is preferably 20-300 meshes, such as 50 meshes, 60 meshes, 80 meshes, 100 meshes, 120 meshes, 140 meshes, 160 meshes, 180 meshes, 200 meshes, 220 meshes, 240 meshes, 260 meshes, 280 meshes and the like.
Preferably, in the step (1), the filtration pressure is 0.1 to 0.5MPa, such as 0.12MPa, 0.14MPa, 0.16MPa, 0.18MPa, 0.2MPa, 0.22MPa, 0.24MPa, 0.26MPa, 0.28MPa, 0.3MPa, 0.32MPa, 0.34MPa, 0.36MPa, 0.38MPa, 0.4MPa, 0.42MPa, 0.44MPa, 0.46MPa, 0.48MPa, etc.
According to the invention, the filtration pressure in the step (1) is preferably 0.1-0.5 MPa, under the condition, the purity and recovery rate of the final perfluorinated sulfonic acid resin solution can be further improved, impurities can enter the filtrate due to overhigh pressure, the purity of the product is influenced, the operation time is prolonged due to overlow pressure, and the impurities are not completely separated.
Preferably, in the step (1), the filtration time is 0.5-5 h, such as 1h, 2h, 3h, 4h, etc., preferably 30-90 min.
According to the invention, the filtering time in the step (1) is preferably 0.5-5 h (especially 30-90 min), and within the time range, the purity and the recovery rate of the final perfluorinated sulfonic acid resin solution can be further improved, the efficiency is reduced due to overlong time, and the impurity separation is incomplete due to overlong time, so that the product purity is influenced.
Preferably, in the step (1), a filter screen with the mesh number of 20-300 meshes is adopted for filtering, the pressure is 0.1-0.5 MPa, and the time is 0.5-5 h.
The technical scheme that a filter screen with a specific mesh number is matched with specific filtering pressure and time is further preferred, and the three conditions are matched, so that the purity and the recovery rate of the product can be further improved.
Preferably, in step (1), after the filtration, washing is performed with a hydrogen peroxide solution, preferably, the concentration of the hydrogen peroxide solution is 10 to 80%, for example, 20%, 30%, 40%, 50%, 60%, 70%, etc. The concentration of hydrogen peroxide refers to mass concentration.
According to the invention, the filter residue is preferably washed by using the hydrogen peroxide solution, and the hydrogen peroxide can remove organic impurities, so that the recovery rate of the product is further improved, and the effect is better when the filter residue is preferably washed by using the hydrogen peroxide solution with the concentration of 10-80%.
Preferably, in step (1), after the filtration, washing with distilled water is performed.
According to the invention, the filter residue is preferably washed by using distilled water, and the distilled water can remove water-soluble impurities, so that the recovery rate of the product is further improved.
Preferably, in the step (1), the drying manner includes heating and drying, and preferably the heating and drying temperature is 60 to 90 ℃, for example, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and the like.
Preferably, in the step (1), the drying time is 1-4 h, such as 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h and the like.
Preferably, in step (1), the perfluorosulfonic acid proton exchange membrane comprises a fuel cell perfluorosulfonic acid proton exchange membrane.
Preferably, in step (1), the solvent is recovered and reused after drying.
The invention preferably recycles the solvent, thereby further reducing the production cost and the pollution caused by organic reagents.
Preferably, step (1) comprises the steps of:
dissolving a perfluorosulfonic acid proton exchange membrane in a mixed solution of an organic solvent and water with a boiling point of 80-90 ℃, heating and stirring, filtering, collecting filtrate, drying to obtain a first solid, and recycling the solvent.
Preferably, step (1) comprises the steps of:
dissolving a perfluorinated sulfonic acid proton exchange membrane in a mixed solution of an organic solvent and water with a boiling point of 80-90 ℃, wherein the volume ratio of the organic solvent and water with the boiling point of 80-90 ℃ is (1-4): 1, heating to 40-80 ℃, stirring for 2-10 h, filtering for 0.5-5 h under the pressure of 0.1-0.5 MPa by using a filter screen with the mesh number of 20-300, washing with a hydrogen peroxide solution with the concentration of 10-80% and distilled water, collecting filtrate, heating to 60-90 ℃, drying for 1-4 h, obtaining a first solid, and recycling the solvent.
Preferably, in the step (2), the organic solvent includes any one or a combination of at least two of n-heptane, n-hexane, isooctane and n-decane.
Preferably, in the step (2), the volume ratio of the organic solvent to the water is (1-10): 1, such as 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, and the like.
Preferably, in the step (2), the chelating agent comprises any one or at least two of sodium dimethyldithiocarbamate, triethanolamine, ethylenediamine tetraacetic acid, sodium tartrate, sodium pyrophosphate, trisodium phosphate and ammonium citrate.
Preferably, in the step (2), a filter screen is used for the filtration, and the mesh number of the filter screen is preferably 300-500 meshes, such as 320 meshes, 340 meshes, 360 meshes, 380 meshes, 400 meshes, 420 meshes, 440 meshes, 460 meshes, 480 meshes and the like.
