CN110172580B - Method for recovering catalyst palladium in proton exchange membrane fuel cell - Google Patents
Method for recovering catalyst palladium in proton exchange membrane fuel cell Download PDFInfo
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- CN110172580B CN110172580B CN201910258401.XA CN201910258401A CN110172580B CN 110172580 B CN110172580 B CN 110172580B CN 201910258401 A CN201910258401 A CN 201910258401A CN 110172580 B CN110172580 B CN 110172580B
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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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B7/007—Wet processes by acid leaching
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Abstract
The invention discloses a method for recovering catalyst palladium in a proton exchange membrane fuel cell, which comprises the following steps: disassembling the proton exchange membrane fuel cell subjected to the brine discharge treatment to obtain a membrane electrode, and immersing the membrane electrode in an organic solvent; separating solid on the upper layer of the suspension by ultrasonic oscillation, filtering the separated suspension by a screen, filtering the filtered suspension by filter paper to obtain filter residue, soaking the filter residue in an acid solution to obtain the suspension, and filtering to obtain the filter residue; washing the obtained filter residue with deionized water, drying, soaking in nitric acid solution to obtain suspension, and filtering; dropwise adding an alkali solution into the obtained filtrate to completely precipitate palladium, and dropwise adding a hydrogen peroxide solution to reduce palladium hydroxide into palladium; and centrifuging the obtained solid-liquid mixture, and filtering to obtain the metal palladium. The method for recovering the catalyst palladium in the proton exchange membrane fuel cell provided by the invention has the advantages of simple process, less pollution and higher recovery rate.
Description
Technical Field
The invention relates to the technical field of battery recovery, in particular to a method for recovering catalyst palladium in a proton exchange membrane fuel cell.
Background
In recent years, the consumption of various energy sources has become larger and larger, and humans are seeking renewable energy sources capable of stable output, and therefore, electricity remains the cleanest, green and efficient energy source at present. Among them, the fuel cell attracts attention at its excellent energy conversion rate. Besides extremely high energy conversion efficiency, the device also has the advantages of diversified similar fuels, clean exhaust, low noise and low environmental pollution. With the optimization of the performance of fuel cells and the popularization of the application range, more and more fuel cells are going into the daily life of people and play an irreplaceable role. We have reason to believe that the commercial impact of fuel cell technology as it evolves into qualitative changes is immeasurable.
If the waste fuel cell is directly discarded without any treatment, on one hand, the waste of resources is caused, and on the other hand, the environmental pollution is also caused. Meanwhile, some fuel cells employ noble metals such as Pt, Pd, etc. in pursuit of good adsorption and catalytic performance. The precious metal resources in China are relatively poor, and the yield of the domestic recycled precious metal is expected to be much higher than that of the mineral precious metal. Therefore, the research on the recovery of the noble metal in the waste fuel cell electrode has very important significance.
At present, in the field of fuel cell recovery, people have matured recovery technical methods for waste proton exchange membrane fuel cells, and particularly, the recovery process for noble metal platinum used as a catalyst is more and more perfect, but research on the recovery of noble metal palladium used as a catalyst in a proton exchange membrane fuel cell is less. Therefore, the invention provides a method for recovering catalyst palladium in a waste proton exchange membrane fuel cell, thereby reducing heavy metal pollution, reducing resource waste, improving the utilization rate of noble metal and being beneficial to sustainable development of related industries in China.
Disclosure of Invention
The invention mainly aims to provide a method for recovering catalyst palladium in a proton exchange membrane fuel cell, which has the advantages of simple process, less pollution and higher recovery rate.
In order to achieve the above object, the present invention provides a method for recovering catalyst palladium in a proton exchange membrane fuel cell, comprising the steps of:
(1) disassembling the proton exchange membrane fuel cell subjected to the brine discharge treatment to obtain a membrane electrode, a bipolar plate and a metal shell, and immersing the membrane electrode in an organic solvent;
(2) separating solid on the upper layer of the suspension by ultrasonic oscillation, filtering the separated suspension by a screen, filtering the filtered suspension by filter paper to obtain a membrane and filter residue, then pouring the filter residue into an acid solution for soaking to obtain the suspension, and filtering to obtain the filter residue;
(3) washing the obtained filter residue with deionized water, drying, soaking in nitric acid solution to obtain suspension, and filtering;
(4) dropwise adding an alkali solution into the obtained filtrate, adjusting the pH value of the solution to 9-10 to completely precipitate palladium, and dropwise adding a hydrogen peroxide solution into the solution to reduce palladium hydroxide into palladium;
(5) and centrifuging the obtained solid-liquid mixture and filtering to obtain the metal palladium.
Preferably, in step (1), the organic solvent is one or more of absolute ethanol, isopropanol and ethylene glycol.
Preferably, in the step (2), the temperature range in the acid leaching process is 25-50 ℃, the ultrasonic oscillation time is 30-60 min, and the number of the screens is 20-50 meshes.
Preferably, in the steps (2) and (3), the acid leaching time is 30-150 min.
