CN110624936A - Waste photovoltaic module disassembling method for realizing silicon wafer integrity recovery - Google Patents
Waste photovoltaic module disassembling method for realizing silicon wafer integrity recovery Download PDFInfo
- Publication number
- CN110624936A CN110624936A CN201910922201.XA CN201910922201A CN110624936A CN 110624936 A CN110624936 A CN 110624936A CN 201910922201 A CN201910922201 A CN 201910922201A CN 110624936 A CN110624936 A CN 110624936A
- Authority
- CN
- China
- Prior art keywords
- silicon wafer
- disassembling
- eva
- photovoltaic module
- organic solvent
- 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 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 42
- 239000010703 silicon Substances 0.000 title claims abstract description 42
- 239000002699 waste material Substances 0.000 title claims abstract description 28
- 238000011084 recovery Methods 0.000 title claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 239000003960 organic solvent Substances 0.000 claims abstract description 38
- 230000008961 swelling Effects 0.000 claims abstract description 34
- 238000000197 pyrolysis Methods 0.000 claims abstract description 24
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 14
- 238000011282 treatment Methods 0.000 claims abstract description 14
- 239000005341 toughened glass Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 46
- 206010042674 Swelling Diseases 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 24
- 239000012752 auxiliary agent Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 238000011369 optimal treatment Methods 0.000 claims 1
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 45
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 45
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 abstract description 44
- 239000013043 chemical agent Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 37
- 239000013078 crystal Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000011978 dissolution method Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- 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
- Y02W30/20—Waste processing or separation
-
- 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)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for disassembling a waste photovoltaic module for realizing the integrity recovery of a silicon wafer, which belongs to the technical field of solid waste recycling and comprises the following steps: mechanically pre-disassembling to remove the aluminum frame and the junction box to obtain the photovoltaic substrate without the aluminum frame and the junction box; placing the fixed photovoltaic substrate into a closed container, and performing steam-type limited swelling on EVA (ethylene vinyl acetate) in the photovoltaic substrate by using the vaporized organic solvent under the high-temperature condition to obtain an evacuated substrate with loose and dispersed EVA, wherein the back plate can be completely peeled off or partially peeled off; and placing the evacuated substrate into a pyrolysis reactor, and carrying out complete thermal decomposition on the residual EVA and the back plate under a high-temperature condition to realize complete separation of the toughened glass and the crystalline silicon wafer and complete recovery of the crystalline silicon wafer. The method disclosed by the invention is short in operation time, needs few chemical agents, can completely strip the crystalline silicon wafer in the photovoltaic component, is beneficial to subsequent treatment and utilization of the crystalline silicon wafer, and improves the recovery value and the economical efficiency of the waste photovoltaic.
Description
Technical Field
The invention discloses a method for disassembling a waste photovoltaic module for realizing silicon wafer integrity recovery, relates to the field of solid waste resource utilization, and particularly relates to a resource utilization method of a waste crystalline silicon photovoltaic module.
Background
Solar energy has recently received much attention as a safe, stable, continuous, clean, renewable energy source. The solar photovoltaic module is a core part of a photoelectric conversion system, the installed photovoltaic capacity is increased in a well-spraying manner along with the maturity of production technology and the reduction of cost, the installed photovoltaic capacity of a grid-connected photovoltaic system is accumulated to exceed 1.7 hundred million kilowatts at the end of 2018 years in China, and the market share of the crystalline silicon photovoltaic module is up to more than 90%. However, the service life of the photovoltaic module is generally between 20 and 25 years, so that huge installed capacity inevitably brings huge photovoltaic waste yield in the future. How to dispose the abandoned photovoltaic module in a high-efficiency resource manner becomes the last ring of the construction of the photovoltaic system.