Preferably, in the step (2), the filtration pressure is 0.2 to 0.8MPa, such as 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa, 0.55MPa, 0.6MPa, 0.65MPa, 0.7MPa, 0.75MPa, etc.
According to the invention, the filtration pressure in the step (2) is preferably 0.2-0.8 MPa, under the condition, the purity and recovery rate of the final perfluorinated sulfonic acid resin solution can be further improved, impurities can enter the filtrate due to overhigh pressure, the purity of the product is influenced, the operation time is prolonged due to overlow pressure, and the impurities are not completely separated.
Preferably, in the step (2), the filtering time is 0.5-5 h, preferably 30-150 min.
According to the invention, the filtering time in the step (2) is preferably 0.5-5 h (especially 30-150 min), and within the time range, the purity and the recovery rate of the final perfluorinated sulfonic acid resin solution can be further improved, the efficiency is reduced due to overlong time, and the impurity separation is incomplete due to overlong time, so that the product purity is influenced.
Preferably, in the step (2), a filter screen with the mesh number of 300-500 meshes is adopted for filtering, the pressure is 0.2-0.8 MPa, and the time is 0.5-5 h.
The technical scheme that a filter screen with a specific mesh number is matched with specific filtering pressure and time is further preferred, and the three conditions are matched, so that the purity and the recovery rate of the product can be further improved.
Preferably, in the step (2), after the filtration, the hydrogen peroxide solution is used for washing, and the concentration of the hydrogen peroxide solution is preferably 10-80%, such as 20%, 30%, 40%, 50%, 60%, 70%, and the like.
The principle and effect of the hydrogen peroxide solution washing in the step (2) are the same as those in the step (1).
Preferably, in step (2), after the filtration, washing with distilled water is performed.
The principle and effect of washing with distilled water in step (2) are the same as those in step (1).
Preferably, in the step (2), the drying manner includes heating and drying, and the temperature of the heating and drying is preferably 100 to 150 ℃, for example, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ and the like.
Preferably, in the step (2), the drying time is 1-4 h, such as 1.5h, 2h, 2.5h, 3h, 3.5h and the like.
Preferably, in the step (2), the solvent is recovered and used after drying.
The invention preferably recycles the solvent, thereby further reducing the production cost and the pollution caused by organic reagents.
Preferably, the step (2) comprises the steps of:
dissolving the first solid in a mixed solution of an organic solvent and water, adding a chelating agent, filtering, collecting filtrate, drying to obtain a second solid, and recycling the solvent.
Preferably, the step (2) comprises the steps of:
dissolving the first solid in a mixed solution of an organic solvent and water, wherein the volume ratio of the organic solvent to the water is (1-10): 1, adding a chelating agent, filtering by using a filter screen with the mesh number of 300-500 meshes for 0.5-5 h under the pressure of 0.2-0.8 MPa, washing by using a hydrogen peroxide solution with the concentration of 10-80% and distilled water, collecting filtrate, heating to 100-150 ℃, drying for 1-4 h, obtaining a second solid, and recycling the solvent.
Preferably, in the step (3), the organic solvent with a boiling point of 300-350 ℃ comprises any one or a combination of at least two of toluene, xylene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Preferably, in the step (3), the volume ratio of the organic solvent with the boiling point of 300-350 ℃ to the water is (1-4): 1.
Preferably, in the step (3), after the mixing, stirring is carried out under the conditions of heating and pressurizing to obtain the perfluorosulfonic acid resin, and the solvent is recycled;
the solvent can be evaporated and recycled by stirring under the conditions of heating and pressurization, thereby obtaining the perfluorosulfonic acid resin.
Preferably, in the step (3), the stirring temperature is 150 to 250 ℃, such as 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 245 ℃ and the like.
Preferably, in the step (3), the stirring pressure is 1 to 10MPa, such as 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa and the like.
Preferably, in the step (3), the stirring time is 1-10 h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h and the like.
Preferably, the step (3) comprises the steps of:
and dissolving the second solid in a mixed solution of an organic solvent with a boiling point of 300-350 ℃ and water, and heating and pressurizing to obtain the perfluorosulfonic acid resin, wherein the solvent is recycled.
Preferably, the step (3) comprises the steps of:
and dissolving the second solid in a mixed solution of an organic solvent with a boiling point of 300-350 ℃ and water, wherein the volume ratio of the organic solvent with the boiling point of 300-350 ℃ to the water is (1-4): 1, stirring for 1-10 h under the conditions of 150-250 ℃ and 1-10MPa to obtain the perfluorinated sulfonic acid resin, and recycling the solvent.
Preferably, the perfluorosulfonic acid proton exchange membrane is subjected to a pretreatment prior to step (1), said pretreatment comprising: the perfluorosulfonic acid proton exchange membrane is physically crushed.
Preferably, the physical shredding tool comprises any one or a combination of at least two of scissors, a paper cutter, a paper shredder, and a shredder.
