CN114833176A - Method for comprehensively recycling all components of waste crystalline silicon photovoltaic module - Google Patents
Method for comprehensively recycling all components of waste crystalline silicon photovoltaic module Download PDFInfo
- Publication number
- CN114833176A CN114833176A CN202210411518.9A CN202210411518A CN114833176A CN 114833176 A CN114833176 A CN 114833176A CN 202210411518 A CN202210411518 A CN 202210411518A CN 114833176 A CN114833176 A CN 114833176A
- Authority
- CN
- China
- Prior art keywords
- pyrolysis
- plate
- complete
- recycling
- crystalline silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002699 waste material Substances 0.000 title claims abstract description 41
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 37
- 238000004064 recycling Methods 0.000 title claims description 32
- 238000000197 pyrolysis Methods 0.000 claims abstract description 134
- 238000002386 leaching Methods 0.000 claims abstract description 55
- 238000011084 recovery Methods 0.000 claims abstract description 47
- 239000011521 glass Substances 0.000 claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 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 23
- 239000002893 slag Substances 0.000 claims abstract description 20
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010970 precious metal Substances 0.000 claims abstract description 19
- 238000005476 soldering Methods 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
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000005336 cracking Methods 0.000 claims abstract description 9
- 238000005520 cutting process Methods 0.000 claims abstract description 9
- 239000012634 fragment Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052718 tin Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 230000000903 blocking effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 2
- 239000000779 smoke Substances 0.000 abstract description 3
- 235000012431 wafers Nutrition 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 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
- 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
- 235000021110 pickles Nutrition 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000000053 physical method Methods 0.000 description 1
- 238000007789 sealing Methods 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
Images
Classifications
-
- 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
-
- 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
-
- 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]
Landscapes
- 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)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Processing Of Solid Wastes (AREA)
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, performing rotary vacuum pyrolysis to obtain first hydrogen-containing pyrolysis gas and pyrolysis slag, and sorting the pyrolysis slag to obtain glass slag, a first soldering tin conduction band, photovoltaic cell panel fragments and first pyrolysis ash; (3) and carrying out mobile microwave enhanced pyrolysis on the complete plate to obtain a second hydrogen-containing pyrolysis gas and a pyrolysis plate, carrying out 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 cracking ash, mixing the second cracking ash and the first cracking ash, and then carrying out nitric acid leaching to obtain leached residues and a precious metal-containing acid leaching solution. The method realizes the high-valued 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 depletion of fossil energy and the increasing prominence of environmental issues, the need for clean energy to overcome the use of fossil fuels and to slow down climate change caused by human activities is a hot spot of global concern. Crystalline silicon photovoltaic power generation technology is considered as a promising technology that can convert sunlight into electric energy without any other energy source. In recent years, photovoltaic power generation has been rapidly developed, and annual growth demand for global photovoltaic power exceeds 20%. Under the targets of carbon peak reaching and carbon neutralization, photovoltaic power generation is rapidly developing in China, and the situation that new energy such as wind, light and the like gradually rises from the auxiliary energy position to the main energy position is clarified. In 2020, the percentage of photovoltaic power generation in China is about 3.5%, and the percentage of photovoltaic power generation will rise to more than 20% in the future.
With the increase of the number of photovoltaic loading machines, the number of waste crystalline silicon photovoltaic cell assemblies is also increased rapidly. The technical life of the photovoltaic module is estimated according to 20-30 years, the domestic photovoltaic module reaches the abandonment climax in 2035 years, and the production of the waste photovoltaic panel reaches 2000 ten thousand tons in 2050 years. 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 sealing compound (EVA), about 5% of silicon wafer, about 3% of TPT back plate, about 2% of other valuable metals such as silver, tin, copper, lead, indium and the like, so that the high recycling value is achieved, and a large amount of heavy metals and organic matters in the glass greatly threaten the environment and even the human safety if the glass is not properly disposed. Therefore, research on recycling of the waste crystalline silicon photovoltaic module is urgently needed.
Most of the research efforts to date have focused on physical sorting, chemical solvent processes, and thermal processes. Publication No. CN 110783428A discloses a physical method for separating and recycling waste photovoltaic panels by fluid, which can obtain complete glass panels but completely damage silicon wafers, and is not suitable for disposing the broken waste photovoltaic panels of the glass panels; publication No. CN 110328216 a discloses two-stage heat treatment for recycling waste photovoltaic panels, but the first preset temperature is low, toxic gas is easily generated, operation environment is deteriorated, and serious challenge is generated to worker operation, and no mention is made of a disposal method of waste photovoltaic panels for breaking glass panels.