An existing crystalline silicon photovoltaic module is mainly composed of an aluminum frame 1 ', toughened glass 2', a crystalline silicon wafer 3 ', a junction box 4', EVA 5 'and a back plate 6', wherein in the figure 1, the toughened glass is transparent, the EVA has certain light transmittance, and how to realize the disassembly and separation of the module is the key to realize the resource treatment of the module. The prior assembly disassembling method mainly comprises three major types, namely an inorganic acid dissolving method, an organic solvent dissolving method and a heat treatment method. The inorganic acid dissolution method mainly depends on corrosion of concentrated acid, the organic solvent dissolution method depends on swelling of an organic solvent, both the inorganic acid dissolution method and the organic solvent dissolution method need to use a large amount of high-concentration chemical agents, the operation time is long, and particularly the swelling period of the organic solvent dissolution method is as long as 7-10 days; in addition, the silicon chip is cracked due to severe corrosion or swelling, and the recovery value of the silicon chip is reduced. Compared with a chemical treatment method, the heat treatment method can completely decompose EVA within a few hours, can realize the integral stripping of silicon wafers with the thickness of 400 mu m and above, but with the thinning development of the silicon wafers, the thickness of the silicon wafers on the market is about 200 mu m generally, and the integral stripping and recovery of the crystal silicon wafers are difficult to realize by simple heat treatment.
The method for disassembling the scrapped photovoltaic module in the Chinese document CN109092842A comprises the following steps: 1) disassembling the aluminum frame; 2) disassembling the junction box; 3) removing the fluorine film; 4) removing the back plate; 5) separating the EVA adhesive layer from the back plate, and separating the silicon chip layer, the welding strip and the glass; 6) the material separates alone, and this scheme is that pressure and the angle through spray gun blowout fluidum separate EVA glue film, backplate, silicon chip layer, weld area and glass, and the silicon chip layer receives the damage easily and is incomplete.
Therefore, the method for disassembling the waste photovoltaic module capable of realizing high-integrity stripping of the silicon wafer is established, has great significance for resource treatment of photovoltaic wastes, meets environmental benefits and economic benefits, and meets the national development requirements.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for disassembling a waste photovoltaic module for realizing the integrity recovery of a silicon wafer, which can realize the complete separation of an aluminum frame, toughened glass, a crystalline silicon wafer, a junction box and a plastic part (EVA and a back plate) and ensure the integrity recovery of the crystalline silicon wafer.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for disassembling a waste photovoltaic module for realizing silicon wafer integrity recovery comprises the following implementation steps:
1) mechanical pre-disassembly
Removing the aluminum frame and the junction box through mechanical disassembly to obtain the photovoltaic substrate without the aluminum frame and the junction box;
2) mixed solvent heat treatment
Clamping the photovoltaic substrate by using a clamp, and limiting the swelling behavior of EVA in the solvent heat treatment process by applying physical pressure; placing the clamped and fixed photovoltaic substrate into a closed container, adding a small amount of organic solvent and pressure auxiliary agent, heating to vaporize the organic solvent and the pressure auxiliary agent, and performing steam type limited swelling on the EVA; after the steam type limited swelling is finished, the photovoltaic substrate is taken out after the organic solvent and the pressure auxiliary agent are condensed, the EVA in the obtained photovoltaic substrate is in a loose and dispersed state, the back plate can be completely peeled off or partially peeled off, and the organic solvent can be repeatedly used after being condensed;
3) pyrolysis heat treatment
The evacuation substrate is placed in a pyrolysis reactor, residual EVA and a back plate are decomposed through high-temperature pyrolysis, so that the complete separation of toughened glass and a crystalline silicon wafer and the integrity recovery of the crystalline silicon wafer are realized, and pyrolysis oil and combustible gas generated in the thermal decomposition process can be used as fuels for supplying heat to the pyrolysis reactor.
Further, the clamp in the step 2) comprises two fixing plates and a clamp connected with the fixing plates, wherein the fixing plates are glass plates or steel plates and are clamped or fixed by the clamp.
Further, in the step 2), the organic solvent is one or a combination of two or more of benzene, toluene, o-dichlorobenzene and trichloroethylene, and the addition amount is 1-5% of the volume of the closed container; preferably, the organic solvent is toluene or trichloroethylene, and the addition amount is 2-3%.
Further, in the step 2), the pressure auxiliary agent is water or an alcohol organic solvent, the addition amount is 2% -10% of the volume of the closed container, and the pressure auxiliary agent steam is used for increasing the pressure in the closed container; preferably, the pressure solvent is water or ethanol, and the addition amount is 3-6%.
Further, in the step 2), the heating temperature is 100-200 ℃ (flexibly adjusted according to the boiling point of the selected solvent), the organic solvent is completely vaporized, and the pressure auxiliary agent is completely or partially vaporized to form a high-temperature high-pressure steam system.
Further, the time required by the steam type limited swelling treatment in the step 2) is 1-4 hours; preferably, the swelling treatment time is 2 to 3 hours.