Preferably, in the step (2), the concentration range of the acid solution for soaking the powder is 5-10 mol/L; the excess of the acid solution for soaking the powder is 0-300 wt%.
Preferably, in the step (2), the acid used for soaking the powder is at least one of sulfuric acid, nitric acid or hydrochloric acid in mass fraction.
Preferably, in the step (3), in the drying process, the filter residue is dried in an electric heating constant temperature blast drying oven, the drying temperature range is 55-65 ℃, and the drying time is 3.5-4.5 h.
Preferably, in the step (3), when the dried filter residue is soaked in the nitric acid solution, the mass ratio of the filter residue to the nitric acid solution is 1: 6-1: 14.
preferably, in the step (3), the mass fraction of the nitric acid solution is in the range of 60-80%.
Preferably, in the step (4), the alkali solution is at least one of sodium hydroxide and ammonia water, and the concentration range of the alkali solution is 0.05-0.2 mol/L.
The method for recovering the catalyst palladium in the proton exchange membrane fuel cell can be used for recycling the components of the proton exchange membrane fuel cell. The battery material is separated and extracted by a chemical method based on an acid leaching method, the reaction in the experimental process is mainly carried out in solution, and the condition is mild; compared with a pyrogenic process and an electrolytic deposition method, the reaction has small energy supply requirement and low energy consumption. Meanwhile, the method also has the advantages of simple process and less pollution in the treatment process.
Drawings
FIG. 1 is a schematic flow chart of a first embodiment of a method for recovering palladium catalyst in a PEM fuel cell according to the present invention;
FIG. 2 is a schematic flow chart of a second embodiment of the method for recovering palladium catalyst in a PEM fuel cell according to the present invention;
FIG. 3 is a schematic flow chart of a third embodiment of the method for recovering palladium catalyst in a PEM fuel cell according to the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Referring to fig. 1, a method for recovering catalyst palladium in a proton exchange membrane fuel cell includes the following steps:
disassembling the waste proton exchange membrane fuel cell subjected to the discharge treatment by using the saline water at 30 ℃ to obtain a membrane electrode, a bipolar plate and a metal shell, directly recovering the bipolar plate and the metal shell, immersing the membrane electrode in absolute ethyl alcohol, and performing ultrasonic oscillation for 30 min; separating out solid on the upper layer of the suspension, filtering the separated suspension through a 30-mesh screen, filtering the filtered suspension through filter paper to obtain a membrane and filter residue, then pouring the filter residue into a 6mol/L nitric acid solution with the acid excess of 200wt%, fully soaking for 60min to obtain the suspension, and filtering to obtain the filter residue; washing the obtained filter residue with deionized water for 2-3 times, drying the filter residue in an electric heating constant-temperature air blast drying oven at 60 ℃ for 4 hours, fully soaking the filter residue in a nitric acid solution for 60 minutes (wherein the mass ratio of the filter residue to the nitric acid solution is 1: 10, and the mass fraction of the nitric acid solution is 70%), obtaining a suspension, and filtering to obtain a filtrate; adding 0.1% NaOH solution dropwise into the filtrate, adjusting pH to 10 to prevent palladium hydroxide precipitation, and filtering to obtain filtrateDropwise adding a hydrogen peroxide solution with the mass fraction of 30% and the hydrogen peroxide excess of 200wt% into the solution, and reducing palladium hydroxide into palladium by using the hydrogen peroxide; and putting the obtained solid-liquid mixture into centrifugal equipment, centrifuging and filtering to obtain the metal palladium. The test shows that the metal palladium is silver white powder, the crystal structure is a close-packed profile surface-centered cubic crystal structure, and the density is 12g/cm3。
Example 2
Referring to fig. 2, a method for recovering palladium catalyst in a proton exchange membrane fuel cell has steps similar to those of the method for recovering palladium catalyst in a spent proton exchange membrane fuel cell in example 1, except that:
1. example 2 was carried out at 25 ℃ during the acid leaching;
2. the organic solvent used for immersing the membrane electrode is isopropanol;
3. the number of the screens used for filtration was 50 mesh;
4. the time for ultrasonic oscillation is 40 min;
5. acid solution for soaking the powder, wherein the used acid is hydrochloric acid with the mass fraction of 36%, the acid is excessive by 300wt%, and the time for acid leaching filter residue is 100 min;
6. when the filter residue is dissolved in the concentrated nitric acid solution, the mass ratio of the filter residue to the concentrated nitric acid solution is 1: 12, the mass fraction of the nitric acid solution for acid leaching the filter residue is 65%, and the time for acid leaching the filter residue is 100 min;
7. the base used for the complete precipitation of palladium is aqueous ammonia.
Example 3
Referring to fig. 3, a method for recovering palladium catalyst in a proton exchange membrane fuel cell has steps similar to those of the method for recovering noble metal palladium in the waste solid oxide fuel cell in example 1, except that:
1. example 3 was carried out at 40 ℃ during the pickling;
2. the organic solvent for immersing the membrane electrode is a mixture of absolute ethyl alcohol and ethylene glycol;
3. the number of screens used for filtration was 60 mesh;
4. the time for ultrasonic oscillation is 50 min;
5. acid solution used for soaking the powder, wherein the acid is concentrated sulfuric acid with the mass fraction of 70%, and the acid is excessive by 100 wt%;
6. when the filter residue is dissolved in the concentrated nitric acid solution, the mass ratio of the filter residue to the concentrated nitric acid solution is 1: 8;
7. the mass fraction of the nitric acid solution used for acid leaching the filter residue is 75 percent;
8. the time of the hydrochloric acid leaching filter residue and the concentrated nitric acid leaching filter residue with the mass fraction of 36% is 150 min.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings, or any other related technical fields, are intended to be covered by the scope of the present invention.
Claims (7)
1. A method for recovering catalyst palladium in a proton exchange membrane fuel cell is characterized by comprising the following steps:
(1) disassembling the proton exchange membrane fuel cell subjected to the brine discharge treatment to obtain a membrane electrode, a bipolar plate and a metal shell, and immersing the membrane electrode in an organic solvent;
(2) separating solid on the upper layer of the suspension by ultrasonic oscillation, filtering the separated suspension by a screen, filtering the filtered suspension by filter paper to obtain a membrane and filter residue, then pouring the filter residue into an acid solution for soaking to obtain the suspension, and filtering to obtain the filter residue;
(3) washing the obtained filter residue with deionized water, drying, soaking in nitric acid solution to obtain suspension, and filtering;
(4) dropwise adding an alkali solution into the obtained filtrate, adjusting the pH value of the solution to 9-10 to completely precipitate palladium, and dropwise adding a hydrogen peroxide solution into the solution to reduce palladium hydroxide into palladium;
(5) centrifuging the obtained solid-liquid mixture and filtering to obtain metal palladium;
in the steps (2) and (3), the acid leaching time is 30-150 min; in the step (2), the concentration range of the acid solution for soaking the powder is 5-10 mol/L; the acid solution for soaking the powder is excessive by 0-300 wt%; in the step (2), the acid used for soaking the powder is at least one of sulfuric acid, nitric acid or hydrochloric acid in percentage by mass.
2. The method for recovering palladium catalyst in a proton exchange membrane fuel cell according to claim 1, wherein in the step (1), the organic solvent is one or more of absolute ethyl alcohol, isopropyl alcohol and ethylene glycol.
3. The method for recovering palladium catalyst in a proton exchange membrane fuel cell according to claim 1, wherein in the step (2), the temperature in the acid leaching process is in the range of 25 ℃ to 50 ℃, the ultrasonic oscillation time is 30min to 60min, and the number of the screens is in the range of 20 meshes to 50 meshes.
4. The method for recovering the catalyst palladium in the proton exchange membrane fuel cell according to claim 1, wherein in the step (3), in the drying process, the filter residue is placed into an electric heating constant temperature air blast drying oven for drying, the drying temperature range is 55-65 ℃, and the drying time is 3.5-4.5 h.
5. The method for recovering the catalyst palladium in the proton exchange membrane fuel cell according to claim 1, wherein in the step (3), when the dried filter residue is soaked in the nitric acid solution, the mass ratio of the filter residue to the nitric acid solution is 1: 6-1: 14.
6. the method for recovering palladium catalyst in a proton exchange membrane fuel cell according to claim 1, wherein in the step (3), the mass fraction of the nitric acid solution is in the range of 60% to 80%.
7. The method for recovering palladium catalyst in a proton exchange membrane fuel cell according to claim 1, wherein in the step (4), the alkali solution is at least one of sodium hydroxide and ammonia water, and the concentration of the alkali solution is in a range of 0.05 to 0.2 mol/L.
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| JP4417907B2 (en) * | 2003-05-30 | 2010-02-17 | カウンシル・オブ・サイエンティフィック・アンド・インダストリアル・リサーチ | Method for recovering palladium from spent catalyst |
| CN101376923B (en) * | 2007-08-27 | 2010-12-01 | 中国石油化工股份有限公司 | Method for recycling noble metal from spent catalyst |
| CN101459245A (en) * | 2009-01-06 | 2009-06-17 | 武汉理工大学 | Recovery method for fuel cell membrane electrode key material |
| CN102382988A (en) * | 2011-11-10 | 2012-03-21 | 常州市武进佳华化工有限公司 | Method for recovering metallic palladium from waste silicon oxide catalyst |
| CN106898790A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of membrane electrode of fuel batter with proton exchange film recovery method |
| CN106086449B (en) * | 2016-06-20 | 2018-11-09 | 昆山鸿福泰环保科技有限公司 | Palladium recovery technique in a kind of alkalinity palladium liquid |
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| CN107435101A (en) * | 2017-08-25 | 2017-12-05 | 昆明理工大学 | A kind of method for reclaiming palladium in useless palladium carbon catalyst |
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