By combining the characteristics of the recovery method, the existing disposal method is mainly characterized in that a binder (EVA) between a glass plate and a silicon wafer is damaged, and the complete silicon wafer and glass plate cannot be obtained, 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 needs to be developed to solve the problem of comprehensive recovery of all 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 recycling all components of a waste crystalline silicon photovoltaic module.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for comprehensively recovering all components of a waste crystalline silicon photovoltaic module comprises the following steps:
(1) pre-sorting: pre-disassembling the collected waste crystalline silicon photovoltaic plate, disassembling to obtain an aluminum frame and a junction box, collecting and comprehensively utilizing the aluminum frame and the junction box, pre-disassembling and then obtaining an incomplete plate and a complete plate according to whether a glass back plate is complete, enabling the incomplete plate to enter a rotary low-temperature vacuum pyrolysis recovery system for recycling, and enabling the complete plate to enter a movable microwave enhanced pyrolysis recovery system for recycling;
(2) and (3) recovering an incomplete plate: the incomplete plate rotary low-temperature vacuum pyrolysis recovery system comprises cutting into blocks, rotary low-temperature vacuum pyrolysis and eddy current separation; cutting the incomplete plate obtained in the step (1) into blocks by a cutting and blocking 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, performing eddy current separation on the pyrolysis slag to obtain glass slag, a first soldering tin conduction band, a photovoltaic cell panel fragment and first pyrolysis ash, comprehensively utilizing the glass slag, the first soldering tin conduction band and the photovoltaic cell panel fragment respectively, and recycling the first pyrolysis ash in the complete plate recycling system in the step (3);
(3) and (3) complete plate recovery: the complete plate mobile microwave enhanced pyrolysis recovery system comprises mobile microwave enhanced pyrolysis, component separation and nitric acid leaching; and (2) carrying out movable microwave enhanced pyrolysis on the complete plate obtained in the step (1) to obtain a second hydrogen-containing pyrolysis gas and a pyrolysis plate, wherein the second hydrogen-containing pyrolysis gas is used for energy utilization, the pyrolysis plate is used for component separation to obtain a complete photovoltaic cell silicon wafer, a complete glass plate, a second soldering tin conduction band and second cracking ash, the complete photovoltaic cell silicon wafer and the complete glass plate are respectively recycled, the second soldering tin conduction band and the first conduction band soldering tin obtained by recycling the incomplete plate in the step (2) are jointly and comprehensively utilized, the second cracking ash and the first cracking ash obtained by recycling the incomplete plate in the step (2) are mixed and then subjected to nitric acid leaching to obtain leaching residues and a precious metal-containing pickle liquor, the leaching residues are subjected to centralized treatment, and the precious metal-containing pickle liquor is returned to a precious metal recycling system for recycling.
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 heating length of the furnace body is 1.5-3.5 m, the rotating 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 heating 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 microwave-enhanced pyrolysis process in the step (3), the pyrolysis reaction is performed in a closed mobile reaction furnace, the glass back plate 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 the 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 the 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 hydrogenous pyrolysis gas and the second hydrogenous pyrolysis gas are used as heat sources of the vacuum pyrolysis and precious metal recovery system. In the non-complete plate recovery system and the complete plate recovery system, the generated hydrogen-containing hot gas has similar components and can be used as a heat source for the pyrolysis process and the precious metal recovery process.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a method for respectively and independently recovering a broken glass incomplete plate and a complete plate waste crystalline silicon photovoltaic module, wherein the incomplete plate is cut into blocks and then subjected to low-temperature vacuum pyrolysis by using a rotary furnace; compared with the traditional pyrolysis mode, the microwave enhanced pyrolysis method has the advantages that the complete board is subjected to microwave enhanced pyrolysis by adopting the movable reaction furnace, organic components are rapidly and completely decomposed, nondestructive photovoltaic silicon wafers and glass backboards can be obtained, the full-component high-valued recovery of the waste crystalline silicon photovoltaic components is realized, and the microwave enhanced pyrolysis method has the characteristics of high comprehensive utilization rate of resources, short process flow, high heat value utilization rate, no smoke pollution and the like.
