CN114678553A - Recycling method of waste proton exchange membrane electrolytic water film electrode - Google Patents
Recycling method of waste proton exchange membrane electrolytic water film electrode Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/008—Disposal or recycling of fuel cells
Abstract
The invention provides a method for recovering an electrolytic water film electrode of a waste proton exchange membrane, in particular to the recovery of a proton exchange membrane and a platinum group noble metal, which is also suitable for the recovery of a membrane electrode of a proton exchange membrane fuel cell. The method firstly uses mild solvent to strip the catalyst layer on both sides of the membrane electrode from the proton exchange membrane, then respectively dissolves and purifies the noble metals of platinum and iridium in the waste catalyst, can respectively realize the recovery and the reutilization of the proton exchange membrane, the platinum and the iridium, has the advantages of simple process flow, high recovery efficiency and low impurity content, is particularly suitable for the recovery of a large batch of waste membrane electrodes in the industrial field, is favorable for relieving the pressure of extremely rare noble metal resources and the pressure of waste on the environment, simultaneously provides a feasible way for the recovery and the reutilization of PEM hydrogen production equipment after the service life is terminated, and is favorable for reducing the cost.
Description
Technical Field
The invention belongs to the technical field of membrane electrode recovery, and particularly relates to a recovery method of a waste proton exchange membrane electrolytic water film electrode, in particular to recovery of a proton exchange membrane and platinum group noble metals. Meanwhile, the invention is also suitable for recycling the membrane electrode of the proton exchange membrane fuel cell.
Background
The Proton Exchange Membrane (PEM) water electrolysis hydrogen production technology is one of the current international mainstream water electrolysis technologies, can be directly supplied to a high-purity hydrogen gas using occasion, has the characteristics of high purity grade, less impurity gas and easy combination with renewable energy sources, and is considered as a green hydrogen energy supply mode with the most development potential in the future. Under the background of large-scale high-proportion development of global renewable energy sources and 'carbon peak reaching' and 'carbon neutralization', the PEM hydrogen production technology becomes a core prime mover for promoting the rapid development of the green hydrogen industry, and an important way is opened for accelerating carbon emission reduction. With the proliferation of global GW-level green hydrogen construction projects, the market share of PEM devices will multiply. However, the expensive membrane electrodes and the relatively short operational lifetime are still the biggest problems facing large scale applications of PEM equipment compared to alkaline electrolysis. The treatment of the spent membrane electrode at the end of the life of the PEM unit from which the recovery of the proton exchange membrane and precious metals would be an important measure for both economic and environmental friendliness.
The membrane electrode used in PEM electrolyzer is composed of proton exchange membrane, cathode and anode catalytic layers, wherein the cathode catalytic layer is composed of platinum black or carbon-supported platinum catalyst and solid polymer electrolyte, and the anode catalytic layer is composed of iridium-based catalyst such as iridium black or iridium oxide and solid polymer electrolyte. Due to the high cost and scarcity of platinum group metals, environmentally friendly recovery of platinum group metals from commercial sources (e.g., PEM fuel cells and PEM electrolyzer electrocatalysts) is of critical strategic importance. The existing research on recycling of waste membrane electrodes mainly aims at the field of PEM fuel cells, and generally dissolves a proton exchange membrane into a resin solution at high temperature and high pressure to serve as a membrane preparation raw material; the precious metal is recovered by dissolving platinum with aqua regia, then removing nitrate and concentrating to obtain chloroplatinic acid, and harmful gases such as NO are generated in the process. Currently, researches on membrane electrode recycling of PEM electrolytic cells are few, and due to different catalytic layer compositions on the cathode/anode sides of the PEM electrolytic water membrane electrode, separation and purification of different kinds of precious metals is a great technical challenge facing recycling of the PEM electrolytic water membrane electrode at present.
Disclosure of Invention
The invention aims to provide a method for respectively recovering a proton exchange membrane, noble metals platinum and iridium from a waste PEM electrolysis water membrane electrode and recycling the components, which has the characteristics of simple process flow, high recovery efficiency, low impurity content and low environmental pollution, is particularly suitable for recovering a large quantity of waste membrane electrodes in the industrial field, can effectively reduce the cost of PEM electrolysis hydrogen production, and reduces the environmental pollution caused by waste perfluorosulfonic acid polymers and heavy metals.