Preferably, the recycling method specifically comprises the following steps:
(1) dissolving a physically crushed perfluorinated sulfonic acid proton exchange membrane in a mixed solution of an organic solvent and water with a boiling point of 80-90 ℃, wherein the volume ratio of the organic solvent and water with the boiling point of 80-90 ℃ is (1-4): 1, heating to 40-80 ℃, stirring for 2-10 h, filtering for 0.5-5 h under the pressure of 0.1-0.5 MPa by using a filter screen with the mesh number of 20-300, washing with a hydrogen peroxide solution with the concentration of 10-80% and distilled water, collecting filtrate, heating to 60-90 ℃, drying for 1-4 h, obtaining a first solid, and recycling the solvent;
(2) dissolving the first solid in a mixed solution of an organic solvent and water, wherein the volume ratio of the organic solvent to the water is (1-10): 1, adding a chelating agent, filtering by using a filter screen with the mesh number of 300-500 meshes under the pressure of 0.2-0.8 MPa for 0.5-5 h, washing by using a hydrogen peroxide solution with the concentration of 10-80% and distilled water, collecting filtrate, heating to 100-150 ℃, drying for 1-4 h to obtain a second solid, and recycling the solvent;
(3) and dissolving the second solid in a mixed solution of an organic solvent with a boiling point of 300-350 ℃ and water, wherein the volume ratio of the organic solvent with the boiling point of 300-350 ℃ to the water is (1-4): 1, stirring for 1-10 h under the conditions of 150-250 ℃ and 1-10MPa to obtain the perfluorinated sulfonic acid resin, and recycling the solvent.
A second object of the present invention is to provide a perfluorosulfonic acid resin obtained by the method for recycling a perfluorosulfonic acid proton exchange membrane according to the first object, wherein the perfluorosulfonic acid resin has a purity of 90 to 99%, for example, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, etc. Purity refers to the ratio of the mass of perfluorosulfonic acid to the total mass of the product.
The third object of the present invention is to provide an application of the perfluorosulfonic acid resin of the second object to a proton exchange membrane, preferably a proton exchange membrane for a fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a recycling method of a perfluorosulfonic acid proton exchange membrane, which comprises the steps of firstly dissolving the perfluorosulfonic acid proton exchange membrane in a low-boiling-point (80-90 ℃) organic solvent for primary treatment, then dissolving the perfluorosulfonic acid proton exchange membrane in the organic solvent for secondary treatment under the action of a chelating agent, further removing metal ions, and finally dissolving the perfluorosulfonic acid proton exchange membrane in a high-boiling-point (300-350 ℃) organic solvent to obtain a perfluorosulfonic acid resin solution, wherein the three specific dissolving operations are matched with two filtering operations, so that the treatment steps are optimized, the perfluorosulfonic acid resin solution with higher purity and higher recovery rate can be obtained, the purity is 90-99%, and the yield is 90-99%;
the recycling method provided by the invention does not generate polluting substances, recycles the solvent, and has the advantages of environmental friendliness, simple operation and low cost.
Drawings
FIG. 1 is a flow chart of the process for recycling the perfluorosulfonic proton exchange membrane of example 2.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a method for recycling a perfluorosulfonic acid proton exchange membrane, which comprises the following steps:
(1) and removing the support membrane from the residual proton exchange membrane after the laboratory test and other available leftover waste proton exchange membranes, and shearing the support membrane by using scissors.
(2) Transferring the solid in the step (1) to a heating stirrer, adding an excessive solution of ethanol and water in a volume ratio of 1:1 to dissolve, heating the container to 60 ℃, and stirring for 4 hours.
(3) And (3) filtering the solid and the solution in the step (2) through a 20-mesh filter screen, controlling the filtering pressure to be 0.1MPa and the filtering time to be 30min, and flushing the filtrate once respectively with 10% hydrogen peroxide and distilled water for later use.
(4) And (4) heating and drying the filtrate (3) at 60 ℃ for 2h, recycling the obtained filtrate, and taking out the solid for later use.
(5) And (3) transferring the solid in the step (4) to a glass beaker, adding a mixed solvent of isooctane and water in a volume ratio of 1:1, adding triethanolamine while continuously stirring, filtering the solution by using a 500-mesh filter screen, and controlling the filtering pressure to be 0.2MPa for 60 min. Each rinse was once with 10% hydrogen peroxide and distilled water.
(6) And (3) heating and drying the filtrate (5) at 150 ℃ for 1h, recycling the obtained filtrate, and taking out the solid for later use.
(7) And (3) transferring the solid in the step (6) to a heating stirring container, adding a mixture of xylene, dimethyl sulfoxide and water in a volume ratio of 1:1:2, heating to 200 ℃, adjusting the pressure in the container to be 1MPa, and stirring for 4 hours to obtain the perfluorosulfonic acid resin, wherein the purity is 90% and the recovery rate is 99%.