2. The pre-disassembly system provided by the invention can realize the classified independent recovery of the photovoltaic panel with the broken glass plate and the photovoltaic panel with the complete glass plate, the complete plate recovery system adopts a microwave pyrolysis technology, and different from the traditional heating mode, microwaves can directly penetrate through the glass plate and the silicon wafer of the photovoltaic panel to selectively and uniformly heat EVA and TPT from inside to outside, so that the pre-disassembly system has the excellent characteristics of high temperature rise rate, high heat utilization rate and capability of obtaining 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 method is particularly suitable for treating the damaged glass plate or the complete waste crystalline silicon photovoltaic module of the glass plate, and has the characteristics of high comprehensive utilization rate of resources, short process flow, high heat value utilization rate, no smoke pollution and the like.
Drawings
FIG. 1 is a process flow diagram of a comprehensive recovery method of all components of a waste crystalline silicon photovoltaic module.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The equipment used in the present invention is a commercially available product conventionally used in the art unless otherwise specified. First and second in this application are for distinguishing names, do not represent sequential relationships, and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical 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-disassembling and judging whether a glass back plate is broken or not; the collected waste crystalline silicon photovoltaic panel is firstly pre-disassembled to obtain an aluminum frame and a junction box, the aluminum frame and the junction box are comprehensively utilized after collection, an incomplete panel and a complete panel are obtained after pre-disassembly according to whether a glass backboard is broken, the incomplete panel enters a rotary low-temperature vacuum pyrolysis recovery system for recycling, and the complete panel enters a movable microwave enhanced pyrolysis recovery system for recycling;
(2) and (3) recovering an incomplete plate: the incomplete plate rotary low-temperature vacuum pyrolysis recovery system comprises cutting into blocks, rotary low-temperature vacuum pyrolysis and eddy current separation; cutting the incomplete plate obtained in the step (1) into blocks, and performing rotary low-temperature vacuum pyrolysis, wherein the pyrolysis reaction is performed in a closed rotary furnace, the diameter of the furnace body is 0.5m, the effective heating length of the furnace body is 1.5m, the rotating speed of the furnace body is 1rpm, the pyrolysis temperature is 300 ℃, and the pyrolysis time is 45min, so that first hydrogen-containing pyrolysis gas and pyrolysis slag are obtained, the first hydrogen-containing pyrolysis gas is used for energy, the pyrolysis slag is subjected to eddy current sorting to obtain glass slag, first conduction band soldering tin, photovoltaic cell panel fragments and first pyrolysis ash slag, the glass slag, the first soldering tin conduction band and the photovoltaic cell panel fragments are respectively comprehensively utilized, and the first pyrolysis ash slag enters a complete plate recovery system in the step (3) for recovery;
(3) and (3) complete plate recovery: the complete plate mobile microwave enhanced pyrolysis recovery system comprises mobile microwave enhanced pyrolysis, component separation and nitric acid leaching; carrying out mobile microwave enhanced pyrolysis on the complete plate obtained in the step (1), wherein the pyrolysis reaction is carried out in a closed mobile reaction furnace, a glass back plate is placed downwards, a TPT surface and a photovoltaic silicon wafer are placed upwards, microwave heating is adopted, the microwave power is 800W, the pyrolysis temperature is 650 ℃, the microwave pyrolysis time is 30min, a second hydrogen-containing pyrolysis gas and a pyrolysis plate are obtained, the second hydrogen-containing pyrolysis gas is used for energy utilization, the pyrolysis plate is subjected to component separation, a complete photovoltaic cell silicon wafer, a complete glass plate, a second soldering tin conduction band and second pyrolysis ash slag are obtained, the complete photovoltaic cell silicon wafer and the complete glass plate are respectively recycled, the second soldering tin is comprehensively utilized together with the first soldering tin conduction band obtained by the incomplete plate recovery system in the step (2), the second soldering tin ash slag is mixed with the first pyrolysis ash slag obtained by the incomplete plate recovery system in the step (2) and then is subjected to nitric acid leaching, the mass percentage of the nitric acid is 20%, the leaching reaction temperature is 35 ℃, the leaching reaction time is 2.5 hours, leaching residues and the acid leaching solution containing the noble metal are obtained, the leaching residues are treated in a centralized manner, and the acid leaching solution containing the noble metal returns to a noble metal recovery system.