The invention provides a recycling method of a waste proton exchange membrane electrolytic water film electrode, which comprises the following steps:
(1) soaking the waste membrane electrode into a solvent A, peeling a catalyst layer and a proton exchange membrane by ultrasonic treatment, scraping and washing, cleaning the proton exchange membrane by using the solvent, then carrying out regeneration treatment on the proton exchange membrane, collecting liquid suspended matters, filtering and centrifugally separating to obtain a first catalyst filter residue, and recycling the filtrate;
(2) drying and grinding the filter residue I, adding the filter residue I into a solvent B, heating the mixture in a high-pressure kettle for a period of time for reaction, dissolving solid polymer electrolyte in the filter residue, and then carrying out centrifugal separation and drying to obtain a filter residue II;
(3) if the second filter residue contains carbon, burning the second filter residue to remove carbon substances, and leaching base metal impurities by using the leaching solution A; if the filter residue II does not contain carbon, directly leaching base metal impurities by using the leaching solution A; then filtering and centrifugally separating to obtain filter residue III;
(4) adding the filter residue III into the leaching solution B for reaction, performing solid-liquid separation after the reaction is completed to obtain a chloroplatinic acid solution and an iridium oxide/iridium insoluble substance respectively, measuring the platinum content in the chloroplatinic acid solution, adjusting the pH value, using the solution as a platinum precursor solution, or reducing/precipitating platinum/platinum salt for recycling;
(5) dissolving the iridium oxide/iridium obtained in the step (4) by using a leaching solution C to obtain a chloroiridate solution, measuring the iridium content in the solution, adjusting the pH value of the solution, using the solution as an iridium precursor solution, or precipitating an ammonium chloroiridate precipitate by using ammonium chloride, and reducing the precipitate by calcining hydrogen to obtain metal iridium for reuse;
wherein the solvent A is lower alkyl alcohol or a mixed solvent of the lower alkyl alcohol and water; the solvent B is a mixed solution of at least one of methanol, ethanol, ethylene glycol, isopropanol, n-propanol, glycerol, butanol, acetone, DMF, DMA, DMSO and NMP and water; the leachate A is at least one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, perchloric acid and periodic acid; the leachate B is a hydrochloric acid solution containing at least one oxidant; the leachate C is a hydrochloric acid solution.
As a further scheme of the invention, the lower alkyl alcohol in the solvent a is at least one of normal alcohol, isomeric alcohol or polyhydric alcohol with a carbon chain length of C1-C8, the water is ultrapure water, the mass percentage of alcohol in the mixed solvent of the lower alkyl alcohol and the water is 10-90%, and the solvent a is used for immersing the membrane electrode; the mass ratio of the solute to water in the solvent B is 0.05-20: 1, the dosage of the solvent B is 1-200 mL/g of filter residue.
As a further scheme of the invention, the heating reaction temperature in the step (2) is 120-300 ℃, and the time is 3-24 h.
As a further scheme of the invention, the firing temperature in the step (3) is 300-800 ℃, and the time is 0.5-15 h; the concentration of the leaching solution A is 0.5-12 mol/L, and the dosage of the leaching solution A is 2-150 mL/g of filter residue.
As a further aspect of the present invention, in the step (4): the oxidant in the leaching solution B is sodium chlorate, sodium hypochlorite, potassium chlorate, potassium hypochlorite, sodium peroxide, potassium peroxide, hydrogen peroxide, peroxyacetic acid or nitric acid, the concentration of the oxidant is 0.5-10 mol/L, the concentration of hydrochloric acid is 1-12 mol/L, and the molar ratio of the oxidant to the hydrochloric acid is 0.05-20: 1, the dosage of the leaching solution B is 2-200 mL/g of filter residue; the reaction temperature is 20-90 ℃, and the reaction time is 0.1-12 h.
As a further scheme of the invention, the concentration of the leachate in the step (5) is 5-12 mol/L, and the dosage of the leachate C is 2-200 mL/g of filter residue.
