CN114678553B - 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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Abstract
The invention provides a recovery method of a waste proton exchange membrane electrolytic water membrane electrode, in particular to recovery of a proton exchange membrane and platinum group noble metal, and is also suitable for recovery of a proton exchange membrane fuel cell membrane electrode. The invention firstly uses mild solvent to strip the catalytic layers on the two sides of the membrane electrode from the proton exchange membrane, then respectively dissolves and purifies the noble metals platinum and iridium in the waste catalyst, can respectively realize the recovery and reutilization of the proton exchange membrane, platinum and iridium, has the advantages of simple process flow, high recovery efficiency and low impurity content, is particularly suitable for the recovery of a large number of waste membrane electrodes in the industrial field, is beneficial to relieving the pressure of scarce noble metal resources and the pressure of wastes on the environment, and simultaneously provides a feasible way for the recovery and reutilization after the service life of PEM hydrogen production equipment, and is beneficial to 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 an electrolytic water membrane electrode of a waste proton exchange membrane, in particular to recovery of a proton exchange membrane and platinum noble metal. 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 taken as one of the current international mainstream water electrolysis technologies, can be directly supplied to the gas application occasion of high-purity hydrogen, has the characteristics of high purity level, less impurity gas and easy combination with renewable energy sources, and is considered as the green hydrogen energy supply mode with the most development potential in the future. Under the background of large-scale high-proportion development of renewable energy sources and 'carbon reaching peak', 'carbon neutralization', the PEM hydrogen production technology becomes a core motive force for promoting the rapid development of the green hydrogen industry, and an important way is provided for accelerating the carbon emission reduction. As global GW-level green hydrogen construction projects proliferate, the market share of PEM facilities will increase exponentially. However, the expensive membrane electrode and relatively short operating life are still the biggest problems faced by the large-scale application of PEM devices compared to alkaline electrolysis. The disposal of the spent membrane electrode at the end of the PEM plant life, from which the proton exchange membrane and noble metals are recovered, would be an important measure of both economy and environmental friendliness.
The membrane electrode used in PEM electrolysers is typically composed of a proton exchange membrane and cathode and anode catalytic layers, wherein the cathode catalytic layer is typically composed of a platinum black or carbon-supported platinum catalyst and a solid polymer electrolyte, and the anode catalytic layer is typically composed of an iridium-based catalyst such as iridium black or iridium oxide and a solid polymer electrolyte. Due to the high cost and scarcity of platinum group metals, it is of great strategic importance to the environmentally friendly recovery of industrial sources of platinum group metals such as PEM fuel cells and PEM electrolyser electrocatalysts. The existing research on recycling of waste membrane electrodes mainly aims at the field of PEM fuel cells, and a proton exchange membrane is generally dissolved into a resin solution at high temperature and high pressure to be used as a membrane preparation raw material; the recovery of noble metal is to dissolve platinum out by aqua regia, then remove nitrate and concentrate to obtain chloroplatinic acid, which can generate NO and other harmful gases. There are few studies on recycling of membrane electrodes of PEM electrolytic cells at present, and separation and purification of different noble metals are a great technical challenge for recycling of PEM electrolytic membrane electrodes at present due to different catalytic layer compositions at both sides of cathode/anode of the PEM electrolytic membrane electrode.
Disclosure of Invention
The invention aims to provide a method for effectively recycling a proton exchange membrane, noble metal platinum and iridium from a waste PEM electrolytic water membrane electrode respectively, and recycling the components, and the method has the characteristics of simple process flow, high recycling efficiency, low impurity content and small environmental pollution, is particularly suitable for recycling a large amount of waste membrane electrodes in the industrial field, can effectively reduce the cost of PEM electrolytic hydrogen production, and reduces the environmental pollution caused by waste perfluorinated sulfonic acid polymer and heavy metal.