In the whole waste crystalline silicon photovoltaic module full-component comprehensive recovery system, the comprehensive decomposition rate of EVA is 99.5%, the comprehensive decomposition rate of TPT is 99.8%, and the generated first hydrogen-containing pyrolysis gas and the generated second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the precious metal recovery process.
Example 2
The same as 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 heating length of the furnace body is 3.5m, the rotating speed of the furnace body is 5rpm, the pyrolysis temperature is 450 ℃, and the pyrolysis time is 20 min.
The conditions of the mobile 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 nitric acid leaching conditions are as follows: the mass percent of the nitric acid is 70 percent, the leaching reaction temperature is 85 ℃, and the leaching reaction time is 0.5 h.
In the whole waste crystalline silicon photovoltaic module full-component comprehensive recovery system, the comprehensive EVA decomposition rate is 100%, the comprehensive TPT decomposition rate is 100%, and the generated first hydrogen-containing pyrolysis gas and the generated second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the precious metal recovery process.
Example 3
The same as 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 heating length of the furnace body is 1.8m, the rotating speed of the furnace body is 2rpm, the pyrolysis temperature is 350 ℃, and the pyrolysis time is 25 min.
The microwave pyrolysis conditions 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 nitric acid leaching conditions are as follows: the mass percentage of the nitric acid is 30 percent, the leaching reaction temperature is 45 ℃, and the leaching reaction time is 2.0 h.
In the whole waste crystalline silicon photovoltaic module full-component comprehensive recovery system, the comprehensive decomposition rate of EVA is 99.6%, the comprehensive decomposition rate of TPT is 99.7%, and the generated first hydrogen-containing pyrolysis gas and the generated second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the precious metal recovery process.
Example 4
The same as 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 heating length of the furnace body is 3.0m, the rotating speed of the furnace body is 4rpm, the pyrolysis temperature is 400 ℃, and the pyrolysis time is 40 min.
The microwave pyrolysis conditions 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 nitric acid leaching conditions are as follows: the mass percentage of the nitric acid is 60 percent, the leaching reaction temperature is 75 ℃, and the leaching reaction time is 1.5 h.
In the whole waste crystalline silicon photovoltaic module full-component comprehensive recovery system, the comprehensive decomposition rate of EVA is 99.8%, the comprehensive decomposition rate of TPT is 99.8%, and the generated first hydrogen-containing pyrolysis gas and the generated second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the precious metal recovery process.
Example 5
The same as 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 heating length of the furnace body is 2.0m, the rotating speed of the furnace body is 3rpm, the pyrolysis temperature is 320 ℃, and the pyrolysis time is 35 min.
The microwave pyrolysis conditions 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 nitric acid leaching conditions are as follows: the mass percentage of the nitric acid is 40%, the leaching reaction temperature is 65 ℃, the leaching reaction time is 1.0h, leaching residues and acid leaching solution containing precious metals are obtained, the leaching residues are treated in a centralized manner, and the acid leaching solution containing the precious metals returns to a precious metal recovery system.
In the whole waste crystalline silicon photovoltaic module full-component comprehensive recovery system, the comprehensive decomposition rate of EVA is 99.7%, the comprehensive decomposition rate of TPT is 99.9%, and the generated first hydrogen-containing pyrolysis gas and the generated second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the precious metal recovery process.
Example 6
The same as 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 heating length of the furnace body is 2.5m, the rotating speed of the furnace body is 4rpm, the pyrolysis temperature is 420 ℃, and the pyrolysis time is 30 min.
The microwave pyrolysis conditions in the step (3) are as follows: microwave power 950W, pyrolysis temperature 800 ℃, microwave pyrolysis time 20min, and nitric acid leaching conditions are as follows: the mass percentage of the nitric acid is 50%, the leaching reaction temperature is 55 ℃, the leaching reaction time is 1.0h, leaching residues and the acid leaching solution containing the noble metal are obtained, the leaching residues are treated in a centralized manner, and the acid leaching solution containing the noble metal returns to a noble metal recovery system.