As a further embodiment of the present invention, the proton exchange membrane regeneration treatment in step (1) is: cleaning and regenerating the proton exchange membrane for 1-5 times by using one or more of 0.5-3 mol/L hydrogen peroxide, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, acetic acid, sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia water, wherein the regeneration temperature is 50-150 ℃, and the regeneration time is 0-48 h; and then, carrying out heat treatment on the membrane for 0.5-24 h at 50-120 ℃ by using ultrapure water, repeating the heat treatment for 1-5 times, drying the membrane to obtain a regenerated proton exchange membrane, and finally coating one or two of a perfluorosulfonic acid membrane solution or a PTFE emulsion with the concentration of 0.5-30 wt% as a modifier on two sides of the proton exchange membrane to modify the proton exchange membrane, wherein the dosage of the modifier is 0-10% of the total mass of the proton exchange membrane.
As a further embodiment of the present invention, the reduction/precipitation of the platinum/platinum salt in the step (4) refers to: reducing chloroplatinic acid by using at least one of formaldehyde, formic acid, methanol, ethanol, ethylene glycol, ethylenediamine, sodium borohydride, potassium borohydride, hydrazine hydrate, ascorbic acid and sodium citrate and precipitating the chloroplatinic acid into metal platinum; or ammonium chloroplatinate precipitate is formed by the reaction of ammonium chloride and the ammonium chloride.
In a further embodiment of the present invention, before dissolving the solid in the leachate C in step (5), at least one of sodium hydroxide, potassium nitrate, sodium peroxide, sodium chlorate, sodium hypochlorite, potassium chlorate, potassium hypochlorite, and hydrogen peroxide is used to melt iridium oxide/iridium at 400 to 800 ℃ for 0.5 to 8 hours.
The application of the above method for recycling the waste proton exchange membrane electrolytic water membrane electrode in the recycling of the membrane electrode of the proton exchange membrane fuel cell is also within the protection scope of the present invention.
The invention has the effective effects that:
1. the method firstly uses mild solvent to strip the catalyst layer on both sides of the membrane electrode from the proton exchange membrane, then respectively dissolves and purifies the noble metals of platinum and iridium in the waste catalyst, can respectively realize the recovery and the reutilization of the proton exchange membrane, the platinum and the iridium, has the advantages of simple process flow, high recovery efficiency and low impurity content, is particularly suitable for the recovery of a large batch of waste membrane electrodes in the industrial field, is favorable for relieving the pressure of extremely rare noble metal resources and the pressure of waste on the environment, simultaneously provides a feasible way for the recovery and the reutilization of PEM hydrogen production equipment after the service life is terminated, and is favorable for reducing the cost.
2. The process related by the invention has both economy and environmental friendliness, for example, the solvent heat treatment is carried out on the waste catalyst before burning and decarbonizing, and the solid polymer electrolyte in the waste catalyst is removed, so that harmful gas HF cannot be generated in the high-temperature burning process, the pollution to the environment is avoided, and an expensive HF absorption device does not need to be matched; in the process of dissolving the noble metal, hydrochloric acid solution containing at least one oxidant is used for replacing aqua regia, NO toxic NO gas is generated, the safety is good, and the environmental pollution is small; meanwhile, the used solvent can be recycled, so that waste is avoided, and the environmental protection pressure is reduced.
3. The chloroplatinic acid or chloroiridic acid recovered by the method can be directly used as a noble metal precursor in the synthesis process, so that the necessary step of recovering noble metal in the form of a metal simple substance or a metal compound is eliminated in some occasions using noble metal solution.
Drawings
Fig. 1 is a flow chart of a method for recycling an electrolytic water film electrode of a waste proton exchange membrane according to an embodiment of the present invention.
FIG. 2 is a schematic diagram of a method for recycling an electrode of an electrolytic water film of a waste proton exchange membrane according to an embodiment of the present invention.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Summary of the invention:
the invention provides a method for recycling a waste proton exchange membrane electrolytic water film electrode, which comprises the following steps of:
(1) soaking the waste membrane electrode into a solvent A, peeling a catalytic layer and a proton exchange membrane by ultrasonic treatment, scraping and washing, cleaning the proton exchange membrane by using the solvent, then carrying out regeneration treatment on the proton exchange membrane, collecting liquid suspended matters, filtering and centrifugally separating to obtain a catalyst filter residue I, and recycling the filtrate.
