CN109088080A - The recovery method of one proton exchanging film fuel battery - Google Patents

The recovery method of one proton exchanging film fuel battery Download PDF

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Publication number
CN109088080A
CN109088080A CN201810765886.7A CN201810765886A CN109088080A CN 109088080 A CN109088080 A CN 109088080A CN 201810765886 A CN201810765886 A CN 201810765886A CN 109088080 A CN109088080 A CN 109088080A
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platinum
nafion
membrane
solution
membrane electrode
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张深根
丁云集
刘波
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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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
    • H01M8/008—Disposal or recycling of fuel cells
    • 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
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The present invention relates to the recovery methods of a proton exchanging film fuel battery, belong to resource circulation utilization field.The method includes Proton Exchange Membrane Fuel Cells dismantling, the dissolution of perfluorinated sulfonic acid (Nafion) film and casting film regeneration, the oxidation complexation of platinum and purification refining, finally obtains bipolar plates, regeneration Nafion membrane and platinum ingot.The present invention is avoided traditional fluoride pollution directly burned and generated, is had significant economic benefit using the Nafion membrane of organic solvent dissolution recycling high value；Using resin cation absorption and pyro-refining removal of impurities, the platinum ingot of 99.99% or more purity is obtained, has the characteristics that process is short, non-pollutant discharge, is suitable for industrial applications.

Description

The recovery method of one proton exchanging film fuel battery
Technical field
The present invention principally falls into resource circulation utilization technical field, and in particular to a proton exchanging film fuel battery is returned Receiving method.
Background technique
Proton exchange film fuel battery system is the core of Proton Exchange Membrane Fuel Cells automobile, by fuel cell pack and auxiliary Auxiliary system composition, cost account for the 63% of integral vehicle cost.The cost of pile has reached 2/3 in fuel cell system, fuel The cost of pile accounts for about the 41% of entire fuel-cell vehicle cost.Fuel cell pack is the heart of fuel cell system, single to fire Material battery core is mainly to be made of bipolar plates (mechanism of hydrogen-oxygen supply) and membrane electrode, and membrane electrode is mainly by proton exchange membrane, expansion Dissipate layer (carbon-fiber film), platinum catalyst composition.The working principle of Proton Exchange Membrane Fuel Cells are as follows: using hydrogen as fuel, with sky Gas or oxygen are that redox reaction, proton exchange membrane one-way conduction H occur under platinum catalysis for oxidant+Form electric current.
Proton exchange membrane is the core component of fuel cell (PEMFC), thickness only 50~180um.Proton exchange membrane is combustion Expect the base of cell electrolyte and electrode active material (catalyst), there is selective penetrated property, i.e., only allow H+Through, and do not allow Perhaps H2Molecule and other ions penetrate.Proton exchange membrane has sufficiently high mechanical strength and structural strength and film surface suitable Close the performances such as in conjunction with catalyst.
Currently, largely using Nafion membrane in fuel cell.Nafion is a kind of perfluorinated sulfonic acid polymer excessively, has fluorine Change copolymer skeleton, sulfonic acid group and its chemical bond, and have fixed position, proton is then coupled freedom, can play electric action. Nafion membrane it is expensive, the cost of film accounts for the 20%~30% of totle drilling cost in the fuel cell system.Bipolar plates are led at present There are metal double polar plates, without empty graphite bi-polar plate, graphite/resin compound bipolar plate.Current most widely used bipolar plates are machines Add graphite plate, since pure graphite plate hardness is big and crisp, needs accurate machining, bipolar plates account for entire fuel cell weight 60%, the 13% of cost.Since pem cell running temperature is lower, it is necessary to using platinum group noble metal for promoting hydrogen With the reaction speed of oxygen, usage amount is in 100g or so at present.The dosage of platinum has been greatly decreased in recent years.Platinum is negative on membrane electrode Carrying capacity is from 10mg/cm2Fall below 0.02mg/cm2, the load capacity of platinum reduces nearly 200 times, according to american energy office target, with The innovation of fuel cell pile technology, platinum dosage will be expected to be reduced to 50g in the following proton exchange membrane pile, and final goal is Dosage is controlled in 20-30g.Therefore, the recycling of Proton Exchange Membrane Fuel Cells can alleviate the supply of platinum and have significant warp Ji benefit.