The invention provides a recycling method of an electrolytic water film electrode of a waste proton exchange membrane, which comprises the following steps:
(1) Soaking the waste membrane electrode into a solvent A, stripping the catalytic layer from the proton exchange membrane by ultrasonic treatment, scraping and flushing, cleaning the proton exchange membrane by using the solvent, performing regeneration treatment on the proton exchange membrane, collecting liquid suspended matters, filtering and centrifugally separating to obtain catalyst filter residues I, and recycling filtrate;
(2) Drying and grinding the first filter residue, adding the first filter residue into the solvent B, heating and reacting for a period of time in an autoclave, dissolving solid polymer electrolyte in the filter residue, and then centrifugally separating and drying to obtain a second filter residue;
(3) If the second filter residue contains carbon, burning the second filter residue to remove carbon substances, and leaching base metal impurities by using a leaching solution A; if the second filter residue contains no carbon, leaching base metal impurities by the leaching solution A directly; filtering and centrifugally separating to obtain filter residue III;
(4) Adding the filter residue III into the leaching solution B for reaction, carrying out solid-liquid separation after the reaction is completed to respectively obtain a chloroplatinic acid solution and iridium oxide/iridium insoluble matters, measuring the platinum content in the chloroplatinic acid solution, adjusting the PH, and using the solution as a platinum precursor solution or carrying out reduction/precipitation to obtain platinum/platinum salt for reuse;
(5) Dissolving iridium oxide/iridium obtained in the step (4) by using a leaching solution C to obtain an iridium chloride solution, measuring the iridium content in the solution, adjusting the PH, and then using the iridium chloride solution as an iridium precursor solution, or precipitating ammonium chloride to obtain an ammonium iridium chloride precipitate, and reducing the ammonium chloride precipitate by calcined hydrogen to obtain metallic iridium for reuse;
wherein the solvent A is lower alkyl alcohol or a mixed solvent of lower alkyl alcohol and water; the solvent B is a mixed solution of water and at least one of methanol, ethanol, glycol, isopropanol, n-propanol, glycerol, butanol, acetone and DMF, DMA, DMSO, NMP; the leaching liquid A is at least one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, perchloric acid and periodic acid; the leaching solution B is hydrochloric acid solution containing at least one oxidant; and the leaching liquid C is 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 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 dosage of the solvent A is that the membrane electrode is immersed; the mass ratio of the solute to the water in the solvent B is 0.05-20: 1, the dosage of the solvent B is 1-200 mL/g 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, peracetic acid or nitric acid, wherein the concentration of the oxidant is 0.5-10 mol/L, the concentration of the 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 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 leaching solution in the step (5) is 5-12 mol/L, and the dosage of the leaching solution C is 2-200 mL/g of filter residue.
As a further scheme of the invention, the proton exchange membrane regeneration treatment in the step (1) is as follows: the proton exchange membrane is cleaned and regenerated for 1 to 5 times by one or more of hydrogen peroxide, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, acetic acid, sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia water with the concentration of 0.5 to 3mol/L, the regeneration temperature is 50 to 150 ℃ and the regeneration time is 0 to 48 hours; then heat-treating with ultra-pure water at 50-120 ℃ for 0.5-24 h, repeating for 1-5 times, drying to obtain regenerated proton exchange membrane, and finally coating one or two of perfluorosulfonic acid membrane solution or PTFE emulsion with concentration of 0.5-30 wt% on both sides of the proton exchange membrane as modifier to modify the membrane, wherein the dosage of the modifier is 0-10% of the total mass of the proton exchange membrane.
As a further aspect of the present invention, the reduction/precipitation of platinum/platinum salt in the step (4) means: reducing and precipitating chloroplatinic acid to metallic platinum with at least one of formaldehyde, formic acid, methanol, ethanol, ethylene glycol, ethylenediamine, sodium borohydride, potassium borohydride, hydrazine hydrate, ascorbic acid, sodium citrate; or ammonium chloride is used to react with the ammonium chloride to generate ammonium chloroplatinate precipitate.
As a further aspect of the present invention, before the leaching solution C in the step (5) dissolves solids, iridium oxide/iridium is subjected to a melting treatment with 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 to 800 ℃ for 0.5 to 8 hours.
The application of the recycling method of the waste proton exchange membrane electrolytic water membrane electrode in recycling the proton exchange membrane fuel cell membrane electrode is also within the protection scope of the invention.