(2) And drying and grinding the filter residue I, adding the filter residue I into a solvent B, heating the mixture in a high-pressure kettle for a period of time for reaction, dissolving solid polymer electrolyte in the filter residue, and then carrying out centrifugal separation and drying to obtain a filter residue II.
(3) If the second filter residue contains carbon, burning the second filter residue to remove carbon substances, and leaching base metal impurities by using the leaching solution A; if the filter residue II does not contain carbon, directly leaching base metal impurities by using the leaching solution A; then filtering and centrifugally separating to obtain filter residue III;
(4) and adding the filter residue III into the leaching solution B for reaction, performing solid-liquid separation after the reaction is completed to obtain a chloroplatinic acid solution and an iridium oxide/iridium insoluble substance respectively, measuring the platinum content in the chloroplatinic acid solution, adjusting the pH value, using the solution as a platinum precursor solution, or reducing/precipitating platinum/platinum salt for recycling.
(5) Dissolving the iridium oxide/iridium obtained in the step (4) by using a leaching solution C to obtain a chloroiridic acid solution, measuring the iridium content in the solution, adjusting the pH value of the solution, using the solution as an iridium precursor solution, or precipitating an ammonium chloroiridate precipitate by using ammonium chloride, and obtaining metal iridium for reuse by calcining hydrogen reduction.
Example 1
Taking a tablet with an active area of 200cm2The cathode of the membrane electrode uses a platinum-carbon catalyst, and the initial platinum loading is 1mg/cm2The anode used an iridium oxide catalyst with an initial iridium loading of 3mg/cm2The total amount of platinum and iridium in the membrane electrode is 200mg and 600 mg.
1) And soaking the waste membrane electrode in ethanol enough to submerge the waste membrane electrode for 10min, and stripping the catalytic layer and the proton exchange membrane by scraping and washing.
2) Cleaning the waste proton exchange membrane obtained in the step 1) by using ethanol and ultrapure water, immersing the waste proton exchange membrane into a 2mol/L sulfuric acid solution, carrying out heat treatment at 90 ℃ for 12h, then carrying out heat treatment at 90 ℃ for 12h, drying, preparing a perfluorosulfonic acid resin solution with the concentration of 2 wt%, and spraying the perfluorosulfonic acid resin solution to two sides of the proton exchange membrane, wherein the loading amount of perfluorosulfonic acid resin is 1mg/cm2And reusing the proton exchange membrane modified by the perfluorinated sulfonic acid resin.
3) Collecting the liquid suspended matters after the proton exchange membrane is stripped in the step 1), performing centrifugal separation to obtain a first filter residue, drying and grinding the first filter residue, which contains the inactivated platinum-carbon and iridium oxide catalyst and the solid polymer electrolyte filter residue, into fine powder, and adding 50mL of ethanol and water in a mass ratio of 1:1, placing the mixture in a high-pressure kettle, reacting for 3 hours at 250 ℃, removing solid polymer electrolyte in filter residue, centrifugally separating and drying to obtain filter residue II, wherein the filter residue II contains inactivated platinum carbon and iridium oxide catalyst. And calcining the filter residue II in the crucible for 5 hours in the air at 450 ℃, so that the carbon material is fully oxidized into carbon dioxide and discharged, and obtaining the residual substances in the crucible, wherein the main components of the residual substances are platinum and iridium oxide. And (3) immersing the residual substance into 2mol/L hydrochloric acid, reacting at 80 ℃ for 2h to remove base metals, and performing centrifugal separation to obtain filter residue III.