Further, the heating temperature required in the thermal decomposition process in the step 3) is 400-600 ℃; preferably, the heating temperature is 450-500 ℃.
Further, the time required by the thermal decomposition process in the step 3) is 0.5-2 hours; preferably, the heating time is 0.5 to 1 hour.
Further, the thermal decomposition atmosphere in the pyrolysis reactor in the step 3) is an air atmosphere or an oxygen-free inert gas atmosphere.
The method has the advantages of short operation time, less required chemical agents, capability of completely stripping the crystal silicon wafer in the photovoltaic module, contribution to subsequent treatment and utilization of the crystal silicon wafer and improvement of the recovery value and the economical efficiency of the waste photovoltaic module. Compared with the prior art, the scheme of the invention has the beneficial effects that:
a. compared with the traditional organic solvent dissolving method, the mixed solvent heat treatment adopted by the invention greatly reduces the required chemical agent amount, can be repeatedly used and has small secondary pollution;
b. the heat treatment of the mixed solvent is adopted, and the EVA is subjected to steam swelling at high temperature and high pressure, so that compared with the traditional organic solvent dissolving method, the required time is greatly reduced, and the actual operability is strong;
c. according to the invention, through the heat treatment of the mixed solvent, the back plate is completely removed or partially removed in advance, so that the generation of fluorine-containing harmful gas in the high-temperature decomposition heat treatment process can be avoided or reduced;
d. according to the invention, through the heat treatment of the mixed solvent, the swelling behavior of EVA in the heat treatment process of the solvent is limited by applying physical pressure, the EVA on the photovoltaic substrate is in a loose and dispersed state while the integrity of the silicon wafer is maintained, a passage is provided for gas generated in the high-temperature decomposition heat treatment process, the silicon wafer fragmentation caused by pyrolysis gas accumulation is avoided, after complete decomposition, the complete stripping of the silicon wafer can be realized, the subsequent treatment and utilization of the crystalline silicon wafer are facilitated, and the recovery value and the economical efficiency of waste photovoltaics are improved.
Drawings
FIG. 1 is a schematic view of a crystalline silicon photovoltaic device.
FIG. 2 is a process flow diagram of an embodiment of the invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings in which:
example (b): referring to fig. 2, a method for disassembling a waste photovoltaic module to achieve silicon wafer integrity recycling includes the following steps:
1) mechanical pre-disassembly
Removing the aluminum frame and the junction box through mechanical disassembly to obtain the photovoltaic substrate without the aluminum frame and the junction box;
2) mixed solvent heat treatment
The photovoltaic substrate is clamped by using a clamp, and the swelling behavior of the EVA in the solvent heat treatment process is limited by applying physical pressure, so that the damage of the EVA and the back plate to the crystal silicon wafer due to deformation in the swelling process can be avoided; placing the clamped and fixed photovoltaic substrate into a closed container, adding a small amount of organic solvent and pressure auxiliary agent, heating to raise the temperature to vaporize the organic solvent and the pressure auxiliary agent, wherein the vaporized organic solvent is used as an EVA (ethylene vinyl acetate) solvent, the vaporized pressure auxiliary agent is used for increasing the pressure in the closed container, and performing steam-type limited swelling on the EVA, and a high-temperature high-pressure system formed in the container can improve the EVA swelling efficiency; after the steam type limited swelling is finished, the photovoltaic substrate is taken out after the organic solvent and the pressure auxiliary agent are condensed, the EVA in the obtained photovoltaic substrate is in a loose dispersion state (an evacuated substrate), the back plate can be completely peeled off or partially peeled off, and the organic solvent can be repeatedly used after being condensed;
3) pyrolysis heat treatment
The evacuation substrate is placed in a pyrolysis reactor or a pyrolysis furnace, residual EVA and a back plate are decomposed through high-temperature pyrolysis, so that the complete separation of toughened glass and a crystalline silicon wafer and the integrity recovery of the crystalline silicon wafer are realized, and pyrolysis oil and combustible gas generated in the thermal decomposition process can be used as fuels for supplying heat to the pyrolysis reactor.