Example 2
The embodiment provides a method for recycling a perfluorosulfonic acid proton exchange membrane, which comprises the following steps:
(1) and sequentially removing the gas diffusion layers from the collected membrane electrode assemblies, and crushing the rest proton exchange membranes by a paper crusher for later use.
(2) Transferring the solid in the step (1) to a heating stirrer, adding an excessive solution of isopropanol and water in a volume ratio of 4:1 to dissolve, heating the container to 80 ℃, and stirring for 10 hours.
(3) And (3) filtering the solid and the solution in the step (2) through a 300-mesh filter screen, controlling the filtering pressure to be 0.3MPa and the filtering time to be 30min, and flushing the filtrate once respectively with 50% of hydrogen peroxide and distilled water for later use.
(4) And (4) heating and drying the filtrate obtained in the step (3) at 90 ℃ for 1h, recycling the obtained filtrate, and taking out the solid for later use.
(5) And (3) transferring the solid in the step (4) to a glass beaker, adding a mixed solvent of n-heptane, isooctane and water in a volume ratio of 1:1:1, adding ethylene diamine tetraacetic acid ethanolamine under continuous stirring, filtering the solution by using a 300-mesh filter screen, and controlling the filtering pressure to be 0.5MPa and the filtering time to be 60 min. Each rinse was once with 50% hydrogen peroxide and distilled water.
(6) And (3) heating and drying the filtrate obtained in the step (5) at 100 ℃ for 4h, recycling the obtained filtrate, and taking out the solid for later use.
(7) And (3) transferring the solid in the step (6) to a heating stirring container, adding a mixture of toluene, N-methyl pyrrolidone and water in a volume ratio of 1:1:2, heating to 250 ℃, adjusting the pressure in the container to be 10MPa, and stirring for 10 hours to obtain the perfluorosulfonic acid resin, wherein the purity is 99% and the recovery rate is 97%.
Fig. 1 is a flow chart of the process for recycling the perfluorosulfonic proton exchange membrane of example 2, wherein the process comprises three operations of dissolution, two times of filtration and three times of solvent removal, and a chelating agent is added to remove impurities in the process of the second step of dissolution, and solvent recovery is performed in each step.
Example 3
The embodiment provides a method for recycling a perfluorosulfonic acid proton exchange membrane, which comprises the following steps:
(1) and sequentially removing the gas diffusion layers from the collected membrane electrode assemblies, and crushing the rest proton exchange membranes by a paper crusher for later use.
(2) Transferring the solid in the step (1) to a heating stirrer, adding an excessive solution of methanol, n-butanol and water in a volume ratio of 1:1:1 to dissolve, heating the container to 40 ℃, and stirring for 10 hours.
(3) Filtering the solid and the solution in the step (2) through a filter screen with 100 meshes, controlling the filtering pressure at 0.5MPa and the filtering time at 60min, and flushing the solid and the solution respectively once by using 80 percent hydrogen peroxide and distilled water.
(4) And (4) heating and drying the filtrate obtained in the step (3) at 80 ℃ for 2h, recycling the obtained filtrate, and taking out the solid for later use.
(5) And (3) transferring the solid in the step (4) to a glass beaker, adding a mixed solvent of n-heptane, n-decane and water in a volume ratio of 1:1:2, adding a mixture of sodium tartrate and ammonium citrate while continuously stirring, filtering the solution by using a 400-mesh filter screen, and controlling the filtering pressure to be 0.8MPa for 30 min. Each rinse was once with 40% hydrogen peroxide and distilled water.
(6) And (3) heating and drying the filtrate obtained in the step (5) at 130 ℃ for 1h, recycling the obtained filtrate, and taking out the solid for later use.
(7) And (3) transferring the solid in the step (6) to a heating stirring container, adding a mixture of N, N-dimethylformamide, N-dimethylacetamide and water in a volume ratio of 1:2:2, heating to 150 ℃, adjusting the pressure in the container to be 6MPa, and stirring for 8 hours to obtain the perfluorosulfonic acid resin, wherein the purity is 99% and the recovery rate is 95%.
Example 4
The embodiment provides a method for recycling a perfluorosulfonic acid proton exchange membrane, which comprises the following steps:
(1) and sequentially removing the gas diffusion layers from the collected membrane electrode assemblies, and crushing the rest proton exchange membranes by a paper crusher for later use.
(2) Transferring the solid in the step (1) to a heating stirrer, adding an excessive solution of isopropanol, ethanol and water in a volume ratio of 3:1:1 to dissolve, heating the container to 60 ℃, and stirring for 5 hours.
(3) Filtering the solid and the solution in the step (2) through a 200-mesh filter screen, controlling the filtering pressure to be 0.1MPa and the filtering time to be 120min, and flushing the solid and the solution with 40% of hydrogen peroxide and distilled water once respectively.
(4) And (4) heating and drying the filtrate obtained in the step (3) at 70 ℃ for 1h, recycling the obtained filtrate, and taking out the solid for later use.