4) And adding the filter residue III into a mixed solution of 25mL hydrochloric acid with the concentration of 1mol/L and 25mL sodium chlorate with the concentration of 1mol/L (the mixing ratio is 1:1), reacting for 3 hours at 60 ℃, standing for layering, reducing chloroplatinic acid solution on the upper layer and iridium oxide solid on the lower layer, separating, reducing the chloroplatinic acid into metal platinum by hydrazine hydrate, weighing to obtain 183mg of platinum, and calculating to obtain the recovery rate of the platinum of 91.5%. Dissolving iridium oxide in 50mL of hydrochloric acid with the concentration of 8mol/L to obtain a chloroiridic acid solution, adding ammonium chloride to the chloroiridic acid solution to obtain ammonium chloroiridate precipitate, reducing the precipitate by calcined hydrogen to obtain metallic iridium, weighing the metallic iridium to 557mg, and calculating to obtain the recovery rate of the iridium to be 92.8%.
Example 2
Taking a tablet with an active area of 200cm2The cathode of the membrane electrode uses a platinum-carbon catalyst, and the initial platinum loading is 1mg/cm2The anode used an iridium black catalyst with an initial iridium loading of 3mg/cm2The total amount of platinum and iridium in the membrane electrode is 200mg and 600 mg.
Soaking the waste membrane electrode in ethanol enough to submerge the waste membrane electrode, stripping a catalytic layer from the waste proton exchange membrane by scraping and washing after soaking for 10min, cleaning the proton exchange membrane by using ethanol and ultrapure water, soaking the proton exchange membrane in 2mol/L sulfuric acid solution, carrying out heat treatment at 90 ℃ for 12h, then carrying out heat treatment at 90 ℃ for 12h, drying, preparing 2 wt% perfluorosulfonic acid resin solution, spraying the perfluorosulfonic acid resin solution on two sides of the proton exchange membrane, wherein the loading amount of the perfluorosulfonic acid resin is 1mg/cm2And reusing the proton exchange membrane modified by the perfluorinated sulfonic acid resin.
And collecting the liquid suspended matters after the proton exchange membrane is stripped, and performing centrifugal separation to obtain a first filter residue, wherein the first filter residue comprises inactivated platinum carbon and iridium black catalysts and solid polymer electrolyte filter residues. Drying the filter residue, grinding the filter residue into fine powder, and adding 50mL of isopropanol and water in a mass ratio of 1:1, placing the mixture into a high-pressure kettle, reacting for 3 hours at 250 ℃, removing solid polymer electrolyte in filter residue, centrifugally separating and drying to obtain filter residue II, wherein the filter residue II comprises inactivated platinum-carbon and iridium black catalysts. And calcining the filter residue II in air at 450 ℃ for 5 hours in a crucible, so that the carbon material is fully oxidized into carbon dioxide and discharged, and obtaining the residual substance in the crucible, wherein the main component of the residual substance is the mixture of the metal platinum and the iridium. And (3) immersing the residual substance into 2mol/L perchloric acid, reacting for 2h at 80 ℃ to remove base metals, and performing centrifugal separation to obtain filter residue III.
And adding the filter residue III into a mixed solution of 5mL of hydrochloric acid with the concentration of 8mol/L and 5mL of sodium peroxide with the concentration of 3mol/L, reacting for 3 hours at 60 ℃, standing for layering, wherein the upper layer is a chloroplatinic acid solution, the lower layer is an iridium solid, performing solid-liquid separation, reducing the chloroplatinic acid into metal platinum by using sodium borohydride, weighing 189mg, calculating to obtain the recovery rate of 94.5% of platinum, calculating to obtain 563mg of iridium, and calculating to obtain the recovery rate of 93.8% of iridium. Iridium was dissolved in 30mL of hydrochloric acid having a concentration of 6mol/L to obtain a chloroiridic acid solution, which was used as an iridium precursor solution.
Example 3
Taking a tablet with an active area of 200cm2The cathode of the membrane electrode uses a platinum black catalyst, and the initial platinum loading is 1mg/cm2The anode used an iridium oxide catalyst with an initial iridium loading of 3mg/cm2The total amount of platinum and iridium in the membrane electrode is 200mg and 600 mg.
Soaking the waste membrane electrode to a condition that the mass ratio of ethanol to water which are enough to submerge the waste membrane electrode is 3: 1, soaking for 10min, peeling off a catalyst layer and a proton exchange membrane by scraping and washing, cleaning the proton exchange membrane by using ethanol and ultrapure water, soaking the proton exchange membrane into 2mol/L hydrochloric acid solution, carrying out heat treatment at 90 ℃ for 12h, then carrying out heat treatment at 90 ℃ for 12h, drying, preparing 5 wt% PTFE solution, spraying the PTFE solution on two sides of the proton exchange membrane, wherein the loading amount of PTFE is 1mg/cm2And reusing the PTFE modified proton exchange membrane.