The invention has the following effective effects:
1. the invention firstly uses mild solvent to strip the catalytic layers on the two sides of the membrane electrode from the proton exchange membrane, then respectively dissolves and purifies the noble metals platinum and iridium in the waste catalyst, can respectively realize the recovery and reutilization of the proton exchange membrane, platinum and iridium, has the advantages of simple process flow, high recovery efficiency and low impurity content, is particularly suitable for the recovery of a large number of waste membrane electrodes in the industrial field, is beneficial to relieving the pressure of scarce noble metal resources and the pressure of wastes on the environment, and simultaneously provides a feasible way for the recovery and reutilization after the service life of PEM hydrogen production equipment, and is beneficial to reducing the cost.
2. The process has economy and environmental friendliness, such as solvent heat treatment is carried out on the waste catalyst before firing to remove carbon, and solid polymer electrolyte is removed, so that harmful gas HF can not be generated in the high-temperature firing process, the environmental pollution is avoided, and an expensive HF absorbing device is not required to be matched; in the process of dissolving noble metal, hydrochloric acid solution containing at least one oxidant is used for replacing aqua regia, NO toxic gas can not be generated, the safety is good, and the environmental pollution is small; meanwhile, the used solvents can be recycled, so that waste is avoided, and environmental protection pressure is reduced.
3. The chloroplatinic acid or chloroiridium acid recovered by the present invention can be directly used as a noble metal precursor for the synthesis process, thus eliminating the necessity of recovering noble metals in the form of elemental metals or metal compounds in some cases where noble metal solutions are used.
Drawings
FIG. 1 is a flow chart of a method for recycling and reusing an electrode of an electrolytic water film of a waste proton exchange membrane provided by an embodiment of the 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 with reference to the following examples, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following examples.
Summary of the invention:
the invention provides a recycling method of an electrolytic water film electrode of a waste proton exchange membrane, wherein a flow chart of the method is shown in fig. 1, a schematic diagram is shown in fig. 2, and the method specifically comprises the following steps:
(1) Soaking the waste membrane electrode into a solvent A, stripping the catalytic layer from the proton exchange membrane by ultrasonic treatment, scraping and flushing, cleaning the proton exchange membrane by using the solvent, then regenerating the proton exchange membrane, collecting liquid suspended matters, filtering and centrifugally separating to obtain a first catalyst filter residue, and recycling the filtrate.
(2) And (3) drying and grinding the first filter residue, adding the first filter residue into the solvent B, heating and reacting for a period of time in an autoclave, dissolving out the solid polymer electrolyte in the filter residue, and then centrifugally separating and drying to obtain a second filter residue.
(3) If the second filter residue contains carbon, burning the second filter residue to remove carbon substances, and leaching base metal impurities by using a leaching solution A; if the second filter residue contains no carbon, leaching base metal impurities by the leaching solution A directly; filtering and centrifugally separating to obtain filter residue III;
(4) Adding the filter residue III into the leaching solution B for reaction, carrying out solid-liquid separation after the reaction is completed to respectively obtain a chloroplatinic acid solution and iridium oxide/iridium insoluble matters, measuring the platinum content in the chloroplatinic acid solution, adjusting the PH, and using the solution as a platinum precursor solution or reducing/precipitating platinum/platinum salt for reuse.
(5) Dissolving iridium oxide/iridium obtained in the step (4) by using a leaching solution C to obtain an iridium chloride solution, measuring the iridium content in the solution, adjusting the PH, using the iridium chloride solution as an iridium precursor solution, or precipitating ammonium chloride by using ammonium chloride to obtain an iridium chloride precipitate, and reducing the iridium chloride precipitate by calcined hydrogen to obtain metallic iridium for reuse.
Example 1
Taking a piece with an active area of 200cm 2 The cathode of the membrane electrode uses platinum carbon catalyst, and the initial platinum loading is 1mg/cm 2 The anode uses iridium oxide catalyst, and the initial iridium loading is 3mg/cm 2 The membrane electrode shares 200mg of platinum and 600mg of iridium.
1) Immersing the abandoned membrane electrode into ethanol which is enough to submerge the abandoned membrane electrode, and stripping the catalytic layer from the proton exchange membrane by scraping and flushing after immersing for 10 min.
2) Washing the waste proton exchange membrane obtained in the step 1) by ethanol and ultrapure water, immersing the waste proton exchange membrane in 2mol/L sulfuric acid solution, performing heat treatment at 90 ℃ for 12 hours, drying, preparing a perfluorosulfonic acid resin solution with the concentration of 2wt% and 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/cm 2 The proton exchange membrane modified by the perfluorinated sulfonic acid resin is reused.