(5) And (3) transferring the solid in the step (4) to a glass beaker, adding a mixed solvent of n-heptane, n-hexane and water in a volume ratio of 2:1:1, adding a mixture of sodium pyrophosphate and trisodium phosphate while continuously stirring, and filtering the solution by using a 300-mesh filter screen, wherein the filtering pressure is controlled to be 0.8MPa and the filtering time is 150 min. The mixture is washed once by 30 percent hydrogen peroxide and distilled water respectively and then taken out for standby.
(6) And (3) heating and drying the filtrate obtained in the step (5) at 110 ℃ for 2h, recycling the obtained filtrate, and taking out the solid for later use.
(7) And (3) transferring the solid in the step (6) to a heating stirring container, adding a mixture of xylene, N-dimethylformamide and water in a volume ratio of 2:1:2, heating to 250 ℃, adjusting the pressure in the container to be 10MPa, and stirring for 10 hours to obtain the perfluorosulfonic acid resin, wherein the purity is 99% and the recovery rate is 94%.
Examples 5 to 8
The difference from example 2 is that in step (3), the mesh number of the filter net is 20 meshes (example 5), 200 meshes (example 6), 10 meshes (example 7) and 350 meshes (example 8), the purity of examples 5 to 8 is 99%, 98%, 90% and 91%, and the recovery rate is 98%, 97%, 92% and 93%.
In comparative examples 2 and 5 to 8, it is understood that the purity and yield of the product can be further improved by combining the filter screens with mesh number of 20 to 300 (examples 2, 5 and 6) with specific filtering parameters in the first filtering, and the purity and yield are reduced by too low mesh number (example 7) or too high mesh number (example 8).
Examples 9 to 12
The difference from example 2 is that in step (3), the filtration pressure was 0.1MPa (example 9), 0.5MPa (example 10), 0.05MPa (example 11) and 0.6MPa (example 12), the purities of examples 9 to 12 were 99%, 92% and 90%, and the recovery rates were 98%, 97%, 92% and 93%, respectively.
It is clear from comparative examples 2 and 9 to 12 that the purity and yield of the product can be further improved when the pressure in the first filtration is 0.1 to 0.5MPa (examples 2, 9 and 10), and that the purity and yield are reduced when the pressure is too low (example 11) or too high (example 12).
Examples 13 to 16
The difference from example 2 is that in step (3), the filtration time was 60min (example 13), 90min (example 14), 20min (example 15) and 100min (example 16), the purity of examples 13 to 16 was 99%, 90% and 90%, and the recovery rate was 98%, 96%, 90% and 91%, respectively.
It is understood from comparative examples 2, 13 to 16 that the purity and yield of the product can be further improved when the filtration time is 30 to 90min in the first filtration (examples 2, 13 and 14), and that the purity and yield are reduced when the filtration time is too short (example 15) or too long (example 16).
Example 17
The difference from example 2 is that the product purity is 98% and the yield is 90% without rinsing with hydrogen peroxide solution in step (3).
Examples 18 to 21
The difference from example 2 is that the hydrogen peroxide solution concentration in step (3) was 10% (example 18), 80% (example 19), 5% (example 20) and 90% (example 21), the purity of examples 18 to 21 was 98%, 99%, 98% and 97%, and the recovery rate was 97%, 96%, 92% and 90%, respectively.
As is clear from comparison of examples 2 and 17 to 21, the recovery rate was further improved by the washing with the hydrogen peroxide solution (examples 2 and 18 to 21), and the recovery rate was further improved by the washing with the hydrogen peroxide solution having a concentration of 10 to 80% (examples 2 and 18 to 19), and the recovery rate was decreased by either excessively low concentration (example 20) or excessively high concentration (example 21).
Example 22
The difference from example 2 is that in step (3), no distilled water is used for washing, and the product purity is 99% and the yield is 92%.
Comparing examples 2 and 22, it is seen that the recovery rate can be further improved by washing with distilled water (example 2) as compared with washing without distilled water (example 22).
Examples 23 to 26
The difference from example 2 is that in step (5), the mesh number of the filter net is 400 meshes (example 23), 500 meshes (example 24), 200 meshes (example 25) and 600 meshes (example 26), the purity of examples 23-26 is 98%, 92% and 91%, and the recovery rate is 96%, 95%, 90% and 90%.
In comparison with examples 2 and 23 to 26, it is found that in the second filtration, the purity and yield of the product can be further improved by matching the filter screens with mesh numbers of 300 to 500 (examples 2, 23 and 24) with specific filtration parameters, and the purity and yield can be reduced by too low mesh number (example 25) or too high mesh number (example 26).
Examples 27 to 30
The difference from example 2 is that in step (5), the filtration pressure was 0.2MPa (example 27), 0.8MPa (example 28), 0.1MPa (example 29) and 0.9MPa (example 30), the purity of examples 27 to 30 was 98%, 99%, 90% and 92%, and the recovery rate was 97%, 96%, 91% and 92%, respectively.