In recent years, the recycling of Proton Exchange Membrane Fuel Cells gradually causes the concern of people.Chinese invention patent (200810011454.3) disclose a kind of ultrasound shake off, your gold in the method recycling fuel cell of high pressure dissolution and centrifuge separation Metal catalyst, this method is inefficient, and centrifuge separation is not thorough, and the purity of platinum is not high, and proton exchange membrane fails effectively to return It receives.Chinese invention patent (200610111901.3) discloses a kind of method of basis material for removing membrane electrode, that is, uses solvent Proton exchange membrane and Catalytic Layer are distinguished, which is not directed to time of platinum in the recycling and reusing and Catalytic Layer of proton exchange membrane It receives.Chinese invention patent (201710047458.6) discloses a kind of method of waste and old fuel cell recycling, and in particular to double The separation of pole plate and membrane electrode, membrane electrode pyrolysis, platinum oxidation leach.This method has recycled bipolar plates and platinum, but proton exchange membrane Thermal cracking does not recycle, and thermal cracking generates a large amount of fluoride and sulfide, and environmental pollution is serious.Chinese invention patent (201510953480.8) ultrasound removing proton exchange membrane, cathode, anode catalyst layer, electron exchange Membrane cleaning, platinum charcoal are disclosed Catalyst recycling, this method has recycled proton exchange membrane and metal platinum, but operation difficulty is big, especially the recycling of dielectric film, It is difficult to directly take out from solid liquid phase.
To sum up, there are fluoride, sulphide staining, the non-high efficiente callbacks of valuable material for existing proton exchange membrane removal process Problem, how to recycle high value material in fuel cell (bipolar plates, proton exchange membrane, platinum) is the emphasis studied from now on With difficult point.
Summary of the invention
The fluoride and sulphide staining problem generated in the process for current burning disposal Proton Exchange Membrane Fuel Cells, And high value material (bipolar plates, proton exchange membrane etc.) the problem of cannot effectively recycling, the present invention provides a proton The recovery method of exchange film fuel battery, be it is a kind of green, environmental protection recycling Proton Exchange Membrane Fuel Cells in valuable material and platinum Method, recycling proton exchange membrane, roast-reduction-oxidation complexation-refining are dissolved using solvent and prepare high-purity platinum ingot, is not only shut out The generation of the pollutants such as fluoride absolutely, while the valuable material in battery has been recycled to greatest extent.
The present invention is achieved by the following technical solutions:
The recovery method of one proton exchanging film fuel battery, the described method comprises the following steps:
(1) battery is disassembled: disassembling the Proton Exchange Membrane Fuel Cells to obtain bipolar plates and membrane electrode；
(2) Nafion membrane dissolves: the membrane electrode being cleaned, impurity is removed, is then dissolved Nafion membrane with solvent, mistake Filter obtains Nafion solution and platinum charcoal filter residue；
(3) casting film: using the Nafion solution as raw material, direct casting film prepares Nafion regeneration membrane；
(4) platinum oxidation is complexed: removing organic matter and charcoal in the platinum charcoal filter residue that step (2) obtain by burning, passes through Hydrazine hydrate reduction, oxidation complexation obtain platiniferous solution；
(5) it platinum purification and refining: is restored after the platiniferous solution is removed metal cation with cation exchange resin Flux is added to simple substance platinum, after high temperature melting further to clean, is finally cast into platinum ingot.