The clamp adopted in the step 2) of the invention comprises two fixing plates and a clamp connected with the fixing plates, wherein the fixing plates are glass plates or steel plates and are clamped or fixed by the clamp. The organic solvent in the step 2) can be one or the combination of two or more of benzene, toluene, o-dichlorobenzene, trichloroethylene and other EVA good solvents, and the addition amount is 1-5% of the volume of the closed container; preferably, the organic solvent is toluene or trichloroethylene, and the addition amount is 2-3%. The pressure auxiliary agent in the step 2) can be nontoxic organic solvents such as water or alcohols, can be a combination of water and organic solvents or a combination of two or more organic solvents, the addition amount is 2-10% of the volume of the closed container, and the pressure auxiliary agent steam is used for increasing the pressure in the closed container; preferably, the pressure solvent is water or ethanol, and the addition amount is 3-6%. In the step 2), the heating temperature is 100-200 ℃ (flexibly adjusted according to the boiling point of the selected solvent), the organic solvent is completely vaporized, and the pressure auxiliary agent is completely or partially vaporized to form a high-temperature high-pressure steam system. The time required by the steam type limited swelling treatment in the step 2) is 1-4 hours; preferably, the swelling treatment time is 2 to 3 hours. The heating temperature required in the thermal decomposition process in the step 3) is 400-600 ℃; preferably, the heating temperature is 450-500 ℃. The time required by the thermal decomposition process in the step 3) is 0.5-2 hours; preferably, the heating time is 0.5 to 1 hour. The thermal decomposition atmosphere in the step 3) can be an air atmosphere or an oxygen-free inert gas atmosphere. The silicon wafer recovered by the method has a complete shape, and is beneficial to subsequent treatment and utilization of the silicon wafer.
Compared with the traditional organic solvent dissolving method, the mixed solvent heat treatment adopted by the invention greatly reduces the required chemical agent amount, can be repeatedly used and has small secondary pollution; the heat treatment of the mixed solvent is adopted, and the EVA is subjected to steam swelling at high temperature and high pressure, so that compared with the traditional organic solvent dissolving method, the required time is greatly reduced, and the actual operability is strong; according to the invention, through the heat treatment of the mixed solvent, the back plate is completely removed or partially removed in advance, so that the generation of fluorine-containing harmful gas in the high-temperature decomposition heat treatment process can be avoided or reduced; according to the invention, through the heat treatment of the mixed solvent, the swelling behavior of EVA in the heat treatment process of the solvent is limited by applying physical pressure, the EVA on the photovoltaic substrate is in a loose and dispersed state while the integrity of the silicon wafer is maintained, a passage is provided for gas generated in the high-temperature decomposition heat treatment process, the silicon wafer fragmentation caused by pyrolysis gas accumulation is avoided, after complete decomposition, the complete stripping of the silicon wafer can be realized, the subsequent treatment and utilization of the crystalline silicon wafer are facilitated, and the recovery value and the economical efficiency of waste photovoltaics are improved.
The crystalline silicon photovoltaic module disassembled in the invention mainly comprises an aluminum frame, toughened glass, a crystalline silicon wafer, a junction box, EVA and a back plate, wherein in some literature data, the EVA and the back plate can also be called as plastic parts together.
The technical solution of the present invention is further illustrated by the following specific embodiments.
Example 1
Firstly, mechanically disassembling and removing an aluminum frame and a junction box of the waste polycrystalline silicon photovoltaic module to obtain a photovoltaic substrate without the aluminum frame and the junction box. The swelling behavior of EVA in the heat treatment process of the solvent is limited by applying physical pressure on the photovoltaic substrate through a fixing plate, the photovoltaic substrate is placed in a closed container, methylbenzene and ethanol are added, the volume of the methylbenzene is 2.5% of that of the closed container, the ethanol is heated to 180 ℃, the methylbenzene and the ethanol are vaporized to form a high-temperature and high-pressure system, the EVA is subjected to steam-type limited swelling for 2 hours, the steam-type limited swelling is finished, the photovoltaic substrate is taken out after the methylbenzene and the ethanol are condensed, the EVA in the obtained photovoltaic substrate is in a loose dispersion state (an evacuated substrate), a back plate can be completely peeled off, and the condensed methylbenzene and the condensed ethanol. And placing the evacuated substrate in a pyrolysis reactor, carrying out heat treatment for 30 minutes at 500 ℃ in an air atmosphere, completely decomposing the residual EVA, completely separating the toughened glass from the crystalline silicon wafer, and obtaining the integral crystalline silicon wafer.