In the whole waste crystalline silicon photovoltaic module full-component comprehensive recovery system, the comprehensive EVA decomposition rate is 99.9%, the comprehensive TPT decomposition rate is 100%, and the generated first hydrogen-containing pyrolysis gas and the generated second hydrogen-containing pyrolysis gas can be used as heat sources in the pyrolysis process and the precious metal recovery process.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (8)
1. A method for comprehensively recovering all components of a waste crystalline silicon photovoltaic module is characterized by comprising the following steps:
(1) pre-sorting: pre-disassembling the collected waste crystalline silicon photovoltaic plate, disassembling to obtain an aluminum frame and a junction box, collecting and comprehensively utilizing the aluminum frame and the junction box, pre-disassembling and then obtaining an incomplete plate and a complete plate according to whether a glass back plate is complete, enabling the incomplete plate to enter a rotary low-temperature vacuum pyrolysis recovery system for recycling, and enabling the complete plate to enter a movable microwave enhanced pyrolysis recovery system for recycling;
(2) and (3) recovering an incomplete plate: the incomplete plate rotary type low-temperature vacuum pyrolysis recovery system comprises a cutting blocking device, a rotary type low-temperature vacuum pyrolysis device and an eddy current sorting device; cutting the incomplete plate obtained in the step (1) into blocks by a cutting and blocking 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, performing eddy current separation on the pyrolysis slag to obtain glass slag, a first soldering tin conduction band, a photovoltaic cell panel fragment and first pyrolysis ash, comprehensively utilizing the glass slag, the first soldering tin conduction band and the photovoltaic cell panel fragment respectively, and recycling the first pyrolysis ash in the complete plate recycling system in the step (3);
(3) and (3) complete plate recovery: the complete plate mobile microwave enhanced pyrolysis recovery system comprises mobile microwave enhanced pyrolysis, component separation and nitric acid leaching; and (2) carrying out movable microwave enhanced pyrolysis on the complete plate obtained in the step (1) to obtain a second hydrogen-containing pyrolysis gas and a pyrolysis plate, wherein the second hydrogen-containing pyrolysis gas is used for energy utilization, the pyrolysis plate is used for component separation to obtain a complete photovoltaic cell silicon wafer, a complete glass plate, a second soldering tin conduction band and second cracking ash, the complete photovoltaic cell silicon wafer and the complete glass plate are respectively recycled, the second soldering tin conduction band and first conduction band soldering tin obtained by recycling the incomplete plate in the step (2) are jointly and comprehensively utilized, the second cracking ash and the first cracking ash obtained by recycling the incomplete plate in the step (2) are mixed and then subjected to nitric acid leaching to obtain leaching residues and acid leaching liquid containing precious metals, the leaching residues are subjected to centralized disposal, and the acid leaching liquid containing the precious metals is returned to a precious metal recycling system for recycling.
2. The method for comprehensively recovering all components of the waste crystalline silicon photovoltaic module according to claim 1, wherein in the rotary low-temperature vacuum pyrolysis process in the step (2), the pyrolysis reaction is carried out in a closed rotary furnace, the diameter of the furnace body is 0.5-1.2 m, the effective heating length of the furnace body is 1.5-3.5 m, the rotating speed of the furnace body is 1-5 rpm, the pyrolysis temperature is 300-450 ℃, and the pyrolysis time is 20-45 min.
3. The method for comprehensively recycling all components of the waste crystalline silicon photovoltaic module according to claim 2, wherein the diameter of the furnace body in the step (2) is 0.6-1.0 m, the effective heating 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.
4. The method for comprehensively recycling all components of the waste crystalline silicon photovoltaic module according to claim 1, wherein in the mobile microwave enhanced pyrolysis process in the step (3), the pyrolysis reaction is carried out in a closed mobile reaction furnace, the glass back plate 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.
5. The method for comprehensively recycling all components of the waste crystalline silicon photovoltaic module according to claim 4, 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.
6. The method for comprehensively recycling all components of the waste crystalline silicon photovoltaic module as claimed in 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.
7. The method for comprehensively recycling all components of the waste crystalline silicon photovoltaic module as claimed in claim 6, 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.