Further, it in step (2), is cleaned using hydrogen peroxide and sulfuric acid cleaned, cleaning removal of impurities specifically: set membrane electrode 30-120min is reacted in the hydrogen peroxide that volume fraction is 1-10%, 60-100 DEG C of reaction temperature；Then it is washed with deionized 2-3 times；30-120min is reacted at 60-90 DEG C with the sulfuric acid of 0.1-2.0mol/L again, is then washed with deionized 2-3 times, Finally dry；
In step (2), Nafion membrane is dissolved with solvent specifically: the membrane electrode after drying is placed in hydrothermal reaction kettle In, using the aqueous solution of ethyl alcohol or isopropanol as solvent, 160-220 DEG C of solution temperature, time 2-4h.
Further, casting film described in step (3) is that the Nafion solution for obtaining step (2) is evaporated to obtain Nafion tree Rouge, by vacuum defoamation, casting film, obtains Nafion regeneration membrane after dmso solution is added.
Further, in step (4), the oxidation complexation agent used is chloroazotic acid, hydrochloric acid+hydrogen peroxide, hydrochloric acid+sodium chlorate, salt One of acid+sodium hypochlorite, hydrochloric acid+sulphuric acid+hydrogen peroxide, hydrochloric acid+sulphuric acid+sodium chlorate, oxidation complexation temperature are 70-100 DEG C, The oxidation complexation time is 2-6h.
Further, in step (5):
After removing metal cation using cation exchange resin, platiniferous GOLD FROM PLATING SOLUTION category cation concn≤200mg/L；
Reducing agent used by reduction process is one of hydrazine hydrate, formic acid, formaldehyde；
The flux being added after high temperature melting be one of sodium nitrate, borax, calcirm-fluoride, sodium carbonate or it is a kind of with On.
Further, in step (5), the purity of the platinum ingot prepared is 99.99% or more.
Advantageous effects of the invention:
1) the method for the invention includes Proton Exchange Membrane Fuel Cells dismantling, the dissolution of perfluorinated sulfonic acid (Nafion) film and casting Film regeneration, the oxidation complexation of platinum and purification refining, finally obtain bipolar plates, regeneration Nafion membrane and platinum ingot；Matter can effectively be recycled Bipolar plates, Nafion membrane and metal platinum in proton exchange film fuel cell realize the fuel cell comprehensive reutilization, have The advantages that economic, environmentally friendly, it is suitable for industrialized production；
2) compared with traditional Proton Exchange Membrane Fuel Cells incineration technology, the method for the invention is molten using organic solvent The regeneration Nafion membrane of solution, casting film recycling high value avoids fluoride and sulfide dirt that traditional technology directly burns generation Dye；
3) the method for the invention is greater than with the platinum ingot product purity that resin cation removal of impurities, high temperature pyro-refining obtain 99.99%；Have the characteristics that process is short, non-pollutant discharge, is suitable for industrial applications.
Detailed description of the invention
Fig. 1 is the process flow chart of the recovery method of a proton exchanging film fuel battery in the embodiment of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and It is not used in the restriction present invention.
On the contrary, the present invention covers any substitution done on the essence and scope of the present invention being defined by the claims, repairs Change, equivalent method and scheme.Further, in order to make the public have a better understanding the present invention, below to of the invention thin It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art The present invention can also be understood completely in description.
Embodiment 1
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 100 DEG C of dioxygens 30min is reacted in the aqueous solution that water concentration is 10.0%, is washed repeatedly with deionized water 3 times；Then by the membrane electrode after washing 30min is reacted at 90 DEG C with the sulfuric acid of 0.1mol/L, is then washed with deionized 2 times, it is dry.Membrane electrode after drying is used Ethanol water reacts 4h in 160 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.Nafion is molten Liquid is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion Regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, finally uses king Water is in 90 DEG C of reaction 3.0h by platinum oxidation complexation leaching.The metal cation in platiniferous solution is removed with cation exchange resin, Metal cation concentration 169mg/L after removal of impurities.Simple substance platinum powder is obtained with hydrazine hydrate reduction, nitric acid is added in platinum powder after high temperature melt Sodium and borax refining, are finally cast into platinum ingot, wherein platinum content 99.993%.