Example 2
Firstly, mechanically disassembling and removing an aluminum frame and a junction box of the waste polycrystalline silicon photovoltaic module to obtain a photovoltaic substrate without the aluminum frame and the junction box. The swelling behavior of EVA in the heat treatment process of the solvent is limited by applying physical pressure on the photovoltaic substrate through a fixing plate, the photovoltaic substrate is placed in a closed container, trichloroethylene accounting for 3% of the volume of the closed container and water accounting for 6% of the volume of the closed container are added, heating is carried out until the temperature is raised to 150 ℃ to vaporize the trichloroethylene and the water, a high-temperature and high-pressure system is formed, the EVA is subjected to steam-type limited swelling for 3 hours, the steam-type limited swelling is finished, the photovoltaic substrate is taken out after the trichloroethylene and the water are condensed, the EVA in the obtained photovoltaic substrate is in a loose and dispersed state (an evacuated substrate), a back plate can be partially peeled off. And placing the evacuated substrate in a pyrolysis reactor, pyrolyzing for 30 minutes at 500 ℃ in a nitrogen atmosphere, completely decomposing the residual EVA, completely separating the toughened glass from the crystal silicon wafer, and obtaining the integral crystal silicon wafer.
Example 3
Firstly, mechanically disassembling and removing an aluminum frame and a junction box of the waste polycrystalline silicon photovoltaic module to obtain a photovoltaic substrate without the aluminum frame and the junction box. The swelling behavior of the EVA in the heat treatment process of the physical pressure limiting solvent is exerted on the photovoltaic substrate through a fixing plate, the photovoltaic substrate is placed in a closed container, methylbenzene accounting for 3% of the volume of the closed container and water accounting for 6% of the volume of the closed container are added, heating is carried out until the temperature is increased to 180 ℃ to vaporize the methylbenzene and the water, a high-temperature and high-pressure system is formed, steam-type limited swelling is carried out on the EVA for 3 hours, the steam-type limited swelling is finished, the photovoltaic substrate is taken out after the methylbenzene and the water are condensed, the EVA in the obtained photovoltaic substrate is in a loose dispersion shape (an evacuated substrate), a back plate can be. And placing the evacuated substrate in a pyrolysis reactor, pyrolyzing for 30 minutes at 500 ℃ in a nitrogen atmosphere, completely decomposing the residual EVA, completely separating the toughened glass from the crystal silicon wafer, and obtaining the integral crystal silicon wafer.
The EVA in the present invention is an ethylene-vinyl acetate copolymer abbreviated as english, and the specific techniques or conditions are not specified in the present embodiment, and the techniques or conditions are described in the literature in the art or according to the product specification. The reagents or instruments used are not indicated by manufacturers, and are all conventional products available on the market.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (10)
1. A method for disassembling a waste photovoltaic module for realizing silicon wafer integrity recovery is characterized by comprising the following implementation steps:
1) mechanical pre-disassembly
Removing the aluminum frame and the junction box through mechanical disassembly to obtain the photovoltaic substrate without the aluminum frame and the junction box;
2) mixed solvent heat treatment
Clamping the photovoltaic substrate by using a clamp, and limiting the swelling behavior of EVA in the solvent heat treatment process by applying physical pressure; placing the clamped and fixed photovoltaic substrate into a closed container, adding a small amount of organic solvent and pressure auxiliary agent, heating to vaporize the organic solvent and the pressure auxiliary agent, and performing steam type limited swelling on the EVA; after the steam type limited swelling is finished, the photovoltaic substrate is taken out after the organic solvent and the pressure auxiliary agent are condensed, the EVA in the obtained photovoltaic substrate is in a loose and dispersed state, the back plate can be completely peeled off or partially peeled off, and the organic solvent can be repeatedly used after being condensed;
3) pyrolysis heat treatment
The evacuation substrate is placed in a pyrolysis reactor, residual EVA and a back plate are decomposed through high-temperature pyrolysis, so that the complete separation of toughened glass and a crystalline silicon wafer and the integrity recovery of the crystalline silicon wafer are realized, and pyrolysis oil and combustible gas generated in the thermal decomposition process can be used as fuels for supplying heat to the pyrolysis reactor.
2. The method for disassembling the waste photovoltaic module for realizing the silicon wafer integrity recovery of the claim 1, wherein the clamp in the step 2) comprises two fixing plates and a clamp for connecting the fixing plates, and the fixing plates are glass plates or steel plates and are clamped or fixed by the clamp.