Collecting the stripped liquid suspended matters, carrying out centrifugal separation to obtain a first filter residue which contains inactivated platinum and iridium oxide catalysts and solid polymer electrolyte filter residues, drying and grinding the first filter residue into fine powder, and then adding 50mL of ethanol and water with the mass ratio of 2: 1, placing the mixture into a high-pressure kettle, reacting for 5 hours at 230 ℃, removing solid polymer electrolyte in filter residue, centrifugally separating and drying to obtain filter residue II, wherein the filter residue II comprises inactivated platinum and iridium oxide catalyst.
And immersing the filter residue II into 1mol/L nitric acid, reacting at 60 ℃ for 2h to remove base metals, and performing centrifugal separation to obtain a filter residue III. And adding the filter residue III into a mixed solution of 35mL hydrochloric acid with the concentration of 1mol/L and 15mL sodium peroxide with the concentration of 1mol/L, reacting for 3h at 90 ℃, standing and layering, wherein the upper layer is a chloroplatinic acid solution, the lower layer is an iridium oxide solid, separating, the chloroplatinic acid solution can be used as a platinum precursor solution, and the iridium oxide is dissolved by 50mL hydrochloric acid with the concentration of 8mol/L to obtain a chloroplatinic acid solution which can be used as an iridium precursor solution. The contents of platinum and iridium in chloroplatinic acid and chloroiridic acid were measured by atomic absorption spectrometry, and the recovery rates of platinum and iridium were calculated to be 95.1% and 93.3%, respectively.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive changes in the technical solutions of the present invention.
Claims (10)
1. A recycling method of a waste proton exchange membrane electrolytic water film electrode is characterized by comprising the following steps:
(1) soaking the waste membrane electrode into a solvent A, peeling a catalyst layer and a proton exchange membrane by ultrasonic treatment, scraping and washing, cleaning the proton exchange membrane by using the solvent, then carrying out regeneration treatment on the proton exchange membrane, collecting liquid suspended matters, filtering and centrifugally separating to obtain a first catalyst filter residue, and recycling the filtrate;
(2) drying and grinding the filter residue I, adding the filter residue I into a solvent B, heating the mixture in a high-pressure kettle for a period of time for reaction, dissolving solid polymer electrolyte in the filter residue, and then carrying out centrifugal separation and drying to obtain a filter residue II;
(3) if the second filter residue contains carbon, burning the second filter residue to remove carbon substances, and leaching base metal impurities by using the leaching solution A; if the filter residue II does not contain carbon, directly leaching base metal impurities by using the leaching solution A; then filtering and centrifugally separating to obtain filter residue III;
(4) adding the filter residue III into the leaching solution B for reaction, performing solid-liquid separation after the reaction is completed to obtain a chloroplatinic acid solution and an iridium oxide/iridium insoluble substance respectively, measuring the platinum content in the chloroplatinic acid solution, adjusting the pH value, using the solution as a platinum precursor solution, or reducing/precipitating platinum/platinum salt for recycling;
(5) dissolving the iridium oxide/iridium obtained in the step (4) by using a leaching solution C to obtain a chloroiridic acid solution, measuring the iridium content in the solution, adjusting the pH value of the solution, using the solution as an iridium precursor solution, or precipitating an ammonium chloroiridate precipitate by using ammonium chloride, and reducing the solution by calcining hydrogen to obtain metal iridium for recycling;
wherein the solvent A is lower alkyl alcohol or a mixed solvent of the lower alkyl alcohol and water; the solvent B is a mixed solution of at least one of methanol, ethanol, ethylene glycol, isopropanol, n-propanol, glycerol, butanol, acetone, DMF, DMA, DMSO and NMP and water; the leachate A is at least one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, perchloric acid and periodic acid; the leachate B is a hydrochloric acid solution containing at least one oxidant; the leachate C is a hydrochloric acid solution.