3) Collecting the liquid suspension after the proton exchange membrane is stripped in the step 1), centrifugally separating to obtain filter residues I, wherein the filter residues I comprise deactivated platinum carbon and iridium oxide catalysts and solid polymer electrolyte filter residues, drying and grinding the filter residues into fine powder, and then adding 50mL of ethanol and water with the mass ratio of 1:1, placing the mixture into an autoclave, reacting for 3 hours at 250 ℃, removing solid polymer electrolyte in filter residues, centrifugally separating and drying to obtain filter residues II, wherein the filter residues II contain deactivated platinum carbon and iridium oxide catalyst. And (3) placing the filter residue II into a crucible, calcining for 5 hours in air at 450 ℃ to fully oxidize the carbon material into carbon dioxide, and discharging the carbon dioxide to obtain residual substances in the crucible, wherein the main components of the residual substances are platinum and iridium oxide. Immersing the residual substances into 2mol/L hydrochloric acid, reacting for 2 hours at 80 ℃ to remove base metals in the residual substances, and centrifugally separating to obtain filter residues III.
4) And adding the filter residue III into a mixed solution of 25mL of hydrochloric acid with the concentration of 1mol/L and 25mL of sodium chlorate with the concentration of 1mol/L (the mixing ratio is 1:1), reacting for 3 hours at 60 ℃, standing for layering, wherein the upper layer is a chloroplatinic acid solution, the lower layer is iridium oxide solid, separating, reducing the chloroplatinic acid into metal platinum by using hydrazine hydrate, weighing to obtain 183mg of platinum, and calculating the recovery rate of the platinum to be 91.5%. The iridium oxide was dissolved with 50mL of hydrochloric acid having a concentration of 8mol/L to obtain an iridium chloride solution, ammonium chloride was added thereto to obtain an ammonium chloride precipitate, and the precipitate was reduced with calcined hydrogen to obtain metallic iridium, which was weighed to obtain 557mg, and the recovery rate of iridium was calculated to be 92.8%.
Example 2
Taking a piece with an active area of 200cm 2 The cathode of the membrane electrode uses platinum carbon catalyst, and the initial platinum loading is 1mg/cm 2 The anode uses iridium black catalyst, and the initial iridium loading is 3mg/cm 2 The membrane electrode shares 200mg of platinum and 600mg of iridium.
Soaking the waste membrane electrode in ethanol enough to submerge the waste membrane electrode, peeling the catalytic layer and the waste proton exchange membrane by scraping and flushing after soaking for 10min, washing the proton exchange membrane by using ethanol and ultrapure water, immersing the proton exchange membrane in 2mol/L sulfuric acid solution, performing heat treatment at 90 ℃ for 12h, performing heat treatment in the ultrapure water at 90 ℃ for 12h, drying, and preparing the catalyst with the concentration of 2wt%The perfluorosulfonic acid resin solution is sprayed on the two sides of the proton exchange membrane, and the loading capacity of the perfluorosulfonic acid resin is 1mg/cm 2 The proton exchange membrane modified by the perfluorinated sulfonic acid resin is reused.
And collecting the liquid suspension after the proton exchange membrane is stripped, and centrifugally separating to obtain filter residue I, wherein the filter residue I comprises deactivated platinum carbon and iridium black catalyst and solid polymer electrolyte filter residues. Drying and grinding the first filter residue into fine powder, and then adding 50mL of isopropanol and water in a mass ratio of 1:1, placing the mixture into an autoclave, reacting for 3 hours at 250 ℃, removing solid polymer electrolyte in filter residues, centrifugally separating and drying to obtain filter residues II, wherein the filter residues II comprise deactivated platinum carbon and iridium black catalyst. And (3) placing the filter residue II into a crucible, calcining for 5 hours in air at 450 ℃ to fully oxidize the carbon material into carbon dioxide, and discharging the carbon dioxide to obtain a residual substance in the crucible, wherein the main component of the residual substance is a mixture of metal platinum and iridium. Immersing the residual substances into 2mol/L perchloric acid, reacting for 2 hours at 80 ℃ to remove base metals in the residual substances, and centrifugally separating to obtain filter residues 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 iridium solid, carrying out solid-liquid separation, reducing the chloroplatinic acid into metal platinum by sodium borohydride, weighing to obtain 189mg, calculating to obtain 94.5% of platinum recovery rate, and 563mg of iridium in the lower layer, and calculating to obtain 93.8% of iridium recovery rate. Iridium is dissolved in 30mL of hydrochloric acid with the concentration of 6mol/L to obtain chloroiridium acid solution which can be used as iridium precursor solution.