3. The method for disassembling the waste photovoltaic module for realizing the integrity recovery of the silicon wafer according to claim 1, wherein the organic solvent in the step 2) is one or a combination of two or more of benzene, toluene, o-dichlorobenzene and trichloroethylene, the addition amount is 1-5% of the volume of the closed container, and the heated and vaporized organic solvent is used as the EVA solvent.
4. The method for disassembling the waste photovoltaic module for realizing the integrity recovery of the silicon wafer according to any one of claims 1 to 3, wherein the pressure auxiliary agent in the step 2) is water or an alcohol organic solvent, the addition amount is 2 to 10 percent of the volume of the closed container, and the pressure auxiliary agent steam is used for increasing the pressure in the closed container.
5. The method for disassembling the waste photovoltaic module for realizing the integrity recovery of the silicon wafer according to claim 1, wherein the heating temperature in the step 2) is 100-200 ℃, the organic solvent is completely vaporized, and the pressure auxiliary agent is completely or partially vaporized to form a high-temperature high-pressure steam system.
6. The method for disassembling the waste photovoltaic module for realizing silicon wafer integrity recovery according to claim 1, wherein the time required for the steam type limited swelling treatment in the step 2) is 1-4 hours.
7. The method for disassembling the waste photovoltaic module for realizing the integrity recovery of the silicon wafer according to claim 1, wherein the heating temperature required in the thermal decomposition process in the step 3 is 400-600 ℃.
8. The method for disassembling the waste photovoltaic module for realizing the silicon wafer integrity recovery according to claim 7, wherein the time required for the thermal decomposition process in the step 3) is 0.5-2 hours.
9. The method for disassembling the waste photovoltaic module for realizing the integrity recovery of the silicon wafer according to claim 1, wherein the thermal decomposition atmosphere in the pyrolysis reactor in the step 3) is an air atmosphere or an oxygen-free inert gas atmosphere.
10. The method for disassembling the waste photovoltaic module for realizing the integrity recovery of the silicon wafer according to claim 1,
in the step 2), the preferable organic solvent is toluene or trichloroethylene, and the addition amount is 2-3%; preferably, the pressure solvent is water or ethanol, and the addition amount is 3% -6%; the steam type limited swelling optimal treatment time is 2-3 hours;
the heating temperature in the thermal decomposition process in the step 3) is preferably 450-500 ℃, and the treatment time is 0.5-1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910922201.XA CN110624936B (en) | 2019-09-27 | 2019-09-27 | Waste photovoltaic module disassembling method for realizing silicon wafer integrity recovery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910922201.XA CN110624936B (en) | 2019-09-27 | 2019-09-27 | Waste photovoltaic module disassembling method for realizing silicon wafer integrity recovery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110624936A true CN110624936A (en) | 2019-12-31 |
| CN110624936B CN110624936B (en) | 2020-10-02 |
Family
ID=68974606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910922201.XA Active CN110624936B (en) | 2019-09-27 | 2019-09-27 | Waste photovoltaic module disassembling method for realizing silicon wafer integrity recovery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110624936B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113560319A (en) * | 2021-07-21 | 2021-10-29 | 中南大学 | Solvent gasification pyrolysis device and method for waste circuit board |
| CN113857216A (en) * | 2021-09-29 | 2021-12-31 | 中国科学院城市环境研究所 | Method for recycling waste photovoltaic modules |
| CN114378099A (en) * | 2021-12-30 | 2022-04-22 | 中国科学院广州能源研究所 | Microwave pyrolysis-based retired photovoltaic module efficient thermal stratification system and method |
| CN114769272A (en) * | 2022-05-25 | 2022-07-22 | 华北电力大学 | Pyrolysis recovery device for waste photovoltaic modules |