Embodiment 2
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 95 DEG C of hydrogen peroxide 40min is reacted in the aqueous solution that concentration is 9.0%, is washed repeatedly with deionized water 2 times；Then the membrane electrode after washing is used The sulfuric acid of 0.2mol/L reacts 35min at 86 DEG C, is then washed with deionized 3 times, dry.Membrane electrode after drying is with different Aqueous propanol solution reacts 3.8h in 165 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.By Nafion Solution is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, most Afterwards with hydrochloric acid+sodium hypochlorite mixed solution in 100 DEG C of reaction 3.5h by platinum oxidation complexation leaching.It is removed with cation exchange resin Metal cation in platiniferous solution, metal cation concentration 120mg/L after removal of impurities.It is restored to obtain simple substance platinum powder, platinum with formaldehyde Sodium nitrate and calcium oxide refining is added in powder after high temperature melt, is finally cast into platinum ingot, wherein platinum content 99.991%.
Embodiment 3
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 90 DEG C of hydrogen peroxide 50min is reacted in the aqueous solution that concentration is 8.0%, is washed repeatedly with deionized water 3 times；Then the membrane electrode after washing is used The sulfuric acid of 0.4mol/L reacts 40min at 84 DEG C, is then washed with deionized 3 times, dry.Membrane electrode after drying is with different Aqueous propanol solution reacts 3.5h in 170 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.By Nafion Solution is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, most Afterwards with hydrochloric acid+sodium chlorate in 100 DEG C of reaction 2.0h by platinum oxidation complexation leaching.With in cation exchange resin removal platiniferous solution Metal cation, metal cation concentration 80mg/L after removal of impurities.It is restored to obtain simple substance platinum powder with formic acid, platinum powder is through high temperature melt Sodium nitrate and sodium carbonate refining are added afterwards, is finally cast into platinum ingot, wherein platinum content 99.997%.
Embodiment 4
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 85 DEG C of hydrogen peroxide 60min is reacted in the aqueous solution that concentration is 7.0%, is washed repeatedly with deionized water 3 times；Then the membrane electrode after washing is used The sulfuric acid of 0.5mol/L reacts 45min at 80 DEG C, is then washed with deionized 2 times, dry.Membrane electrode second after drying Alcohol solution reacts 3.3h in 175 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.Nafion is molten Liquid is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion Regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, finally uses salt Acid+sulfuric acid+hydrogen peroxide mixed solution is in 70 DEG C of reaction 5.5h by platinum oxidation complexation leaching.Platiniferous is removed with cation exchange resin Metal cation in solution, metal cation concentration 195mg/L after removal of impurities.Simple substance platinum powder, platinum powder are obtained with hydrazine hydrate reduction Sodium nitrate, borax and calcium oxide refining are added after high temperature melt, is finally cast into platinum ingot, wherein platinum content 99.994%.
Embodiment 5
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 80 DEG C of hydrogen peroxide 70min is reacted in the aqueous solution that concentration is 6.0%, is washed repeatedly with deionized water 2 times；Then the membrane electrode after washing is used The sulfuric acid of 0.7mol/L reacts 50min at 76 DEG C, is then washed with deionized 3 times, dry.Membrane electrode after drying is with different Aqueous propanol solution reacts 3h in 180 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.Nafion is molten Liquid is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion Regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, finally uses salt Acid+dioxygen water mixed liquid is in 80 DEG C of reaction 3.0h by platinum oxidation complexation leaching.With in cation exchange resin removal platiniferous solution Metal cation, metal cation concentration 153mg/L after removal of impurities.Simple substance platinum powder is obtained with hydrazine hydrate reduction, platinum powder is through high temperature Sodium nitrate, calcium oxide and sodium carbonate refining are added after thawing, is finally cast into platinum ingot, wherein platinum content 99.992%.