2. The method for recycling the waste proton exchange membrane electrolytic water film electrode according to claim 1, wherein the lower alkyl alcohol in the solvent A is at least one of normal alcohol, isomeric alcohol or polyhydric alcohol with a carbon chain length of C1-C8, the water is ultrapure water, the mass percent of the alcohol in the mixed solvent of the lower alkyl alcohol and the water is 10-90%, and the solvent A is used for immersing the membrane electrode; the mass ratio of the solute to water in the solvent B is 0.05-20: 1, the dosage of the solvent B is 1-200 mL/g of filter residue.
3. The method for recycling the waste proton exchange membrane electrolytic water film electrode according to claim 1, wherein the heating reaction temperature in the step (2) is 120-300 ℃ and the time is 3-24 h.
4. The method for recycling the waste proton exchange membrane electrolytic water film electrode according to claim 1, wherein the burning temperature in the step (3) is 300-800 ℃, and the time is 0.5-15 h; the concentration of the leaching solution A is 0.5-12 mol/L, and the dosage of the leaching solution A is 2-150 mL/g of filter residue.
5. The method for recycling the discarded proton exchange membrane electrolytic water film electrode according to claim 1, wherein in the step (4): the oxidant in the leaching solution B is sodium chlorate, sodium hypochlorite, potassium chlorate, potassium hypochlorite, sodium peroxide, potassium peroxide, hydrogen peroxide, peroxyacetic acid or nitric acid, the concentration of the oxidant is 0.5-10 mol/L, the concentration of hydrochloric acid is 1-12 mol/L, and the molar ratio of the oxidant to the hydrochloric acid is 0.05-20: 1, the dosage of the leaching solution B is 2-200 mL/g of filter residue; the reaction temperature is 20-90 ℃, and the reaction time is 0.1-12 h.
6. The method for recycling the waste proton exchange membrane electrolytic water film electrode according to claim 1, wherein the concentration of the leachate in the step (5) is 5-12 mol/L, and the dosage of the leachate C is 2-200 mL/g of filter residue.
7. The method for recycling the waste proton exchange membrane electrolysis water film electrode according to any one of claims 1 to 6, wherein the proton exchange membrane regeneration treatment in the step (1) is as follows: cleaning and regenerating the proton exchange membrane for 1-5 times by using one or more of 0.5-3 mol/L hydrogen peroxide, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, acetic acid, sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia water, wherein the regeneration temperature is 50-150 ℃, and the regeneration time is 0-48 h; and then, carrying out heat treatment on the membrane for 0.5-24 h at 50-120 ℃ by using ultrapure water, repeating the heat treatment for 1-5 times, drying the membrane to obtain a regenerated proton exchange membrane, and finally coating one or two of a perfluorosulfonic acid membrane solution or a PTFE emulsion with the concentration of 0.5-30 wt% as a modifier on two sides of the proton exchange membrane to modify the proton exchange membrane, wherein the dosage of the modifier is 0-10% of the total mass of the proton exchange membrane.
8. The method for recycling the discarded proton exchange membrane electrolytic water film electrode according to claim 7, wherein the reduction/precipitation of the platinum/platinum salt in the step (4) is: reducing chloroplatinic acid by using at least one of formaldehyde, formic acid, methanol, ethanol, ethylene glycol, ethylenediamine, sodium borohydride, potassium borohydride, hydrazine hydrate, ascorbic acid and sodium citrate and precipitating the chloroplatinic acid into metal platinum; or ammonium chloroplatinate precipitate is formed by the reaction of ammonium chloride and the ammonium chloride.
9. The method for recycling the waste proton exchange membrane electrolysis water film electrode according to claim 8, wherein before the leachate C in the step (5) dissolves solids, the iridium oxide/iridium is melted by at least one of sodium hydroxide, potassium nitrate, sodium peroxide, sodium chlorate, sodium hypochlorite, potassium chlorate, potassium hypochlorite and hydrogen peroxide at a temperature of 400-800 ℃ for 0.5-8 h.
10. The use of the method of recycling a spent proton exchange membrane electrolytic water membrane electrode of any one of claims 1 to 9 in the recycling of a membrane electrode for a proton exchange membrane fuel cell.
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