In comparative examples 2, 27 to 30, it is understood that the purity and yield of the product can be further improved when the pressure in the second filtration is 0.2 to 0.8MPa (examples 2, 27 and 28), and that the purity and yield are lowered when the pressure is too low (example 29) or too high (example 30).
Examples 31 to 34
The difference from example 2 is that in step (5), the filtration time was 150min (example 31), 30min (example 32), 20min (example 33) and 180min (example 34), the purity of examples 31 to 34 was 98%, 91% and 90%, and the recovery rate was 97%, 96%, 90% and 91%, respectively.
As is clear from comparison of examples 2, 31 to 34, in the second filtration, when the filtration time is 30 to 150min (examples 2, 31 and 32), the purity and yield of the product can be further improved, and when the filtration time is too short (example 33) or too long (example 34), the purity and yield are lowered.
Example 35
The embodiment provides a method for recycling a perfluorosulfonic acid proton exchange membrane, which comprises the following steps:
(1) and sequentially removing the gas diffusion layers from the collected membrane electrode assemblies, and crushing the rest proton exchange membranes by a paper crusher for later use.
(2) Transferring the solid in the step (1) to a heating stirrer, adding an excessive solution of isopropanol and water in a volume ratio of 4:1 to dissolve, heating the container to 80 ℃, and stirring for 2 hours.
(3) And (3) filtering the solid and the solution in the step (2) through a 300-mesh filter screen, controlling the filtering pressure to be 0.3MPa and the filtering time to be 60min, and flushing the filtrate once respectively with 50% of hydrogen peroxide and distilled water for later use.
(4) And (4) heating and drying the filtrate obtained in the step (3) at 90 ℃ for 4h, recycling the obtained filtrate, and taking out the solid for later use.
(5) And (3) transferring the solid in the step (4) to a glass beaker, adding a mixed solvent of n-heptane, isooctane and water in a volume ratio of 5:5:1, adding ethylene diamine tetraacetic acid ethanolamine under continuous stirring, filtering the solution by using a 300-mesh filter screen, and controlling the filtering pressure to be 0.5MPa and the filtering time to be 90 min. Each rinse was once with 50% hydrogen peroxide and distilled water.
(6) And (3) heating and drying the filtrate obtained in the step (5) at 100 ℃ for 4h, recycling the obtained filtrate, and taking out the solid for later use.
(7) And (3) transferring the solid in the step (6) to a heating stirring container, adding a mixture of toluene, N-methyl pyrrolidone and water in a volume ratio of 4:4:2, heating to 250 ℃, adjusting the pressure in the container to be 10MPa, and stirring for 1h to obtain the perfluorosulfonic acid resin with the purity of 99% and the recovery rate of 98%.
Comparative example 1
The difference from example 2 is that in step (2), isopropanol was replaced with an equal volume of toluene, purity was 70%, and recovery was 80%.
Comparative example 2
The difference from example 2 is that in step (5), no ethylenediamine tetraamine-ethanol amine was added, the purity was 65%, and the recovery rate was 85%.
Comparative example 3
The difference from example 2 is that in step (7), toluene was replaced by a volume of ethanol and N-methylpyrrolidone was replaced by an equal volume of methanol, resulting in a purity of 68% and a recovery of 86%.
The results prove that the method for recycling the perfluorinated sulfonic acid proton exchange membrane can obtain a product with high purity (90-99%) and high recovery rate (90-99%); the comparative example 1 uses a high-boiling-point organic solvent in the first dissolution, the comparative example 2 does not add a chelating agent in the second dissolution, and the comparative example 3 uses a low-boiling-point organic solvent in the third dissolution, so that the purity and the recovery rate of the products in the comparative examples 1-3 are obviously reduced.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A recycling method of a perfluorosulfonic acid proton exchange membrane is characterized by comprising the following steps:
(1) mixing a perfluorinated sulfonic acid proton exchange membrane, an organic solvent with a boiling point of 80-90 ℃ and water, filtering, collecting filtrate, and drying to obtain a first solid;
(2) mixing the first solid, an organic solvent, water and a chelating agent, filtering, collecting filtrate, and drying to obtain a second solid;
(3) and mixing the second solid, an organic solvent with a boiling point of 300-350 ℃ and water to obtain a perfluorinated sulfonic acid resin solution.