Embodiment 6
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 75 DEG C of hydrogen peroxide 80min is reacted in the aqueous solution that concentration is 5.0%, is washed repeatedly with deionized water 2 times；Then the membrane electrode after washing is used The sulfuric acid of 0.85mol/L reacts 60min at 72 DEG C, is then washed with deionized 3 times, dry.Membrane electrode after drying is used Ethanol water reacts 2.8h in 185 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.By Nafion Solution is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, most Afterwards with hydrochloric acid+hydrogen peroxide mixed solution in 75 DEG C of reaction 4.0h by platinum oxidation complexation leaching.Contained with cation exchange resin removal Metal cation in platinum solution, metal cation concentration 30mg/L after removal of impurities.It is restored to obtain simple substance platinum powder, platinum powder warp with formaldehyde Sodium nitrate and calcium oxide refining are added after high temperature melt, is finally cast into platinum ingot, wherein platinum content 99.993%.
Embodiment 7
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 70 DEG C of hydrogen peroxide 90min is reacted in the aqueous solution that concentration is 4.0%, is washed repeatedly with deionized water 3 times；Then the membrane electrode after washing is used The sulfuric acid of 0.95mol/L reacts 70min at 70 DEG C, is then washed with deionized 2 times, dry.Membrane electrode after drying is used Isopropanol water solution reacts 2.6h in 190 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.It will Nafion solution is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains To Nafion regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, Finally with hydrochloric acid+sodium chlorate in 80 DEG C of reaction 4.0h by platinum oxidation complexation leaching.Platiniferous solution is removed with cation exchange resin In metal cation, metal cation concentration 67mg/L after removal of impurities.It is restored to obtain simple substance platinum powder with formic acid, platinum powder is through high-temperature molten Sodium nitrate and sodium carbonate refining are added after change, is finally cast into platinum ingot, wherein platinum content 99.995%.
Embodiment 8
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 65 DEG C of hydrogen peroxide 100min is reacted in the aqueous solution that concentration is 3.0%, is washed repeatedly with deionized water 3 times；Then the membrane electrode after washing is used The sulfuric acid of 1.05mol/L reacts 80min at 68 DEG C, is then washed with deionized 2 times, dry.Membrane electrode after drying is used Ethanol water reacts 2.5h in 195 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.By Nafion Solution is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, most Afterwards with hydrochloric acid+sodium hypochlorite mixed liquor in 95 DEG C of reaction 2.5h by platinum oxidation complexation leaching.Contained with cation exchange resin removal Metal cation in platinum solution, metal cation concentration 114mg/L after removal of impurities.Simple substance platinum powder, platinum are obtained with hydrazine hydrate reduction Sodium nitrate and borax refining is added in powder after high temperature melt, is finally cast into platinum ingot, wherein platinum content 99.990%.
Embodiment 9
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 60 DEG C of hydrogen peroxide 110min is reacted in the aqueous solution that concentration is 2.0%, is washed repeatedly with deionized water 2 times；Then the membrane electrode after washing is used The sulfuric acid of 1.3mol/L reacts 90min at 65 DEG C, is then washed with deionized 2 times, dry.Membrane electrode second after drying Alcohol solution reacts 2.4h in 200 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.Nafion is molten Liquid is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion Regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, finally uses king Water is in 85 DEG C of reaction 4.0h by platinum oxidation complexation leaching.The metal cation in platiniferous solution is removed with cation exchange resin, Metal cation concentration 92mg/L after removal of impurities.Restore to obtain simple substance platinum powder with formaldehyde, platinum powder be added after high temperature melt sodium nitrate, Calcium oxide and sodium carbonate refining, are finally cast into platinum ingot, wherein platinum content 99.991%.
