CN114833176B - Method for comprehensively recovering all components of waste crystalline silicon photovoltaic module - Google Patents
Method for comprehensively recovering all components of waste crystalline silicon photovoltaic module Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 39
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 38
- 238000000197 pyrolysis Methods 0.000 claims abstract description 144
- 238000002386 leaching Methods 0.000 claims abstract description 56
- 238000011084 recovery Methods 0.000 claims abstract description 39
- 239000011521 glass Substances 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 239000002893 slag Substances 0.000 claims abstract description 31
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 26
- 238000007158 vacuum pyrolysis Methods 0.000 claims abstract description 24
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 22
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 238000005476 soldering Methods 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000005520 cutting process Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229910052718 tin Inorganic materials 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims 1
- 239000000779 smoke Substances 0.000 abstract description 3
- 239000012634 fragment Substances 0.000 abstract 1
- QPILZZVXGUNELN-UHFFFAOYSA-N sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-N 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 13
- 238000010248 power generation Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
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- 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
-
- 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
-
- 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
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
-
- 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
- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/15—Electronic waste
- B09B2101/16—Batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a method for comprehensively recovering all components of a waste crystalline silicon photovoltaic module. The method comprises the following steps: (1) Pre-disassembling the collected waste crystalline silicon photovoltaic panel to obtain an incomplete panel and a complete panel; (2) Cutting the incomplete plate into blocks, and performing rotary vacuum pyrolysis to obtain first hydrogen-containing pyrolysis gas and pyrolysis slag, wherein the pyrolysis slag is separated to obtain glass slag, a first soldering tin conduction band, photovoltaic cell panel fragments and first pyrolysis slag; (3) The complete board is subjected to movable type microwave enhanced pyrolysis to obtain second hydrogen-containing pyrolysis gas and a pyrolysis board, the pyrolysis board is subjected to component separation to obtain a complete photovoltaic cell silicon wafer, a complete glass board, a second soldering tin conduction band and second pyrolysis ash, and nitric acid leaching is carried out after the second pyrolysis ash is mixed with the first pyrolysis ash to obtain leaching residues and acid leaching liquid containing noble metals. The invention realizes the high-value recovery of all components of the waste crystalline silicon photovoltaic module and has the characteristics of high comprehensive utilization rate of resources, short process flow, no smoke pollution and the like.
Description
Technical Field
The invention relates to the technical field of comprehensive recovery of all components of a waste crystalline silicon photovoltaic module, in particular to a method for comprehensively recovering all components of a waste crystalline silicon photovoltaic module.
Background
With the increasing exhaustion of fossil energy and the increasing emergence of environmental problems, the need for clean energy to overcome the use of fossil fuels and slow down the climate change caused by human activities has become a hotspot of global concern. Crystalline silicon photovoltaic power generation technology is considered a promising technology for converting sunlight into electrical energy without any other energy source. In recent years, photovoltaic power generation has rapidly progressed, and the annual growth demand of global photovoltaic power exceeds 20%. Under the targets of carbon peak and carbon neutralization in China, photovoltaic power generation is rapidly developed, and it is clear that new energy sources such as wind, light and the like gradually rise from auxiliary energy positions to main energy positions. In 2020, the photovoltaic power generation ratio in China is about 3.5%, and the photovoltaic power generation ratio in the future is increased to more than 20%.
As the amount of photovoltaic packaging increases, the number of spent crystalline silicon photovoltaic cell modules will also proliferate. The technical life of the photovoltaic module is estimated according to 20-30 years, the photovoltaic module in China can reach the scrapped climax in 2035 years, and the scrapped photovoltaic panel production amount in 2050 years can reach 2000 ten thousand tons. The waste crystalline silicon photovoltaic module comprises the following components in percentage by mass: about 68% of glass, about 16% of aluminum, about 6% of adhesive sealant (EVA), about 5% of silicon wafer, about 3% of TPT backboard, about 2% of other valuable metals such as silver, tin, copper, lead, indium and the like, not only has higher recovery value, but also causes great threat to environment and even human safety if the heavy metals and organic matters are improperly disposed. Therefore, research on recycling of the waste crystalline silicon photovoltaic modules is needed.
To date, most research efforts have focused on methods such as physical sorting, chemical solvent methods, and heat treatment. Publication number CN 110783428A discloses a physical method for separating and recovering waste photovoltaic panels from fluid, which can obtain a complete glass panel, but the silicon wafer is completely damaged, and which is not suitable for disposing of waste photovoltaic panels broken by the glass panel; publication number CN 110328216A discloses a two-stage heat treatment recovery waste photovoltaic panel, but the first preset temperature is low, toxic gas is easily generated, the operating environment is deteriorated, serious challenges are generated for the operation of workers, and no mention is made of a waste photovoltaic panel disposal method for breaking glass panels.
In view of the above characteristics of the recovery method, the existing disposal method focuses on destroying the adhesive (EVA) between the glass plate and the silicon wafer, and cannot guarantee to obtain the complete silicon wafer and the glass plate, and more importantly, the existing technical method is mostly suitable for disposing the waste crystalline silicon photovoltaic module with the complete glass plate, which is obviously incomplete, so that a new method is necessary to be developed to solve the problem of comprehensive recovery of the whole components of the waste crystalline silicon photovoltaic module.
Disclosure of Invention
The invention solves the problems in the prior art, and aims to provide a method for comprehensively recovering all components of a waste crystalline silicon photovoltaic module.
In order to achieve the above purpose, the invention adopts the following technical scheme: a method for comprehensively recovering all components of a waste crystalline silicon photovoltaic module comprises the following steps:
(1) Pre-sorting: pre-dismantling the collected waste crystalline silicon photovoltaic plates, comprehensively utilizing the collected waste crystalline silicon photovoltaic plates after dismantling to obtain an aluminum frame and a junction box, obtaining incomplete plates and complete plates according to whether the glass backboard is complete or not after pre-dismantling, recycling the incomplete plates in a rotary low-temperature vacuum pyrolysis recycling system, and recycling the complete plates in a mobile microwave reinforced pyrolysis recycling system;
(2) And (5) recycling incomplete plates: the incomplete plate rotary low-temperature vacuum pyrolysis recovery system comprises cutting blocks, rotary low-temperature vacuum pyrolysis and eddy current separation; cutting the incomplete plate obtained in the step (1) into blocks by a block cutting device, performing rotary low-temperature vacuum pyrolysis to obtain first hydrogen-containing pyrolysis gas and pyrolysis slag, utilizing energy of the first hydrogen-containing pyrolysis gas, separating the pyrolysis slag by eddy current to obtain glass slag, a first soldering tin conduction band, photovoltaic cell panel residues and first pyrolysis slag, respectively comprehensively utilizing the glass slag, the first soldering tin conduction band and the photovoltaic cell panel residues, and recycling the first pyrolysis slag in a complete plate recycling system in the step (3);
(3) And (3) recycling the complete plate: the complete board movable type microwave enhanced pyrolysis recovery system comprises movable type microwave enhanced pyrolysis, component separation and nitric acid leaching; performing mobile microwave enhanced pyrolysis on the complete plate obtained in the step (1) to obtain second hydrogen-containing pyrolysis gas and a pyrolysis plate, performing energy utilization on the second hydrogen-containing pyrolysis gas, performing component separation on the pyrolysis plate to obtain a complete photovoltaic cell silicon wafer, a complete glass plate, a second soldering tin conduction band and second pyrolysis ash, respectively performing recycling on the complete photovoltaic cell silicon wafer and the complete glass plate, jointly and comprehensively utilizing the second soldering tin conduction band and the first soldering tin conduction band obtained by recycling the incomplete plate in the step (2), mixing the second pyrolysis ash and the first pyrolysis ash obtained by recycling the incomplete plate in the step (2), performing nitric acid leaching to obtain leaching slag and acid leaching liquid containing noble metals, performing concentrated treatment on the leaching slag, and recycling the acid leaching liquid containing noble metals by a noble metal recycling system.
Preferably, in the rotary low-temperature vacuum pyrolysis process in the step (2), the pyrolysis reaction is performed in a closed rotary furnace, the diameter of the furnace body is 0.5-1.2 m, the effective heated length of the furnace body is 1.5-3.5 m, the rotation speed of the furnace body is 1-5 rpm, the pyrolysis temperature is 300-450 ℃, and the pyrolysis time is 20-45 min.
Further preferably, the diameter of the furnace body in the step (2) is 0.6-1.0 m, the effective heated length of the furnace body is 1.8-3.0 m, the rotating speed of the furnace body is 2-4 rpm, the pyrolysis temperature is 320-420 ℃, and the pyrolysis time is 25-40 min.