2. The recycling method of the perfluorinated sulfonic acid proton exchange membrane according to claim 1, wherein in the step (1), the organic solvent of the organic solvent with the boiling point of 80-90 ℃ comprises any one or a combination of at least two of methanol, ethanol, propanol, isopropanol and n-butanol;
preferably, in the step (1), the volume ratio of the organic solvent with the boiling point of 80-90 ℃ to water is (1-4): 1;
preferably, in step (1), after the mixing, heating and stirring;
preferably, in the step (1), the stirring temperature is 40-80 ℃;
preferably, in the step (1), the stirring time is 2-10 h;
preferably, in the step (1), a filter screen is adopted for filtering, and the mesh number of the filter screen is preferably 20-300 meshes;
preferably, in the step (1), the pressure of the filtration is 0.1-0.5 MPa;
preferably, in the step (1), the filtering time is 0.5-5 h, preferably 30-90 min;
preferably, in the step (1), a filter screen with the mesh number of 20-300 meshes is adopted for filtering, the pressure is 0.1-0.5 MPa, and the time is 0.5-5 h;
preferably, in the step (1), after the filtration, washing with a hydrogen peroxide solution, preferably, the concentration of the hydrogen peroxide solution is 10-80%;
preferably, in step (1), after the filtration, washing with distilled water;
preferably, in the step (1), the drying manner includes heating and drying, and preferably, the temperature of the heating and drying is 60-90 ℃;
preferably, in the step (1), the drying time is 1-4 h;
preferably, in step (1), the perfluorosulfonic acid proton exchange membrane comprises a fuel cell perfluorosulfonic acid proton exchange membrane;
preferably, in step (1), the solvent is recovered and reused after drying.
3. The recycling method of the perfluorinated sulfonic acid proton exchange membrane according to claim 1 or 2, wherein the step (1) comprises the following steps:
dissolving a perfluorosulfonic acid proton exchange membrane in a mixed solution of an organic solvent and water with a boiling point of 80-90 ℃, heating and stirring, filtering, collecting filtrate, drying to obtain a first solid, and recycling the solvent;
preferably, step (1) comprises the steps of:
dissolving a perfluorinated sulfonic acid proton exchange membrane in a mixed solution of an organic solvent and water with a boiling point of 80-90 ℃, wherein the volume ratio of the organic solvent and water with the boiling point of 80-90 ℃ is (1-4): 1, heating to 40-80 ℃, stirring for 2-10 h, filtering for 0.5-5 h under the pressure of 0.1-0.5 MPa by using a filter screen with the mesh number of 20-300, washing with a hydrogen peroxide solution with the concentration of 10-80% and distilled water, collecting filtrate, heating to 60-90 ℃, drying for 1-4 h, obtaining a first solid, and recycling the solvent.
4. The recycling method of the perfluorinated sulfonic acid proton exchange membrane according to any one of claims 1 to 3, wherein in the step (2), the organic solvent comprises any one or a combination of at least two of n-heptane, n-hexane, isooctane and n-decane;
preferably, in the step (2), the volume ratio of the organic solvent to the water is (1-10): 1;
preferably, in the step (2), the chelating agent comprises any one or at least two of sodium dimethyldithiocarbamate, triethanolamine, ethylenediamine tetraacetic acid, sodium tartrate, sodium pyrophosphate, trisodium phosphate and ammonium citrate;
preferably, in the step (2), a filter screen is adopted for filtering, and the mesh number of the filter screen is preferably 300-500 meshes;
preferably, in the step (2), the pressure of the filtration is 0.2-0.8 MPa;
preferably, in the step (2), the filtering time is 0.5-5 h, preferably 30-150 min;
preferably, in the step (2), a filter screen with the mesh number of 300-500 meshes is adopted for filtering, the pressure is 0.2-0.8 MPa, and the time is 0.5-5 h;
preferably, in the step (2), after the filtration, washing with a hydrogen peroxide solution, preferably, the concentration of the hydrogen peroxide solution is 10-80%;
preferably, in step (2), after the filtration, washing with distilled water;
preferably, in the step (2), the drying manner includes heating and drying, and preferably, the heating and drying temperature is 100-150 ℃;
preferably, in the step (2), the drying time is 1-4 h;
preferably, in the step (2), the solvent is recovered and used after drying.
5. The recycling method of the perfluorinated sulfonic acid proton exchange membrane according to any one of claims 1 to 4, wherein the step (2) comprises the following steps:
dissolving the first solid in a mixed solution of an organic solvent and water, adding a chelating agent, filtering, collecting filtrate, drying to obtain a second solid, and recycling the solvent;
preferably, the step (2) comprises the steps of:
dissolving the first solid in a mixed solution of an organic solvent and water, wherein the volume ratio of the organic solvent to the water is (1-10): 1, adding a chelating agent, filtering by using a filter screen with the mesh number of 300-500 meshes for 0.5-5 h under the pressure of 0.2-0.8 MPa, washing by using a hydrogen peroxide solution with the concentration of 10-80% and distilled water, collecting filtrate, heating to 100-150 ℃, drying for 1-4 h, obtaining a second solid, and recycling the solvent.