| CN114798690A (en) * | 2022-04-26 | 2022-07-29 | 中国科学院赣江创新研究院 | Method for separating and recycling waste crystalline silicon photovoltaic panels |
| CN114833176A (en) * | 2022-04-19 | 2022-08-02 | 中国科学院广州能源研究所 | Method for comprehensively recycling all components of waste crystalline silicon photovoltaic module |
| CN114871237A (en) * | 2022-04-19 | 2022-08-09 | 中国科学院广州能源研究所 | Method for continuous pyrolysis treatment of waste crystalline silicon photovoltaic module |
| CN115026108A (en) * | 2022-03-31 | 2022-09-09 | 珠海全岂科技有限公司 | Photovoltaic module recycling method |
| CN115090645A (en) * | 2022-05-23 | 2022-09-23 | 深圳先进技术研究院 | Photovoltaic module recycling method and device |
| CN115156265A (en) * | 2022-07-08 | 2022-10-11 | 中国石油大学(华东) | Waste photovoltaic module separation and recovery method based on low-toxicity chemical method |
| CN115447258A (en) * | 2022-08-30 | 2022-12-09 | 浙江中聚材料有限公司 | Photovoltaic module disassembling method |
| WO2023207191A1 (en) * | 2022-04-29 | 2023-11-02 | 西安热工研究院有限公司 | Waste photovoltaic assembly recovery method based on supercritical fluid |
| WO2023239296A3 (en) * | 2022-06-06 | 2024-01-18 | Etavolt Pte Ltd | Assembly and method for photovoltaic (pv) system recycling |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140025003A (en) * | 2012-08-20 | 2014-03-04 | 강원대학교산학협력단 | Device for recycling cell from solar module |
| CN205096223U (en) * | 2015-10-22 | 2016-03-23 | 娄智 | Photovoltaic module recycle device |
| WO2016110825A1 (en) * | 2015-01-08 | 2016-07-14 | OMIZZOLO, Giacomo | Method and apparatus for the disposal of photovoltaic panels |
| TWM559208U (en) * | 2018-01-22 | 2018-05-01 | Xu Ren Cheng | Vapor removal system for waste solar photovoltaic module |
| CN108043863A (en) * | 2017-12-12 | 2018-05-18 | 青海黄河上游水电开发有限责任公司光伏产业技术分公司 | A kind of heating auxiliary recovery method of photovoltaic 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 |
| CN109570195A (en) * | 2018-11-27 | 2019-04-05 | 河海大学常州校区 | A kind of double glass construction packages separation and recovery method |
| CN110016566A (en) * | 2019-05-17 | 2019-07-16 | 河海大学常州校区 | A method of recycling indium in discarded photovoltaic module |
-
2019
- 2019-09-27 CN CN201910922201.XA patent/CN110624936B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140025003A (en) * | 2012-08-20 | 2014-03-04 | 강원대학교산학협력단 | Device for recycling cell from solar module |
| WO2016110825A1 (en) * | 2015-01-08 | 2016-07-14 | OMIZZOLO, Giacomo | Method and apparatus for the disposal of photovoltaic panels |
| CN205096223U (en) * | 2015-10-22 | 2016-03-23 | 娄智 | Photovoltaic module recycle device |
| CN108043863A (en) * | 2017-12-12 | 2018-05-18 | 青海黄河上游水电开发有限责任公司光伏产业技术分公司 | A kind of heating auxiliary recovery method of photovoltaic module |
| TWM559208U (en) * | 2018-01-22 | 2018-05-01 | Xu Ren Cheng | Vapor removal system for waste solar photovoltaic 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 |
| CN109570195A (en) * | 2018-11-27 | 2019-04-05 | 河海大学常州校区 | A kind of double glass construction packages separation and recovery method |
| CN110016566A (en) * | 2019-05-17 | 2019-07-16 | 河海大学常州校区 | A method of recycling indium in discarded photovoltaic module |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602930A (en) * | 2021-07-21 | 2022-06-10 | 中南大学 | Solvent gasification pyrolysis device of abandonment circuit board |
| CN114602930B (en) * | 2021-07-21 | 2023-08-29 | 中南大学 | Solvent gasification pyrolysis device for abandoned circuit board |
| CN113560319A (en) * | 2021-07-21 | 2021-10-29 | 中南大学 | Solvent gasification pyrolysis device and method for waste circuit board |
| CN113560319B (en) * | 2021-07-21 | 2022-04-29 | 中南大学 | Solvent gasification pyrolysis device and method for waste circuit board |
| CN113857216B (en) * | 2021-09-29 | 2022-11-15 | 中国科学院城市环境研究所 | Method for recycling waste photovoltaic modules |
| CN113857216A (en) * | 2021-09-29 | 2021-12-31 | 中国科学院城市环境研究所 | Method for recycling waste photovoltaic modules |
| CN114378099A (en) * | 2021-12-30 | 2022-04-22 | 中国科学院广州能源研究所 | Microwave pyrolysis-based retired photovoltaic module efficient thermal stratification system and method |