8. The method for comprehensively recycling the full components of the waste crystalline silicon photovoltaic module as claimed in claim 1, wherein the first hydrogen-containing pyrolysis gas and the second hydrogen-containing pyrolysis gas are used as heat sources of a vacuum pyrolysis and precious metal recycling system.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210411518.9A CN114833176B (en) | 2022-04-19 | 2022-04-19 | Method for comprehensively recovering all components of waste crystalline silicon photovoltaic module |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210411518.9A CN114833176B (en) | 2022-04-19 | 2022-04-19 | Method for comprehensively recovering all components of waste crystalline silicon photovoltaic module |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114833176A true CN114833176A (en) | 2022-08-02 |
CN114833176B CN114833176B (en) | 2023-07-25 |
Family
ID=82566755
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210411518.9A Active CN114833176B (en) | 2022-04-19 | 2022-04-19 | Method for comprehensively recovering all components of waste crystalline silicon photovoltaic module |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114833176B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023239296A3 (en) * | 2022-06-06 | 2024-01-18 | Etavolt Pte Ltd | Assembly and method for photovoltaic (pv) system recycling |
CN117600203A (en) * | 2024-01-24 | 2024-02-27 | 江苏云洋电力科技有限公司 | Recycling equipment and recycling method for waste electronic components |
Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6063995A (en) * | 1998-07-16 | 2000-05-16 | First Solar, Llc | Recycling silicon photovoltaic modules |
JP2001030249A (en) * | 1999-07-21 | 2001-02-06 | Bridgestone Corp | Method for disposing of laminate |
CN102069086A (en) * | 2010-11-17 | 2011-05-25 | 山东大学 | Method for reclaiming and treating electronic waste |
JP2014024037A (en) * | 2012-07-27 | 2014-02-06 | Mitsubishi Materials Corp | Decomposition method for solar battery panel |
JP2014108375A (en) * | 2012-11-30 | 2014-06-12 | Shinryo Corp | Method of recovering constituent material of solar cell element |
CN103978021A (en) * | 2014-05-08 | 2014-08-13 | 刘景洋 | Waste crystalline silicon solar cell panel disassembling and recovering method |
EP2998038A1 (en) * | 2014-09-16 | 2016-03-23 | SASIL S.p.A. | Method and apparatus for detaching glass form a mono- or polycrystalline silicon-based photovoltaic panel |
WO2017083290A1 (en) * | 2015-11-09 | 2017-05-18 | Eauterre Consulting, Llc | Method and apparatus for separation and size reduction of noble metal containing sources |
US20170190977A1 (en) * | 2015-12-31 | 2017-07-06 | Chz Technologies, Llc | Multistage thermolysis method for safe and efficient conversion of e-waste materials |
CN107828974A (en) * | 2017-10-23 | 2018-03-23 | 广东绿晟环保股份有限公司 | A kind of waste printed circuit board combined treatment process |
US20180315884A1 (en) * | 2015-07-15 | 2018-11-01 | Université de Liège | Method for recycling photovoltaic solar cells module |
CN109092842A (en) * | 2018-06-20 | 2018-12-28 | 常州瑞赛环保科技有限公司 | Scrap photovoltaic module disassembling method |
CN109719117A (en) * | 2018-12-30 | 2019-05-07 | 沈阳化工研究院有限公司 | A kind of method that recovery processing waste lithium cell is pyrolyzed in the process |
CN110328216A (en) * | 2019-07-12 | 2019-10-15 | 晶科能源有限公司 | A kind of photovoltaic module recovery method |
TWI678243B (en) * | 2018-10-19 | 2019-12-01 | 國立臺南大學 | Recovery method of solar battery module (3) |
CN110624936A (en) * | 2019-09-27 | 2019-12-31 | 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 |
-
2022
- 2022-04-19 CN CN202210411518.9A patent/CN114833176B/en active Active
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6063995A (en) * | 1998-07-16 | 2000-05-16 | First Solar, Llc | Recycling silicon photovoltaic modules |
JP2001030249A (en) * | 1999-07-21 | 2001-02-06 | Bridgestone Corp | Method for disposing of laminate |
CN102069086A (en) * | 2010-11-17 | 2011-05-25 | 山东大学 | Method for reclaiming and treating electronic waste |
JP2014024037A (en) * | 2012-07-27 | 2014-02-06 | Mitsubishi Materials Corp | Decomposition method for solar battery panel |
JP2014108375A (en) * | 2012-11-30 | 2014-06-12 | Shinryo Corp | Method of recovering constituent material of solar cell element |
CN103978021A (en) * | 2014-05-08 | 2014-08-13 | 刘景洋 | Waste crystalline silicon solar cell panel disassembling and recovering method |