6. The recycling method of the perfluorinated sulfonic acid proton exchange membrane according to any one of claims 1 to 5, wherein in the step (3), the organic solvent with a boiling point of 300 to 350 ℃ comprises any one or at least two of toluene, xylene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone;
preferably, in the step (3), the volume ratio of the organic solvent with the boiling point of 300-350 ℃ to the water is (1-4): 1;
preferably, in the step (3), after the mixing, stirring is carried out under the conditions of heating and pressurizing to obtain the perfluorosulfonic acid resin, and the solvent is recycled;
preferably, in the step (3), the stirring temperature is 150-250 ℃;
preferably, in the step (3), the stirring pressure is 1-10 MPa;
preferably, in the step (3), the stirring time is 1-10 h;
preferably, the step (3) comprises the steps of:
dissolving the second solid in a mixed solution of an organic solvent with a boiling point of 300-350 ℃ and water, stirring under the conditions of heating and pressurizing to obtain perfluorinated sulfonic acid resin, and recycling the solvent;
preferably, the step (3) comprises the steps of:
and dissolving the second solid in a mixed solution of an organic solvent with a boiling point of 300-350 ℃ and water, wherein the volume ratio of the organic solvent with the boiling point of 300-350 ℃ to the water is (1-4): 1, stirring for 1-10 h under the conditions of 150-250 ℃ and 1-10MPa to obtain the perfluorinated sulfonic acid resin, and recycling the solvent.
7. The recycling method of the perfluorinated sulfonic acid proton exchange membrane according to any one of claims 1 to 6, wherein the perfluorinated sulfonic acid proton exchange membrane is subjected to a pretreatment before the step (1), and the pretreatment comprises the following steps: physically crushing the perfluorinated sulfonic acid proton exchange membrane;
preferably, the physical shredding tool comprises any one or a combination of at least two of scissors, a paper cutter, a paper shredder, and a shredder.
8. The recycling method of the perfluorosulfonic acid proton exchange membrane according to any one of claims 1 to 7, comprising the steps of:
(1) dissolving a physically crushed perfluorinated sulfonic acid proton exchange membrane in a mixed solution of an organic solvent and water with a boiling point of 80-90 ℃, wherein the volume ratio of the organic solvent and water with the boiling point of 80-90 ℃ is (1-4): 1, heating to 40-80 ℃, stirring for 2-10 h, filtering for 0.5-5 h under the pressure of 0.1-0.5 MPa by using a filter screen with the mesh number of 20-300, washing with a hydrogen peroxide solution with the concentration of 10-80% and distilled water, collecting filtrate, heating to 60-90 ℃, drying for 1-4 h, obtaining a first solid, and recycling the solvent;
(2) dissolving the first solid in a mixed solution of an organic solvent and water, wherein the volume ratio of the organic solvent to the water is (1-10): 1, adding a chelating agent, filtering by using a filter screen with the mesh number of 300-500 meshes under the pressure of 0.2-0.8 MPa for 0.5-5 h, washing by using a hydrogen peroxide solution with the concentration of 10-80% and distilled water, collecting filtrate, heating to 100-150 ℃, drying for 1-4 h to obtain a second solid, and recycling the solvent;
(3) and dissolving the second solid in a mixed solution of an organic solvent with a boiling point of 300-350 ℃ and water, wherein the volume ratio of the organic solvent with the boiling point of 300-350 ℃ to the water is (1-4): 1, stirring for 1-10 h under the conditions of 150-250 ℃ and 1-10MPa to obtain the perfluorinated sulfonic acid resin, and recycling the solvent.
9. The perfluorinated sulfonic acid resin obtained by the recycling method of the perfluorinated sulfonic acid proton exchange membrane according to any one of claims 1 to 8, wherein the purity of the perfluorinated sulfonic acid resin is 90 to 99%.
10. Use of a perfluorosulphonic resin according to claim 10 in a proton exchange membrane, preferably a fuel cell.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020128430A1 (en) * | 2001-03-09 | 2002-09-12 | Asahi Glass Company, Limited | Process for recovering fluoropolymers |
| CN1414652A (en) * | 2001-10-24 | 2003-04-30 | 中国科学院大连化学物理研究所 | Method of preparing membrane electrode using recasted perfluro sulfonic acid proton exchange film |
| CN1699450A (en) * | 2005-05-13 | 2005-11-23 | 华东理工大学 | Process for preparing perfluorinated sulfonic resin solution by using waste perfluorinated ion membrane |
| US20060177719A1 (en) * | 2005-02-08 | 2006-08-10 | Fuller Timothy J | Sulfonated polyelectrolyte membranes containing perfluorosulfonate ionomers |
-
2019
- 2019-12-09 CN CN201911248857.4A patent/CN111116979A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020128430A1 (en) * | 2001-03-09 | 2002-09-12 | Asahi Glass Company, Limited | Process for recovering fluoropolymers |
| CN1414652A (en) * | 2001-10-24 | 2003-04-30 | 中国科学院大连化学物理研究所 | Method of preparing membrane electrode using recasted perfluro sulfonic acid proton exchange film |
| US20060177719A1 (en) * | 2005-02-08 | 2006-08-10 | Fuller Timothy J | Sulfonated polyelectrolyte membranes containing perfluorosulfonate ionomers |
| CN1699450A (en) * | 2005-05-13 | 2005-11-23 | 华东理工大学 | Process for preparing perfluorinated sulfonic resin solution by using waste perfluorinated ion membrane |
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