| CN115026108A (en) * | 2022-03-31 | 2022-09-09 | 珠海全岂科技有限公司 | Photovoltaic module recycling method |
| CN114833176A (en) * | 2022-04-19 | 2022-08-02 | 中国科学院广州能源研究所 | Method for comprehensively recycling all components of waste crystalline silicon photovoltaic module |
| CN114871237A (en) * | 2022-04-19 | 2022-08-09 | 中国科学院广州能源研究所 | Method for continuous pyrolysis treatment of waste crystalline silicon photovoltaic module |
| CN114798690B (en) * | 2022-04-26 | 2023-08-04 | 中国科学院赣江创新研究院 | Method for separating and recycling waste crystalline silicon photovoltaic panels |
| CN114798690A (en) * | 2022-04-26 | 2022-07-29 | 中国科学院赣江创新研究院 | Method for separating and recycling waste crystalline silicon photovoltaic panels |
| WO2023207191A1 (en) * | 2022-04-29 | 2023-11-02 | 西安热工研究院有限公司 | Waste photovoltaic assembly recovery method based on supercritical fluid |
| CN115090645A (en) * | 2022-05-23 | 2022-09-23 | 深圳先进技术研究院 | Photovoltaic module recycling method and device |
| CN114769272A (en) * | 2022-05-25 | 2022-07-22 | 华北电力大学 | Pyrolysis recovery device for waste photovoltaic modules |
| WO2023239296A3 (en) * | 2022-06-06 | 2024-01-18 | Etavolt Pte Ltd | Assembly and method for photovoltaic (pv) system recycling |
| CN115156265A (en) * | 2022-07-08 | 2022-10-11 | 中国石油大学(华东) | Waste photovoltaic module separation and recovery method based on low-toxicity chemical method |
| CN115447258A (en) * | 2022-08-30 | 2022-12-09 | 浙江中聚材料有限公司 | Photovoltaic module disassembling method |
| CN115447258B (en) * | 2022-08-30 | 2023-11-14 | 浙江中聚材料有限公司 | Photovoltaic module disassembling method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110624936B (en) | 2020-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110624936B (en) | Waste photovoltaic module disassembling method for realizing silicon wafer integrity recovery | |
| Wang et al. | Recycling of materials from silicon base solar cell module | |
| CN114505329A (en) | Decommissioning photovoltaic module disassembling method based on low-temperature pyrolysis | |
| MX2022007075A (en) | Photovoltaic power generation systems and methods regarding same. | |
| WO2022252418A1 (en) | Coal-fired power plant-based microwave cracking treatment system and method for waste wind-turbine blade | |
| KR20130080950A (en) | Method for dismantling eco-friendly waste solar module | |
| CN114410320A (en) | Retired photovoltaic module pyrolysis treatment cooperative full-component recovery method and system | |
| CN114248369A (en) | Method for recovering solar backboard material | |
| CN105057323A (en) | Copper-indium-gallium-selenium flexible thin film solar battery recycling method | |
| CN105355709A (en) | Glass separation method for crystalline silicon solar cell module | |
| CN112133791A (en) | Method for recycling photovoltaic module | |
| CN114833176B (en) | Method for comprehensively recovering all components of waste crystalline silicon photovoltaic module | |
| CN114602953A (en) | Method for disassembling photovoltaic module through heat-assisted machinery | |
| CN115647007A (en) | Comprehensive recovery method of waste photovoltaic module | |
| Chen et al. | The application of organic solvents and thermal process for eliminating EVA resin layer from waste photovoltaic modules | |
| TWI722963B (en) | Photoelectric panel glue processing system | |
| CN113857216B (en) | Method for recycling waste photovoltaic modules | |
| CN115786713A (en) | Method and system for recovering silver and aluminum from retired solar cell panel | |
| CN110743892A (en) | Method for recycling crystalline silicon photovoltaic material | |
| Xu et al. | Overview of the production background and treatment methods of waste photovoltaic modules | |
| CN112404091B (en) | Recovery method of solar cell module | |
| CN117123604A (en) | Method for processing photovoltaic module by chemical method and cooperative segmented pyrolysis | |
| CN210296400U (en) | Recovery device for crystalline silicon photovoltaic module | |
| Xu et al. | Separation of backsheets from waste photovoltaic (PV) modules by ultrasonic irradiation | |
| CN201665640U (en) | Methanol process purge gas energy recovery device and methanol process system |
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 |