Embodiment 10
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 60 DEG C of hydrogen peroxide 120min is reacted in the aqueous solution that concentration is 1.0%, is washed repeatedly with deionized water 3 times；Then the membrane electrode after washing is used The sulfuric acid of 1.5mol/L reacts 100min at 62 DEG C, is then washed with deionized 3 times, dry.Membrane electrode after drying is used Ethanol water reacts 2.3h in 205 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.By Nafion Solution is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, most Afterwards with hydrochloric acid+liquor natrii hypochloritis in 90 DEG C of reaction 4.5h by platinum oxidation complexation leaching.Platiniferous is removed with cation exchange resin Metal cation in solution, metal cation concentration 58mg/L after removal of impurities.It is restored to obtain simple substance platinum powder with formaldehyde, platinum powder is through height Sodium nitrate and borax refining is added in temperature after melting, be finally cast into platinum ingot, wherein platinum content 99.993%.
Embodiment 11
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 88 DEG C of hydrogen peroxide 100min is reacted in the aqueous solution that concentration is 2.5%, is washed repeatedly with deionized water 3 times；Then the membrane electrode after washing is used The sulfuric acid of 1.7mol/L reacts 110min at 60 DEG C, is then washed with deionized 3 times, dry.Membrane electrode after drying is used Ethanol water reacts 2.2h in 210 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.By Nafion Solution is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, most Afterwards with hydrochloric acid+hydrogen peroxide mixed solution in 90 DEG C of reaction 4.5h by platinum oxidation complexation leaching.Contained with cation exchange resin removal Metal cation in platinum solution, metal cation concentration 13mg/L after removal of impurities.It is restored to obtain simple substance platinum powder, platinum powder warp with formic acid Sodium nitrate and calcium oxide refining are added after high temperature melt, is finally cast into platinum ingot, wherein platinum content 99.992%.
Embodiment 12
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 72 DEG C of hydrogen peroxide 90min is reacted in the aqueous solution that concentration is 3.5%, is washed repeatedly with deionized water 2 times；Then the membrane electrode after washing is used The sulfuric acid of 1.8mol/L reacts 120min at 70 DEG C, is then washed with deionized 3 times, dry.Membrane electrode after drying is used Ethanol water reacts 2.0h in 215 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.By Nafion Solution is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, most Afterwards with hydrochloric acid+sulphuric acid+sodium chlorate mixed solution in 80 DEG C of reaction 6.0h by platinum oxidation complexation leaching.It is gone with cation exchange resin Except the metal cation in platiniferous solution, metal cation concentration 46mg/L after removal of impurities.It is restored to obtain simple substance platinum powder, platinum with formic acid Sodium nitrate, calcium oxide and sodium carbonate refining is added in powder after high temperature melt, is finally cast into platinum ingot, wherein platinum content 99.996%.
Embodiment 13
Proton Exchange Membrane Fuel Cells is disassembled first to obtain bipolar plates and membrane electrode, membrane electrode is placed in 63 DEG C of hydrogen peroxide 70min is reacted in the aqueous solution that concentration is 5.5%, is washed repeatedly with deionized water 3 times；Then the membrane electrode after washing is used The sulfuric acid of 2.0mol/L reacts 40min at 85 DEG C, is then washed with deionized 3 times, dry.Membrane electrode second after drying Alcohol solution reacts 2.0h in 220 DEG C of hydrothermal reaction kettle, and Nafion solution and platinum charcoal filter residue is obtained by filtration.Nafion is molten Liquid is evaporated to obtain Nafion resin, after dimethyl sulfoxide (DMSO) dissolution is added, carries out vacuum defoamation, casting film, obtains Nafion Regeneration membrane.Platinum charcoal filter residue roasts at 800 DEG C removes organic matter and charcoal, then uses hydrazine hydrate reduction product of roasting, finally uses salt Acid+hydrogen peroxide mixed solution is in 95 DEG C of reaction 4.0h by platinum oxidation complexation leaching.Platiniferous solution is removed with cation exchange resin In metal cation, metal cation concentration 131mg/L after removal of impurities.Simple substance platinum powder is obtained with hydrazine hydrate reduction, platinum powder is through height Sodium nitrate, borax and sodium carbonate refining is added in temperature after melting, be finally cast into platinum ingot, wherein platinum content 99.994%.

Claims (6)

1. the recovery method of a proton exchanging film fuel battery, which is characterized in that the described method comprises the following steps:
(1) battery is disassembled: disassembling the Proton Exchange Membrane Fuel Cells to obtain bipolar plates and membrane electrode；
(2) Nafion membrane dissolves: the membrane electrode being cleaned, impurity is removed, then dissolves Nafion membrane with solvent, filter To Nafion solution and platinum charcoal filter residue；
(3) casting film: using the Nafion solution as raw material, direct casting film prepares Nafion regeneration membrane；
(4) platinum oxidation is complexed: removing organic matter and charcoal in the platinum charcoal filter residue that step (2) obtain by burning, passes through hydration Hydrazine reduction, oxidation complexation obtain platiniferous solution；
(5) platinum purification and refining: reduction obtains list after the platiniferous solution cation exchange resin is removed metal cation Flux is added after high temperature melting and further cleans, is finally cast into platinum ingot for matter platinum.
2. the recovery method of a proton exchanging film fuel battery according to claim 1, which is characterized in that in step (2), It is cleaned using hydrogen peroxide and sulfuric acid cleaned, cleaning removal of impurities specifically: membrane electrode is placed in the hydrogen peroxide that volume fraction is 1-10% Middle reaction 30-120min, 60-100 DEG C of reaction temperature；Then it is washed with deionized 2-3 times；The sulphur of 0.1-2.0mol/L is used again Acid reacts 30-120min at 60-90 DEG C, is then washed with deionized 2-3 times, finally dries；
In step (2), Nafion membrane is dissolved with solvent specifically: the membrane electrode after drying is placed in hydrothermal reaction kettle, with The aqueous solution of ethyl alcohol or isopropanol be solvent, 160-220 DEG C of solution temperature, time 2-4h.
3. the recovery method of a proton exchanging film fuel battery according to claim 1, which is characterized in that in step (3) The casting film is that the Nafion solution for obtaining step (2) is evaporated to obtain Nafion resin, after dmso solution is added, warp Vacuum defoamation, casting film are crossed, Nafion regeneration membrane is obtained.
4. the recovery method of a proton exchanging film fuel battery according to claim 1, which is characterized in that in step (4), The oxidation complexation agent used is chloroazotic acid, hydrochloric acid+hydrogen peroxide, hydrochloric acid+sodium chlorate, hydrochloric acid+sodium hypochlorite, hydrochloric acid+sulphuric acid+dioxygen One of water, hydrochloric acid+sulphuric acid+sodium chlorate, oxidation complexation temperature are 70-100 DEG C, and the oxidation complexation time is 2-6h.
5. the recovery method of a proton exchanging film fuel battery according to claim 1, which is characterized in that in step (5):
After removing metal cation using cation exchange resin, platiniferous GOLD FROM PLATING SOLUTION category cation concn≤200mg/L；
Reducing agent used by reduction process is one of hydrazine hydrate, formic acid, formaldehyde；
The flux being added after high temperature melting be one of sodium nitrate, borax, calcirm-fluoride, sodium carbonate or more than one.
6. the recovery method of a proton exchanging film fuel battery according to claim 1, which is characterized in that in step (5), The purity of the platinum ingot prepared is 99.99% or more.
CN201810765886.7A 2018-07-12 2018-07-12 The recovery method of one proton exchanging film fuel battery Pending CN109088080A (en)

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CN114892018B (en) * 2022-05-19 2023-10-24 广东先导稀材股份有限公司 Method for separating and recovering platinum and manganese in platinum-manganese alloy
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Application publication date: 20181225