EP2998038A1 (en) * | 2014-09-16 | 2016-03-23 | SASIL S.p.A. | Method and apparatus for detaching glass form a mono- or polycrystalline silicon-based photovoltaic panel |
US20180315884A1 (en) * | 2015-07-15 | 2018-11-01 | Université de Liège | Method for recycling photovoltaic solar cells module |
WO2017083290A1 (en) * | 2015-11-09 | 2017-05-18 | Eauterre Consulting, Llc | Method and apparatus for separation and size reduction of noble metal containing sources |
US20170190977A1 (en) * | 2015-12-31 | 2017-07-06 | Chz Technologies, Llc | Multistage thermolysis method for safe and efficient conversion of e-waste materials |
CN107828974A (en) * | 2017-10-23 | 2018-03-23 | 广东绿晟环保股份有限公司 | A kind of waste printed circuit board combined treatment process |
CN109092842A (en) * | 2018-06-20 | 2018-12-28 | 常州瑞赛环保科技有限公司 | Scrap photovoltaic module disassembling method |
TWI678243B (en) * | 2018-10-19 | 2019-12-01 | 國立臺南大學 | Recovery method of solar battery module (3) |
CN109719117A (en) * | 2018-12-30 | 2019-05-07 | 沈阳化工研究院有限公司 | A kind of method that recovery processing waste lithium cell is pyrolyzed in the process |
CN110328216A (en) * | 2019-07-12 | 2019-10-15 | 晶科能源有限公司 | A kind of photovoltaic module recovery method |
CN110624936A (en) * | 2019-09-27 | 2019-12-31 | 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 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023239296A3 (en) * | 2022-06-06 | 2024-01-18 | Etavolt Pte Ltd | Assembly and method for photovoltaic (pv) system recycling |
CN117600203A (en) * | 2024-01-24 | 2024-02-27 | 江苏云洋电力科技有限公司 | Recycling equipment and recycling method for waste electronic components |
CN117600203B (en) * | 2024-01-24 | 2024-04-12 | 江苏云洋电力科技有限公司 | Recycling equipment and recycling method for waste electronic components |
Also Published As
Publication number | Publication date |
---|---|
CN114833176B (en) | 2023-07-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN114833176A (en) | Method for comprehensively recycling all components of waste crystalline silicon photovoltaic module | |
Xu et al. | Global status of recycling waste solar panels: A review | |
Wang et al. | A review of end-of-life crystalline silicon solar photovoltaic panel recycling technology | |
Padoan et al. | Recycling of end of life photovoltaic panels: A chemical prospective on process development | |
CN100531943C (en) | Electronic refuse treatment method | |
Lovato et al. | Application of supercritical CO2 for delaminating photovoltaic panels to recover valuable materials | |
CN113410534A (en) | Method for recovering graphite and copper foil in anode of waste lithium ion battery through microwave radiation | |
CN106319222A (en) | Copper-indium-gallium-selenium photovoltaic module recycling method | |
CN114871237A (en) | Method for continuous pyrolysis treatment of waste crystalline silicon photovoltaic module | |
CN111014229B (en) | Pyrolysis recovery device utilizing waste heat of fuel cell and working method | |
Komoto et al. | Recycling of PV modules and its environmental impacts | |
CN108339831B (en) | Method for disposing silicon solar cell | |
Cheema et al. | Comprehensive review of the global trends and future perspectives for recycling of decommissioned photovoltaic panels | |
CN106032553A (en) | Method for recovering copper-indium-gallium-selenium photovoltaic assembly | |
Palaniappan et al. | Recycling of solar panels | |
CN218903043U (en) | Recovery system of waste photovoltaic module | |
CN106586988A (en) | Method for comprehensive recovery of indium and phosphorus from indium phosphide waste material | |
CN115430692A (en) | Novel method for separating and recycling retired photovoltaic module | |
CN112760109A (en) | Method for comprehensively utilizing waste computer circuit boards through microwave pyrolysis | |
CN108866340B (en) | Microwave irradiation recovery processing method for cadmium telluride thin-film solar cell | |
Zhou et al. | Status quo on recycling of waste crystalline silicon for photovoltaic modules and its implications for China’s photovoltaic industry | |
CN106829955A (en) | A kind of method that utilization scrap tire rubber vacuum microwave prepares activated carbon | |
Rozing et al. | Recyclability and ecological-economic analysis of a simple photovoltaic panel | |
CN113571791A (en) | Method for separating active material layer from current collector in electrode plate | |
Kamano et al. | Glass separation process for recycling of solar photovoltaic panels by microwave heating |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |