CN115591540A - Method for recycling and preparing hydrogen production catalyst by utilizing waste solar panel - Google Patents
Method for recycling and preparing hydrogen production catalyst by utilizing waste solar panel Download PDFInfo
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- CN115591540A CN115591540A CN202211303709.XA CN202211303709A CN115591540A CN 115591540 A CN115591540 A CN 115591540A CN 202211303709 A CN202211303709 A CN 202211303709A CN 115591540 A CN115591540 A CN 115591540A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 69
- 239000001257 hydrogen Substances 0.000 title claims abstract description 68
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 68
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000002699 waste material Substances 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000004064 recycling Methods 0.000 title claims description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 239000002184 metal Substances 0.000 claims abstract description 56
- 230000007062 hydrolysis Effects 0.000 claims abstract description 54
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 54
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 25
- 229910052718 tin Inorganic materials 0.000 claims abstract description 25
- 238000011084 recovery Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 40
- 229910045601 alloy Inorganic materials 0.000 claims description 16
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- 229910001128 Sn alloy Inorganic materials 0.000 claims description 9
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- 230000008569 process Effects 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 abstract description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910052738 indium Inorganic materials 0.000 abstract description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
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- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/35—Shredding, crushing or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/38—Stirring or kneading
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of solid waste recovery, and particularly relates to a method for preparing a catalyst for hydrogen production by hydrolysis by recovering a waste solar panel. After the waste solar cell is separated out, the hydrolysis hydrogen production catalyst can be prepared by adjusting the proportion of each metal, combining the steps of high-temperature melting, readjusting crystal atom arrangement and the like, the preparation method is simple and convenient, chemical reagents such as acid, alkali and the like are not required to be added, secondary pollution is avoided, energy consumption and cost are low, and metals such as aluminum, indium, gallium, tin and the like in the waste solar cell can be fully utilized; the prepared hydrolysis hydrogen production catalyst has high catalytic efficiency, high value of recovered products and good economic utilization benefit.
Description
Technical Field
The invention belongs to the technical field of solid waste recovery. And more particularly, to a method for recycling and preparing a catalyst for hydrogen production by hydrolysis by using a waste solar panel.
Background
Solar energy is a clean and green renewable energy source, and the photovoltaic industry is rapidly developed in China in recent years. In 2018, the power generation capacity of the solar cell only accounts for 1% of the total power generation capacity of China, and according to the prediction of the industry, in the future, in 2030, the solar power generation capacity accounts for about 10% of the total power generation capacity of the market, and in 2040, the solar power generation capacity reaches 20% of the total power generation capacity of the market. The solar cell mainly comprises an EVA/PET organic matter component and a cell piece component, wherein the cell piece component mainly comprises a glass piece, a silicon chip, an Ag/Al electrode and a multi-component compound, and the multi-component compound mainly comprises elements such As Se, cd, zn, as, si, ga, in, cu and Sn. Therefore, the solar cell panel contains abundant metal resources and has high resource recycling value. With the use and scrapping of more and more solar cells in the coming years, the treatment of waste solar panels can cause huge pressure on the environment. Therefore, recycling of metals from waste solar cells is a necessary process for both secondary resource utilization and environmental protection.
The existing method for recycling the metal of the waste solar cell mainly combines the technologies of wet leaching and selective precipitation separation, and in addition, the method also has the technology of vacuum evaporation separation recycling. For example, chinese patent application CN111719043A discloses a method for recycling waste solar cells, which comprises the steps of soaking cleaned and dried waste solar cells in a sodium hydroxide solution to obtain an aluminum-removed solar cell and a solution containing sodium metaaluminate, soaking the aluminum-removed solar cell in a nitric acid solution to obtain a silver-removed cell and a silver nitrate solution, then respectively recovering aluminum and silver through two-step precipitation, calcination, hydrolysis and the like, and soaking the silver-removed cell in a phosphoric acid solution to obtain a silicon material with silicon nitride removed. The method can efficiently recover and separate aluminum, silver and silicon materials from the solar panel, but the use of strong acid and strong alkali can generate a large amount of hazardous waste water and sludge, which easily causes environmental pollution, and metals such as indium, gallium, tin and the like in the solar cell are not properly recovered.