Preferably, in the mobile type microwave enhanced pyrolysis process in the step (3), the pyrolysis reaction is performed in a closed mobile type reaction furnace, the glass backboard is placed downwards, the TPT surface and the photovoltaic silicon wafer are placed upwards, and microwave heating is adopted, wherein the microwave power is 800-1200W, the pyrolysis temperature is 650-950 ℃, and the microwave pyrolysis time is 5-30 min.
Further preferably, the microwave power in the step (3) is 900-1100W, the pyrolysis temperature is 700-850 ℃, and the microwave pyrolysis time is 10-25 min.
Preferably, in the nitric acid leaching process in the step (3), the mass percentage of nitric acid is 20% -70%, the leaching reaction temperature is 35-85 ℃, and the leaching reaction time is 0.5-2.5 h.
Further preferably, in the nitric acid leaching process in the step (3), the mass percentage of nitric acid is 30% -60%, the leaching reaction temperature is 45-75 ℃, and the leaching reaction time is 1.0-2.0 h.
Preferably, the first hydrogen-containing pyrolysis gas and the second hydrogen-containing pyrolysis gas serve as heat sources for the vacuum pyrolysis and precious metal recovery system. In the incomplete board recovery system and the complete board recovery system, the generated hydrogen-containing hot gas has similar components and can be used as a heat source in the pyrolysis process and the noble metal recovery process.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the method for independently recycling the broken glass incomplete plate and the complete plate waste crystalline silicon photovoltaic module, the incomplete plate is cut into blocks and then subjected to low-temperature vacuum pyrolysis by the rotary furnace, and compared with a traditional pyrolysis mode, the rotary vacuum pyrolysis is more sufficient, the heating while rolling can be realized, the pyrolysis speed is increased, and the pyrolysis time is shortened; compared with the traditional pyrolysis mode, the method not only can realize rapid and complete decomposition of organic components, but also can obtain a harmless photovoltaic silicon wafer and a glass backboard, realize high-value recovery of all components of the waste crystalline silicon photovoltaic module, and has the characteristics of high comprehensive utilization rate of resources, short process flow, high utilization rate of heat value, no smoke pollution and the like.
2. The pre-disassembly system provided by the invention can realize the classified independent recovery of the photovoltaic plate with broken glass plates and the photovoltaic plate with complete glass plates, adopts a microwave pyrolysis technology in the complete plate recovery system, and can directly penetrate through the glass plate and the silicon wafer of the photovoltaic plate to selectively and uniformly heat EVA and TPT from inside to outside, different from the traditional heating mode, has the excellent characteristics of high heating rate and high heat utilization rate, and can obtain the glass plate and the silicon wafer without damage; the hydrogen-containing hot gas generated by the whole system can be used as a heat source for the pyrolysis process and the valuable metal recovery process.
3. The invention is particularly suitable for disposing the waste crystalline silicon photovoltaic module with damaged glass plate or complete glass plate, and has the characteristics of high comprehensive utilization rate of resources, short process flow, high utilization rate of heat value, no smoke pollution and the like.
Drawings
FIG. 1 is a process flow diagram of a method for comprehensively recovering all components of a waste crystalline silicon photovoltaic module.
Detailed Description
The following examples are further illustrative of the invention and are not intended to be limiting thereof. The apparatus used in the present invention is a conventional commercially available product in the art unless specifically described otherwise. The first and second are provided herein for the purpose of distinguishing between them and not for the purpose of describing a sequential relationship and should not be construed as indicating or implying any particular importance or order of magnitude of the features indicated.
Example 1
A method for comprehensively recovering all components of a waste crystalline silicon photovoltaic module comprises the following steps:
(1) Pre-sorting: the method comprises the steps of pre-disassembly and judging whether the glass backboard is broken; firstly, pre-dismantling the collected waste crystalline silicon photovoltaic plates to obtain an aluminum frame and a junction box, comprehensively utilizing the collected waste crystalline silicon photovoltaic plates according to whether the glass backboard is broken or not after pre-dismantling to obtain incomplete plates and complete plates, recycling the incomplete plates in a rotary low-temperature vacuum pyrolysis recovery system, and recycling the complete plates in a mobile microwave reinforced pyrolysis recovery system;
(2) And (5) recycling incomplete plates: the incomplete plate rotary low-temperature vacuum pyrolysis recovery system comprises cutting blocks, rotary low-temperature vacuum pyrolysis and eddy current separation; cutting the incomplete plate obtained in the step (1) into blocks, then carrying out rotary low-temperature vacuum pyrolysis, wherein the pyrolysis reaction is carried out in a closed rotary furnace, the diameter of a furnace body is 0.5m, the effective heated length of the furnace body is 1.5m, the rotating speed of the furnace body is 1rpm, the pyrolysis temperature is 300 ℃, the pyrolysis time is 45min, first hydrogen-containing pyrolysis gas and pyrolysis slag are obtained, the first hydrogen-containing pyrolysis gas is utilized, the pyrolysis slag is subjected to eddy current separation to obtain glass slag, a first soldering tin conduction band, photovoltaic cell panel residues and first pyrolysis slag, the glass slag, the first soldering tin conduction band and the photovoltaic cell panel residues are respectively and comprehensively utilized, and the first pyrolysis slag enters a complete plate recycling system in the step (3) for recycling;
(3) And (3) recycling the complete plate: the complete board movable type microwave enhanced pyrolysis recovery system comprises movable type microwave enhanced pyrolysis, component separation and nitric acid leaching; the method comprises the steps of carrying out movable type microwave enhanced pyrolysis on a complete plate obtained in the step (1), wherein pyrolysis reaction is carried out in a closed movable type reaction furnace, a glass backboard is placed downwards, a TPT surface and a photovoltaic silicon wafer are placed upwards, microwave heating is adopted, microwave power is 800W, pyrolysis temperature is 650 ℃, microwave pyrolysis time is 30min, second hydrogen-containing pyrolysis gas and a pyrolysis plate are obtained, energy utilization is carried out on the second hydrogen-containing pyrolysis gas, component separation is carried out on the pyrolysis plate, a complete photovoltaic cell silicon wafer, a complete glass plate, a second soldering tin conduction band and second pyrolysis ash are obtained, the complete photovoltaic cell silicon wafer and the complete glass plate are respectively recycled, the second soldering tin conduction band is comprehensively utilized with the first soldering tin conduction band obtained in the step (2) non-complete plate recycling system, nitric acid leaching is carried out after the second pyrolysis ash is mixed with the first pyrolysis ash obtained in the step (2) non-complete plate recycling system, the mass percentage of nitric acid is 20%, leaching reaction temperature is 35 ℃ and leaching reaction time is 2.5h, leaching slag and noble metal contained acid leaching solution is obtained, concentrated.
In the whole comprehensive recovery system of the waste crystalline silicon photovoltaic module, the EVA comprehensive decomposition rate is 99.5%, the TPT comprehensive decomposition rate is 99.8%, and the generated first hydrogen-containing pyrolysis gas and second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the noble metal recovery process.
Example 2
The same as in example 1, except that:
in the rotary low-temperature vacuum pyrolysis condition in the step (2), the diameter of the furnace body is 1.2m, the effective heated length of the furnace body is 3.5m, the rotation speed of the furnace body is 5rpm, the pyrolysis temperature is 450 ℃, and the pyrolysis time is 20min.
The conditions of the movable microwave enhanced pyrolysis in the step (3) are as follows: the microwave power is 1200W, the pyrolysis temperature is 950 ℃, the microwave pyrolysis time is 5min, and the conditions of nitric acid leaching are as follows: the mass percentage of nitric acid is 70%, the leaching reaction temperature is 85 ℃, and the leaching reaction time is 0.5h.
In the whole comprehensive recovery system of the waste crystalline silicon photovoltaic module, the EVA comprehensive decomposition rate is 100%, the TPT comprehensive decomposition rate is 100%, and the generated first hydrogen-containing pyrolysis gas and second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the noble metal recovery process.
Example 3
The same as in example 1, except that:
in the rotary low-temperature vacuum pyrolysis condition in the step (2), the diameter of the furnace body is 0.6m, the effective heated length of the furnace body is 1.8m, the rotation speed of the furnace body is 2rpm, the pyrolysis temperature is 350 ℃, and the pyrolysis time is 25min.
The conditions of microwave pyrolysis in the step (3) are as follows: the microwave power is 900W, the pyrolysis temperature is 750 ℃, the microwave pyrolysis time is 25min, and the conditions of nitric acid leaching are as follows: the mass percentage of nitric acid is 30%, the leaching reaction temperature is 45 ℃, and the leaching reaction time is 2.0h.
In the whole comprehensive recovery system of the waste crystalline silicon photovoltaic module, the EVA comprehensive decomposition rate is 99.6%, the TPT comprehensive decomposition rate is 99.7%, and the generated first hydrogen-containing pyrolysis gas and second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the noble metal recovery process.
Example 4
The same as in example 1, except that:
in the rotary low-temperature vacuum pyrolysis condition in the step (2), the diameter of the furnace body is 1.0m, the effective heated length of the furnace body is 3.0m, the rotation speed of the furnace body is 4rpm, the pyrolysis temperature is 400 ℃, and the pyrolysis time is 40min.
The conditions of microwave pyrolysis in the step (3) are as follows: the microwave power is 1100W, the pyrolysis temperature is 850 ℃, the microwave pyrolysis time is 10min, and the conditions of nitric acid leaching are as follows: the mass percentage of nitric acid is 60%, the leaching reaction temperature is 75 ℃, and the leaching reaction time is 1.5h.
In the whole comprehensive recovery system of the waste crystalline silicon photovoltaic module, the EVA comprehensive decomposition rate is 99.8%, the TPT comprehensive decomposition rate is 99.8%, and the generated first hydrogen-containing pyrolysis gas and second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the noble metal recovery process.
Example 5
The same as in example 1, except that:
in the rotary low-temperature vacuum pyrolysis condition in the step (2), the diameter of the furnace body is 0.8m, the effective heated length of the furnace body is 2.0m, the rotation speed of the furnace body is 3rpm, the pyrolysis temperature is 320 ℃, and the pyrolysis time is 35min.
The conditions of microwave pyrolysis in the step (3) are as follows: the microwave power is 1000W, the pyrolysis temperature is 700 ℃, the microwave pyrolysis time is 15min, and the conditions of nitric acid leaching are as follows: the mass percentage of nitric acid is 40%, the leaching reaction temperature is 65 ℃, the leaching reaction time is 1.0h, the leaching slag and the acid leaching liquid containing noble metal are obtained, the leaching slag is treated in a concentrated way, and the acid leaching liquid containing noble metal returns to the noble metal recovery system.
In the whole comprehensive recovery system of the waste crystalline silicon photovoltaic module, the EVA comprehensive decomposition rate is 99.7%, the TPT comprehensive decomposition rate is 99.9%, and the generated first hydrogen-containing pyrolysis gas and second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the noble metal recovery process.
Example 6
The same as in example 1, except that:
in the rotary low-temperature vacuum pyrolysis condition in the step (2), the diameter of the furnace body is 1.0m, the effective heated length of the furnace body is 2.5m, the rotation speed of the furnace body is 4rpm, the pyrolysis temperature is 420 ℃, and the pyrolysis time is 30min.
The conditions of microwave pyrolysis in the step (3) are as follows: the microwave power is 950W, the pyrolysis temperature is 800 ℃, the microwave pyrolysis time is 20min, and the conditions of nitric acid leaching are as follows: the mass percentage of nitric acid is 50%, the leaching reaction temperature is 55 ℃, the leaching reaction time is 1.0h, the leaching slag and the acid leaching liquid containing noble metal are obtained, the leaching slag is treated in a concentrated way, and the acid leaching liquid containing noble metal returns to the noble metal recovery system.
In the whole comprehensive recovery system of the waste crystalline silicon photovoltaic module, the comprehensive decomposition rate of EVA is 99.9%, the comprehensive decomposition rate of TPT is 100%, and the generated first hydrogen-containing pyrolysis gas and second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the noble metal recovery process.
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.
Claims (6)
1. The method for comprehensively recovering all components of the waste crystalline silicon photovoltaic module is characterized by comprising the following steps of:
(1) Pre-sorting: pre-dismantling the collected waste crystalline silicon photovoltaic plates, comprehensively utilizing the collected waste crystalline silicon photovoltaic plates after dismantling to obtain an aluminum frame and a junction box, obtaining incomplete plates and complete plates according to whether the glass backboard is complete or not after pre-dismantling, recycling the incomplete plates in a rotary low-temperature vacuum pyrolysis recycling system, and recycling the complete plates in a mobile microwave reinforced pyrolysis recycling system;
(2) And (5) recycling incomplete plates: the incomplete plate rotary low-temperature vacuum pyrolysis recovery system comprises a cutting and blocking device, rotary low-temperature vacuum pyrolysis and eddy current separation; cutting the incomplete plate obtained in the step (1) into blocks by a cutting block device, performing rotary low-temperature vacuum pyrolysis to obtain first hydrogen-containing pyrolysis gas and pyrolysis slag, performing energy utilization on the first hydrogen-containing pyrolysis gas, separating the pyrolysis slag by eddy current to obtain glass slag, a first soldering tin conduction band, photovoltaic cell panel residues and first pyrolysis slag, respectively comprehensively utilizing the glass slag, the first soldering tin conduction band and the photovoltaic cell panel residues, and recycling the first pyrolysis slag in a complete plate recycling system in the step (3), wherein in the rotary low-temperature vacuum pyrolysis process, pyrolysis reaction is performed in a closed rotary furnace, the furnace body diameter is 0.5-1.2 m, the effective heating length of the furnace body is 1.5-3.5 m, the furnace body rotation speed is 1-5 rpm, the pyrolysis temperature is 300-450 ℃, and the pyrolysis time is 20-45 min;
(3) And (3) recycling the complete plate: the complete board movable type microwave enhanced pyrolysis recovery system comprises movable type microwave enhanced pyrolysis, component separation and nitric acid leaching; performing mobile microwave enhanced pyrolysis on the complete board obtained in the step (1) to obtain second hydrogen-containing pyrolysis gas and a pyrolysis board, performing energy utilization on the second hydrogen-containing pyrolysis gas, performing component separation on the pyrolysis board to obtain a complete photovoltaic cell silicon wafer, a complete glass board, a second soldering tin conduction band and second pyrolysis ash, respectively performing recycling on the complete photovoltaic cell silicon wafer and the complete glass board, jointly and comprehensively utilizing the second soldering tin conduction band and the first soldering tin conduction band recovered from the incomplete board obtained in the step (2), mixing the second pyrolysis ash and the first pyrolysis ash recovered from the incomplete board obtained in the step (2), performing nitric acid leaching to obtain leaching slag and acid leaching liquid containing noble metals, performing concentrated treatment on the leaching slag, returning the acid leaching liquid containing noble metals to a noble metal recovery system, and recovering the noble metal in the mobile microwave enhanced pyrolysis process, wherein the pyrolysis reaction is performed in a closed mobile reaction furnace, the glass backboard is placed downwards, the TPT surface and the photovoltaic silicon wafer are placed upwards, and microwave heating is adopted, wherein the microwave power is 800-1200W, and the pyrolysis temperature is 650-950 ℃ and the microwave pyrolysis time is 5-30 min.
2. The method for comprehensively recovering all components of the waste crystalline silicon photovoltaic module according to claim 1, wherein the diameter of the furnace body in the step (2) is 0.6-1.0 m, the effective heated length of the furnace body is 1.8-3.0 m, the rotating speed of the furnace body is 2-4 rpm, the pyrolysis temperature is 320-420 ℃, and the pyrolysis time is 25-40 min.
3. The method for comprehensively recovering all components of the waste crystalline silicon photovoltaic module according to claim 1, wherein the microwave power in the step (3) is 900-1100W, the pyrolysis temperature is 700-850 ℃, and the microwave pyrolysis time is 10-25 min.
4. The method for comprehensively recovering all components of the waste crystalline silicon photovoltaic module according to claim 1, wherein in the nitric acid leaching process in the step (3), the mass percentage of nitric acid is 20% -70%, the leaching reaction temperature is 35 ℃ -85 ℃, and the leaching reaction time is 0.5-2.5 h.
5. The method for comprehensively recovering all components of the waste crystalline silicon photovoltaic module according to claim 4, wherein in the nitric acid leaching process in the step (3), the mass percentage of nitric acid is 30% -60%, the leaching reaction temperature is 45 ℃ -75 ℃, and the leaching reaction time is 1.0-2.0 h.
6. The method for comprehensive recovery of all components of a spent crystalline silicon photovoltaic module of claim 1, wherein the first hydrogen-containing pyrolysis gas and the second hydrogen-containing pyrolysis gas are used as heat sources for a vacuum pyrolysis and precious metal recovery system.
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| CN110624936B (en) * | 2019-09-27 | 2020-10-02 | 中国科学院城市环境研究所 | Waste photovoltaic module disassembling method for realizing silicon wafer integrity recovery |
| CN215198902U (en) * | 2021-04-25 | 2021-12-17 | 陕西青朗万城环保科技有限公司 | Device for treating waste circuit board based on microwave |
| CN215198903U (en) * | 2021-04-26 | 2021-12-17 | 陕西青朗万城环保科技有限公司 | Device for recovering metals in electronic garbage by microwaves |
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