Example 3
Taking a piece with an active area of 200cm 2 The cathode of the membrane electrode uses a platinum black catalyst, and the initial platinum loading is 1mg/cm 2 The anode uses iridium oxide catalyst, and the initial iridium loading is 3mg/cm 2 The membrane electrode shares 200mg of platinum and 600mg of iridium.
Immersing the abandoned membrane electrode into ethanol and water with mass ratio of 3:1, soaking in the mixed solventStripping the catalytic layer from the proton exchange membrane after 10min, cleaning the proton exchange membrane with ethanol and ultrapure water, immersing the proton exchange membrane in 2mol/L hydrochloric acid solution, heat treating at 90 ℃ for 12h, heat treating at 90 ℃ with ultrapure water for 12h, drying, preparing PTFE solution with concentration of 5wt%, spraying the PTFE solution on both sides of the proton exchange membrane, wherein the loading amount of PTFE is 1mg/cm 2 The PTFE modified proton exchange membrane is reused.
Collecting the stripped liquid suspension, and centrifugally separating to obtain a filter residue I, wherein the filter residue I comprises an inactivated platinum and iridium oxide catalyst and a solid polymer electrolyte filter residue, and is dried and ground into fine powder, and then added into 50mL of ethanol and water with the mass ratio of 2:1, placing the mixture into an autoclave, reacting for 5 hours at 230 ℃, removing solid polymer electrolyte in filter residues, centrifugally separating and drying to obtain filter residues II, wherein the filter residues II comprise deactivated platinum and iridium oxide catalysts.
Immersing the second filter residue into 1mol/L nitric acid, reacting for 2 hours at 60 ℃ to remove base metals in the second filter residue, and centrifugally separating to obtain the third filter residue. And adding the filter residue III into a mixed solution of 35mL of hydrochloric acid with the concentration of 1mol/L and 15mL of sodium peroxide with the concentration of 1mol/L, reacting for 3 hours at 90 ℃, standing for layering, wherein the upper layer is a chloroplatinic acid solution, the lower layer is iridium oxide solid, separating, wherein the chloroplatinic acid solution can be used as a platinum precursor solution, and the iridium oxide is dissolved by 50mL of hydrochloric acid with the concentration of 8mol/L to obtain a chloroiridium acid solution which can be used as an iridium precursor solution. The contents of platinum and iridium in chloroplatinic acid and chloroiridium acid were measured by atomic absorption spectrometry, respectively, and the recovery rates of platinum and iridium were calculated to be 95.1% and 93.3%, respectively.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended 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 such modifications and adaptations are intended to be comprehended within the scope of the invention.
While the foregoing description of the embodiments of the present invention has been presented in conjunction with the drawings, it should be understood that it is not intended to limit the scope of the invention, but rather, it is intended to cover all modifications or variations within the scope of the invention as defined by the claims of the present invention.