In addition, chinese patent application CN108823411A discloses a method for recovering metal and energy gas from waste solar panels, which includes performing vacuum pyrolysis treatment on the waste solar panels to separate and recover organic components therein, then gasifying the metal components by vacuum metallurgy, and recovering each metal simple substance by gradient condensation of temperature by utilizing the difference of boiling points of different metals under vacuum conditions. The method has the characteristic of efficiently separating each metal, but the vacuum gasification-condensation separation method has higher requirements on equipment and operation, the highest temperature of metal gasification needs to reach not less than 1400 ℃, the condition of maintaining high vacuum under the temperature condition needs to consume huge energy cost, the value of the metal product obtained by recycling is low, and the metal product needs to be further processed for subsequent production and utilization.
Therefore, in order to overcome the defects and the blank of the existing technology for recovering metals such as indium, gallium and tin from the waste solar panels, the development of a method for recovering metals such as indium, gallium and tin from the waste solar panels with clean environment and high value is urgently needed.
Disclosure of Invention
The invention aims to solve the technical problems that the existing waste solar panel metal recovery needs to add a large amount of acid, alkali and chemical reagents, the production waste is increased, and secondary pollution is caused; the method for preparing the catalyst for hydrogen production by hydrolysis by recycling the waste solar panels has the defects of incomplete recycling of metals such as indium, gallium, tin and the like, low value of the recycled products and high energy consumption of the recycling method, and does not need hydrometallurgy, and the recycled products have high value and low energy consumption in the recycling process.
The invention aims to provide a catalyst for hydrogen production by hydrolysis, which is prepared by the method.
The invention also aims to provide the catalyst for hydrogen production by hydrolysis and application of the method in the field of recycling waste solar panels or hydrogen production by hydrolysis.
The above purpose of the invention is realized by the following technical scheme:
a method for preparing a catalyst for hydrogen production by hydrolysis by recycling a waste solar panel specifically comprises the following steps:
s1, disassembling a waste solar panel to obtain a waste solar cell and an aluminum outer frame, crushing the aluminum outer frame to obtain aluminum outer frame crushing particles, separating the cell to remove organic components to obtain a metal wire and a cell chip, and crushing the cell chip to obtain cell chip powder;
s2, mixing the chip powder obtained In the step S1 with a metal wire, heating to 660-800 ℃ under a vacuum condition, fully liquefying and separating to obtain a Ga, in and Sn mixed block, and grinding to obtain mixed metal powder;
s3, measuring the proportion of Ga, in and Sn In the mixed metal powder obtained In the step S2, adding a Ga source, an Al source and an Sn source according to the mass ratio of Al to Ga to In to Sn = (10-90) to 7;
and S4, heating the mixed raw material powder obtained In the step S3 to a molten state at an aerobic high temperature of 660-800 ℃, cooling to obtain an Al-Ga-In-Sn alloy block, heating the alloy block to 200-400 ℃ under a vacuum and oxygen-free condition to adjust atomic arrangement, cooling and crushing to obtain the Al-Ga-In-Sn alloy block.
The mixed film type waste solar cell has semiconductor compounds of Ga, in and the like, gaAs, inP and the like, and Sn exists In a simple substance form In a lead and a welding spot; there are two existing forms of Al, alN compounds, and Al alloy rims. It can be seen that the metal elements in the waste solar cells are complex in form and components, and the semiconductor compounds in the waste solar cells are plated and connected in the metal plate in a vacuum deposition manner, so that the separation difficulty is high, and the waste solar cells are difficult to separate by a conventional separation and impurity removal means. The method decomposes, liquefies and separates Ga, in and Sn In the waste solar cell piece from the polynary compound at the high temperature of 660-800 ℃, measures and adjusts the proportion of Al, ga, in and Sn, continuously heats the mixed metal to a state of melting and mixing uniformly, then adjusts the crystal atom arrangement of the material under the vacuum high temperature condition, controls the Ga content In all alpha-Al phases to be 0.8 wt%, and forms a spherical microstructure, thereby preparing the hydrolysis hydrogen production alloy catalyst, and the method has high catalytic efficiency and higher application value. Aiming at the condition control for adjusting the atom arrangement process of the solid solution crystal, the method is based on the property that the phase distribution in a multi-phase metal system changes along with the change of components and temperature, the movement and distribution trends of different metals in the mixed solid solution are observed under the complex conditions of multiple temperatures, aerobic/anaerobic/vacuum, multiple pressures and the like, and the method can be obtained through controlling various conditions.
Preferably, in step S2, the Ga source is GaAs powder, the Al source is crushed particles of the aluminum outer frame obtained in step S1, and the Sn source is Sn particles.
Further, in step S1, the method for removing organic components includes: separating the battery piece plastic packaging film from the battery piece, and heating the battery piece at 350-450 ℃ under the anaerobic condition to remove residual organic components.
Furthermore, in the step S2, the reaction is carried out for 1 to 3 hours by heating to 660 to 800 ℃.
Further, in steps S2 and S4, the vacuum condition is 0 to 10 -3 Pa。
Furthermore, in the step S4, the aerobic reaction is carried out for 1 to 3 hours at the high temperature of 660 to 800 ℃.
Further, in step S4, the molten mixture is stirred every 0.1 to 0.5 hours to remove the upper layer of dross impurities.
Further, in step S4, the oxygen is in an air atmosphere.
Further, in the step S4, the reaction is carried out for 1 to 3 hours at the temperature of between 200 and 400 ℃ under the anaerobic condition.
Further, in step S3, the error ranges of the Al, ga, in, sn ratios and product impurities are 0 to 0.01wt.%.
Further, after the hydrolysis hydrogen production catalyst is deactivated In hydrolysis hydrogen production reaction, the hydrolysis hydrogen production catalyst can be heated to 660-800 ℃ under a vacuum condition, fully liquefied and separated to obtain a mixed block of Ga, in and Sn, ground to obtain mixed metal powder, and the steps S3 and S4 are repeated to obtain the regenerated hydrolysis hydrogen production catalyst.
In addition, the invention also claims a catalyst for hydrolysis hydrogen production prepared by the method.
In addition, the invention also claims the application of the catalyst for hydrolysis hydrogen production and the method in the field of recycling waste solar panels or hydrolysis hydrogen production
The invention has the following beneficial effects:
according to the invention, after the waste solar cell is separated out, the hydrolysis hydrogen production catalyst can be prepared by adjusting the proportion of each metal, and combining the steps of high-temperature melting, crystal atom arrangement and the like, the preparation method is simple and convenient, chemical reagents such as acid and alkali are not required to be added, secondary pollution is avoided, the energy consumption and the cost are lower, and metals such as indium, gallium, tin and the like in the waste solar cell can be fully utilized; the prepared hydrolysis hydrogen production catalyst has high catalytic efficiency, high value of recovered products and good economic utilization benefit.
Detailed Description
The present invention will be further described with reference to the following specific examples, which are not intended to limit the invention in any manner. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1 method for preparing catalyst for hydrogen production by hydrolysis by recycling waste solar panel
The method for recovering and preparing the catalyst for hydrogen production by hydrolysis by using the waste solar panel specifically comprises the following steps:
s1, obtaining 10kg of waste solar cells and 10kg of an aluminum outer frame from a waste solar panel in a disassembling mode; crushing an aluminum outer frame into particles through hammer type crushing, separating a cell plastic packaging film from a cell respectively through the steps of shearing type crushing and screening, and heating the cell at 400 ℃ under an oxygen-free condition to remove residual organic components (mainly comprising adhesive glue and plastic packaging film fragments) to obtain 600g of solar cell chip powder and 500g of metal wires;
s2, mixing the chip powder obtained in the step S1 with a metal wire, placing the mixture on an inclined surface of an inclined crucible, and carrying out vacuum condition under the pressure of 10 -3 Heating to 800 deg.C under Pa, standing for 1h to obtain liquefied and separated Ga, in, sn mixed block at the bottom of the inclined crucible, and grinding to obtain mixed metal powder600g；
S3, taking a small amount of the mixed metal powder obtained In the step S2, measuring the proportion of Ga, in and Sn by adopting ICP-MS, calculating and weighing 297.7g of GaAs to be added, 1845g of the aluminum outer frame crushed particles of the waste solar cell obtained In the step S1 and 2g of Sn foil according to the proportion of Al to Ga to In to Sn = 90;
s4, heating the mixed raw material powder obtained In the step S3 to a molten state at an aerobic high temperature of 800 ℃, keeping the temperature for 3 hours, continuously removing upper-layer scum impurities during the heating, and cooling to obtain about 2000g of Al-Ga-In-Sn alloy blocks; putting the alloy block under vacuum condition and pressure 10 -3 Heating to 400 ℃ under Pa, keeping the temperature for 3 hours, cooling to obtain an alloy product with the atomic arrangement adjusted, and crushing the alloy product to obtain the final product, namely the catalyst powder for hydrogen production by hydrolysis.
And (3) product performance determination:
1. hydrogen production efficiency: putting the obtained hydrolysis hydrogen production catalyst powder into constant-temperature water at 40-60 ℃ for hydrolysis test: when the water temperature is 60 ℃ and the reaction time is 5min, the hydrogen production reaction rate reaches the highest value, and the peak value is 700mL (H) 2 ) Per g (catalyst), the hydrogen production rate is 90%.
2. Deactivation and regeneration of the catalyst:
the catalytic principle of the hydrolysis hydrogen production catalyst is that the Al phase reacts with the water phase to produce hydrogen, and the Al phase is converted into aluminum oxide after the hydrogen production is finished, so that the catalyst is deactivated; putting the deactivated hydrolysis hydrogen production catalyst on an inclined crucible slope, and performing vacuum condition under the pressure of 10 -3 Heating to 800 ℃ under Pa, keeping the temperature for 1h, obtaining liquefied and separated Ga, in and Sn mixed blocks at the bottom of the inclined crucible, and repeating the steps S3 and S4 to obtain the regenerated hydrolysis hydrogen production catalyst.
Embodiment 2 method for preparing catalyst for hydrogen production by hydrolysis by recycling waste solar panel
The method for recycling and preparing the catalyst for hydrogen production by hydrolysis by using the waste solar panel specifically comprises the following steps:
s1, obtaining 10kg of waste solar cells and 10kg of an aluminum outer frame from a waste solar panel in a disassembling mode; crushing an aluminum outer frame into particles through hammer type crushing, separating a cell plastic packaging film from a cell respectively through the steps of shearing type crushing and screening, and heating the cell at 400 ℃ under an oxygen-free condition to remove residual organic components (mainly comprising adhesive glue and plastic packaging film fragments) to obtain 600g of solar cell chip powder and 500g of metal wires;
s2, mixing the chip powder obtained in the step S1 with a metal wire, placing the mixture on an inclined surface of an inclined crucible, and carrying out vacuum condition under the pressure of 10 -3 Heating to 700 ℃ under Pa, staying for 2 hours, obtaining liquefied and separated Ga, in and Sn mixed blocks at the bottom of the inclined crucible, and grinding to obtain 300g of mixed metal powder;
s3, taking a small amount of the mixed metal powder obtained In the step S2, measuring the proportion of Ga, in and Sn by adopting ICP-MS, calculating and weighing 150g of GaAs to be added, 925g of crushed particles of the aluminum outer frame of the waste solar cell obtained In the step S1 and 1g of Sn foil according to the proportion of Al to Ga to In to Sn = 90;
s4, heating the mixed raw material powder obtained In the step S3 to a molten state at an aerobic high temperature of 800 ℃, keeping the temperature for 2 hours, continuously removing upper-layer scum impurities during the heating, and cooling to obtain about 1000g of Al-Ga-In-Sn alloy blocks; subjecting the alloy ingot to vacuum condition pressure 10 -3 And heating to 400 ℃ under Pa, keeping the temperature for 2 hours, cooling to obtain an alloy product with the atomic arrangement adjusted, and crushing the alloy product to obtain the final product, namely the catalyst powder for hydrogen production by hydrolysis.
And (3) product performance determination:
hydrogen production efficiency: putting the obtained hydrolysis hydrogen production catalyst powder into constant-temperature water at 40-60 ℃ for hydrolysis test: when the water temperature is 60 ℃ and the reaction time is 5min, the hydrogen production reaction rate reaches the highest value, and the peak value is 600mL (H) 2 ) Per g (catalyst), the hydrogen production rate is 80%.
Embodiment 3 method for recycling and preparing hydrogen production catalyst by hydrolysis by using waste solar panel
The method for recovering and preparing the catalyst for hydrogen production by hydrolysis by using the waste solar panel specifically comprises the following steps:
s1, obtaining 10kg of waste solar cells and 10kg of an aluminum outer frame from a waste solar panel in a disassembling mode; crushing an aluminum outer frame into particles through hammer type crushing, separating a battery piece plastic packaging film from a battery piece through the steps of shearing type crushing and screening, and heating the battery piece at 400 ℃ under the anaerobic condition to remove residual organic components (mainly comprising adhesive glue and plastic packaging film fragments) to obtain 600g of solar battery chip powder and 500g of metal wires;
s2, mixing the chip powder obtained in the step S1 with a metal wire, placing the mixture on an inclined surface of an inclined crucible, and carrying out vacuum condition under the pressure of 10 -3 Heating to 700 ℃ under Pa, staying for 2h, obtaining liquefied and separated Ga, in and Sn mixed blocks at the bottom of the inclined crucible, and grinding to obtain 600g of mixed metal powder;
s3, taking a small amount of the mixed metal powder obtained In the step S2, measuring the proportion of Ga, in and Sn by adopting ICP-MS, calculating and weighing 297.7g of GaAs to be added, 1845g of the aluminum outer frame crushed particles of the waste solar cell obtained In the step S1 and 2g of Sn foil according to the proportion of Al to Ga to In to Sn = 90;
s4, heating the mixed raw material powder obtained In the step S3 to a molten state at an aerobic high temperature of 700 ℃, keeping the temperature for 3 hours, continuously removing upper-layer scum impurities during the heating, and cooling to obtain about 2000g of Al-Ga-In-Sn alloy blocks; putting the alloy block under vacuum condition and pressure 10 -3 Heating to 450 ℃ under Pa, keeping the temperature for 3h, cooling to obtain an alloy product with the atomic arrangement adjusted, and crushing the alloy product to obtain the final product, namely the catalyst powder for hydrogen production by hydrolysis.
And (3) product performance determination:
hydrogen production efficiency: putting the obtained hydrolysis hydrogen production catalyst powder into constant-temperature water at 40-60 ℃ for hydrolysis test: when the water temperature is 60 ℃ and the reaction time is 5min, the hydrogen production reaction rate reaches the highest value, and the peak value is 660mL (H) 2 ) The hydrogen production rate per gram (catalyst) was 88%.
Comparative example 1 method for preparing catalyst for hydrogen production by hydrolysis by recycling waste solar panel
The method for recycling and preparing the catalyst for hydrogen production by hydrolysis by using the waste solar panel specifically comprises the following steps:
s1, obtaining 10kg of waste solar cells and 10kg of an aluminum outer frame from a waste solar panel in a disassembling mode; crushing an aluminum outer frame into particles through hammer type crushing, separating a battery piece plastic packaging film from a battery piece through the steps of shearing type crushing and screening, and heating the battery piece at 400 ℃ under the anaerobic condition to remove residual organic components (mainly comprising adhesive glue and plastic packaging film fragments) to obtain 600g of solar battery chip powder and 500g of metal wires;
s2, mixing the chip powder obtained in the step S1 with a metal wire, placing the mixture on an inclined surface of an inclined crucible, and carrying out vacuum condition under the pressure of 10 -3 Heating to 800 ℃ under Pa, staying for 1h, obtaining liquefied and separated Ga, in and Sn mixed blocks at the bottom of the inclined crucible, and grinding to obtain 600g of mixed metal powder;
s3, taking a small amount of the mixed metal powder obtained In the step S2, measuring the proportion of Ga, in and Sn by adopting ICP-MS, calculating and weighing 297.7g of GaAs to be added, 1845g of the aluminum outer frame crushed particles of the waste solar cell obtained In the step S1 and 2g of Sn foil according to the proportion of Al to Ga to In to Sn = 90;
and S4, heating the mixed raw material powder obtained In the step S3 to a molten state at an aerobic high temperature of 800 ℃, keeping the temperature for 3 hours, continuously removing upper-layer scum impurities during the time, cooling to obtain about 2000g of Al-Ga-In-Sn alloy block, and crushing the alloy block to obtain the final product of the catalyst powder for hydrogen production by hydrolysis.
The difference of comparative example 1 from example 1 is that in step S4, vacuum heating is not performed at 400 ℃ after heating at 800 ℃ with oxygen, the reaction for adjusting the atomic arrangement is omitted, and the rest of the operation and parameters refer to example 1.
And (3) product performance determination:
hydrogen production efficiency: putting the obtained hydrolysis hydrogen production catalyst powder into constant-temperature water at 40-60 ℃ for hydrolysis test: when the water temperature is 60 ℃ and the reaction time is 5min, the hydrogen production reaction rate reaches the highest value and the peak value50mL (H) 2 ) Per g (catalyst), the hydrogen production rate is 7%.
Comparative example 2 recovery method of waste solar panel
The method for recycling the waste solar panel specifically comprises the following steps:
s1, obtaining 10kg of waste solar cells and 10kg of an aluminum outer frame from a waste solar panel in a disassembling mode; crushing an aluminum outer frame into particles through hammer type crushing, separating a cell plastic packaging film from a cell respectively through the steps of shearing type crushing and screening, and heating the cell at 400 ℃ under an oxygen-free condition to remove residual organic components (mainly comprising adhesive glue and plastic packaging film fragments) to obtain 600g of solar cell chip powder and 500g of metal wires; mixing and grinding the chip powder and the metal wire to obtain 1100g of mixed powder;
and S2, taking a small amount of the mixed powder obtained In the step S1, measuring the proportions of Ga, in and Sn by ICP-MS, calculating and weighing 297.7g of GaAs to be added, 1845g of the aluminum outer frame crushed particles of the waste solar cell obtained In the step S1 and 2g of Sn foil according to the proportion of Al to Ga to In to Sn = 90.
Comparative example 2 is different from example 1 in that the metal raw materials are directly mixed without performing the reaction of removing impurities by heating and adjusting the atomic arrangement by heating, and the rest of the operation and parameters are referred to example 1.
And (3) product performance determination:
hydrogen production efficiency: putting the mixed catalytic powder into constant-temperature water at 40-60 ℃ for hydrolysis test: because impurity removal and heating reaction are not carried out, the obtained mixed catalytic powder contains a large amount of impurities such as iron, copper and the like, and a catalyst is not formed, so that the hydrogen production effect is not obvious.
Comparative example 3 method for preparing catalyst for hydrogen production by hydrolysis by recycling waste solar panel
The method for recycling and preparing the catalyst for hydrogen production by hydrolysis by using the waste solar panel specifically comprises the following steps:
s1, obtaining 10kg of waste solar cells and 10kg of an aluminum outer frame from a waste solar panel in a disassembling mode; crushing an aluminum outer frame into particles through hammer type crushing, separating a cell plastic packaging film from a cell respectively through the steps of shearing type crushing and screening, and heating the cell at 400 ℃ under an oxygen-free condition to remove residual organic components (mainly comprising adhesive glue and plastic packaging film fragments) to obtain 600g of solar cell chip powder and 500g of metal wires;
s2, mixing the chip powder obtained in the step S1 with a metal wire, placing the mixture on an inclined surface of an inclined crucible, and carrying out vacuum condition under the pressure of 10 -3 Heating to 800 ℃ under Pa, staying for 1h, obtaining liquefied and separated Ga, in and Sn mixed blocks at the bottom of the inclined crucible, and grinding to obtain 600g of mixed metal powder;
s3, taking a small amount of the mixed metal powder obtained In the step S2, measuring the proportion of Ga, in and Sn by adopting ICP-MS, calculating and weighing GaAs to be added, crushed particles of the aluminum outer frame of the waste solar cell obtained In the step S1 and Sn foil according to the proportion of Al to Ga to In to Sn = 1;
s4, heating the mixed raw material powder obtained In the step S3 to a molten state at an aerobic high temperature of 800 ℃, keeping the temperature for 3 hours, continuously removing upper-layer scum impurities during the heating, and cooling to obtain about 2000g of Al-Ga-In-Sn alloy blocks; putting the alloy block under vacuum condition and pressure 10 -3 And heating to 400 ℃ under Pa, keeping the temperature for 3 hours, cooling to obtain an alloy product with the atomic arrangement adjusted, and crushing the alloy product to obtain the final product, namely the catalyst powder for hydrogen production by hydrolysis.
Comparative example 3 differs from example 1 In that the ratio of Al to Ga to In to Sn is defined as 1.
And (3) product performance determination:
hydrogen production efficiency: putting the obtained hydrolysis hydrogen production catalyst powder into constant-temperature water at 40-60 ℃ for hydrolysis test: when the water temperature is 60 ℃ and the reaction time is 5min, the hydrogen production reaction rate reaches the maximum value, and the peak value is 500mL (H) 2 ) The total hydrogen production rate per g (catalyst) was 90%, but the total hydrogen production rate was only about 1/3 of that of example 1 because of the low total Al phase content.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for recycling and preparing a catalyst for hydrogen production by hydrolysis by using a waste solar panel is characterized by comprising the following steps:
s1, disassembling a waste solar panel to obtain a waste solar cell and an aluminum outer frame, crushing the aluminum outer frame to obtain aluminum outer frame crushing particles, separating the cell to remove organic components to obtain a metal wire and a cell chip, and crushing the cell chip to obtain cell chip powder;
s2, mixing the chip powder obtained In the step S1 with a metal wire, heating to 660-800 ℃ under a vacuum condition, fully liquefying and separating to obtain a mixed block of Ga, in and Sn, and grinding to obtain mixed metal powder;
s3, measuring the proportion of Ga, in and Sn In the mixed metal powder obtained In the step S2, adding a Ga source, an Al source and an Sn source according to the mass ratio of Al to Ga to In to Sn = (10-90) to 7;
and S4, heating the mixed raw material powder obtained In the step S3 to a molten state at an aerobic high temperature of 660-800 ℃, cooling to obtain an Al-Ga-In-Sn alloy block, heating the alloy block to 200-400 ℃ under a vacuum and oxygen-free condition to adjust atomic arrangement, cooling and crushing to obtain the Al-Ga-In-Sn alloy block.
2. The method according to claim 1, wherein in step S1, the method for removing the organic component is: separating the battery piece plastic packaging film from the battery piece, and heating the battery piece at 350-450 ℃ under the anaerobic condition to remove residual organic components.
3. The method of claim 1, wherein in step S2, the reaction is carried out by heating to 660-800 ℃ for 1-3 h.
4. The method according to claim 1, wherein the vacuum condition in steps S2 and S4 is 0-10 -3 Pa。
5. The method of claim 1, wherein in step S4, the aerobic reaction is carried out at 660-800 ℃ for 1-3 h.
6. The method of claim 5, wherein in step S4, the molten state is stirred every 0.1-0.5 h to remove impurities of upper layer scum.
7. The method of claim 1, wherein the aerobic condition in step S4 is an air atmosphere.
8. The method of claim 1, wherein in step S4, the reaction is carried out at 200-400 ℃ for 1-3 h under anaerobic condition.
9. A catalyst for hydrogen production by hydrolysis, obtainable by a process according to any one of claims 1 to 8.
10. Use of the catalyst for hydrogen production from hydrolysis according to claim 9 and the method according to any one of claims 1 to 8 for the recovery of waste solar panels or for hydrogen production from hydrolysis.
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