Claims (10)
1. The method for recycling the waste proton exchange membrane electrolytic water film electrode is characterized by comprising the following steps of:
(1) Soaking the waste membrane electrode into a solvent A, stripping the catalytic layer from the proton exchange membrane by ultrasonic treatment, scraping and flushing, cleaning the proton exchange membrane by using the solvent, performing regeneration treatment on the proton exchange membrane, collecting liquid suspended matters, filtering and centrifugally separating to obtain catalyst filter residues I, and recycling filtrate;
(2) Drying and grinding the first filter residue, adding the first filter residue into the solvent B, heating and reacting for a period of time in an autoclave, dissolving solid polymer electrolyte in the filter residue, and then centrifugally separating and drying to obtain a second filter residue;
(3) If the second filter residue contains carbon, burning the second filter residue to remove carbon substances, and leaching base metal impurities by using a leaching solution A; if the second filter residue contains no carbon, leaching base metal impurities by the leaching solution A directly; filtering and centrifugally separating to obtain filter residue III;
(4) Adding the filter residue III into the leaching solution B for reaction, carrying out solid-liquid separation after the reaction is completed to respectively obtain a chloroplatinic acid solution and iridium oxide/iridium insoluble matters, measuring the platinum content in the chloroplatinic acid solution, adjusting the PH, and using the solution as a platinum precursor solution or carrying out reduction/precipitation to obtain platinum/platinum salt for reuse;
(5) Dissolving iridium oxide/iridium obtained in the step (4) by using a leaching solution C to obtain an iridium chloride solution, measuring the iridium content in the solution, adjusting the PH, and then using the iridium chloride solution as an iridium precursor solution, or precipitating ammonium chloride to obtain an ammonium iridium chloride precipitate, and reducing the ammonium chloride precipitate by calcined hydrogen to obtain metallic iridium for reuse;
wherein the solvent A is lower alkyl alcohol or a mixed solvent of lower alkyl alcohol and water; the solvent B is a mixed solution of water and at least one of methanol, ethanol, glycol, isopropanol, n-propanol, glycerol, butanol, acetone and DMF, DMA, DMSO, NMP; the leaching liquid A is at least one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, perchloric acid and periodic acid; the leaching solution B is hydrochloric acid solution containing at least one oxidant; and the leaching liquid C is hydrochloric acid solution.
2. The recycling method of 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 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 dosage of the solvent A is that the membrane electrode is immersed; the mass ratio of the solute to the water in the solvent B is 0.05-20: 1, the dosage of the solvent B is 1-200 mL/g filter residue.
3. The method for recycling the electrolyte membrane electrode of the waste proton exchange membrane 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 electrolyte membrane electrode of the waste proton exchange membrane according to claim 1, wherein 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.
5. The method for recycling the electrolyte membrane electrode of the waste proton exchange membrane 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, peracetic acid or nitric acid, wherein the concentration of the oxidant is 0.5-10 mol/L, the concentration of the 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 filter residue; the reaction temperature is 20-90 ℃ and the reaction time is 0.1-12 h.
6. The method for recycling the electrolyte membrane electrode of the waste proton exchange membrane according to claim 1, wherein the concentration of the leaching solution in the step (5) is 5-12 mol/L, and the amount of the leaching solution C is 2-200 mL/g of filter residue.
7. The method for recycling the electrolyte membrane electrode of the waste proton exchange membrane according to any one of claims 1 to 6, wherein the regeneration treatment of the proton exchange membrane in the step (1) is as follows: the proton exchange membrane is cleaned and regenerated for 1 to 5 times by one or more of hydrogen peroxide, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, acetic acid, sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia water with the concentration of 0.5 to 3mol/L, the regeneration temperature is 50 to 150 ℃ and the regeneration time is 0 to 48 hours; then heat-treating with ultra-pure water at 50-120 ℃ for 0.5-24 h, repeating for 1-5 times, drying to obtain regenerated proton exchange membrane, and finally coating one or two of perfluorosulfonic acid membrane solution or PTFE emulsion with concentration of 0.5-30 wt% on both sides of the proton exchange membrane as modifier to modify the 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 electrolyte membrane electrode of the waste proton exchange membrane according to claim 7, wherein the reduction/precipitation of platinum/platinum salt in the step (4) means: reducing and precipitating chloroplatinic acid to metallic platinum with at least one of formaldehyde, formic acid, methanol, ethanol, ethylene glycol, ethylenediamine, sodium borohydride, potassium borohydride, hydrazine hydrate, ascorbic acid, sodium citrate; or ammonium chloride is used to react with the ammonium chloride to generate ammonium chloroplatinate precipitate.
9. The method for recycling the waste proton exchange membrane electrolytic water membrane electrode according to claim 8, wherein the iridium oxide/iridium is subjected to a melting treatment with 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 hours before the solid is dissolved in the leachate C in the step (5).
10. Use of the recycling method of the waste proton exchange membrane electrolytic water membrane electrode according to any one of claims 1 to 9 for recycling of proton exchange membrane fuel cell membrane electrode.
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