CN115090645A - Photovoltaic module recycling method and device - Google Patents
Photovoltaic module recycling method and device Download PDFInfo
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- CN115090645A CN115090645A CN202210566221.XA CN202210566221A CN115090645A CN 115090645 A CN115090645 A CN 115090645A CN 202210566221 A CN202210566221 A CN 202210566221A CN 115090645 A CN115090645 A CN 115090645A
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 12
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 12
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- 238000003860 storage Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- Environmental & Geological Engineering (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
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- Processing Of Solid Wastes (AREA)
Abstract
The application discloses a recovery method and a recovery device of a photovoltaic module, wherein the recovery method comprises the following steps: preprocessing the photovoltaic module to obtain a photovoltaic laminated part; the photovoltaic laminating piece comprises a glass substrate, a first organic film layer, a battery sheet layer, a second organic film layer and a back plate which are sequentially laminated; placing the photovoltaic laminated part in a closed container, adding an organic cosolvent and an organic solvent, injecting carbon dioxide through pumping pressure, and swelling the first organic film layer and the second organic film layer after the carbon dioxide reaches a supercritical state; wherein the time required for swelling is not more than 30 min; and after the swelling is finished, taking out the photovoltaic laminated part to obtain the glass substrate, the cell sheet layer and the back plate which are separated from each other. The supercritical carbon dioxide and organic cosolvent synergistic effect is adopted, so that the layering of the EVA layer and the glass substrate, the battery sheet layer and the back plate can be promoted in a short reaction time, and the complete recovery of materials can be realized.
Description
Technical Field
The application relates to the technical field of photovoltaic module recycling, in particular to a photovoltaic module recycling method and device.
Background
A photovoltaic module is a device that can convert solar energy into electric energy, and is generally composed of a glass substrate, an encapsulating material, a silicon wafer (cell sheet), a back sheet, and a metal. The encapsulant is typically Ethylene-Vinyl Acetate Copolymer (EVA), which has good adhesion to glass, battery sheet, and back sheet. Most of the glass, silicon, aluminum, silver and other component materials in the glass substrate, the silicon wafer and the back plate can be recycled by recovery. How to separate materials such as a glass substrate, a silicon wafer and a back plate in the recycling process becomes a technical problem in the recycling process of the photovoltaic module.
The existing photovoltaic module recycling method generally comprises two steps of module disassembly and component recycling. The main difficulty in disassembling the components is how to destroy the adhesive force of the EVA. The major processing techniques at present can be divided into physical, pyrolytic and chemical methods, depending on the method of breaking the EVA cohesion. The physical method mainly adopts a physical crushing mode to separate and recover the components, and the crushed materials need to be further screened and classified; the pyrolysis method is mainly characterized in that high temperature is adopted to pyrolyze EVA which plays a role in bonding in the assembly into various gases so as to realize the separation between the cell and the glass substrate; whereas the chemical process mainly employs an organic solvent to dissolve or swell the EVA, separating it from the rest, and thus obtaining the various parts of the assembly.
However, the physical method cannot obtain complete batteries and glass substrates, and the subsequent screening and separation are difficult; the reaction time of the pyrolysis method is short, but the silicon wafer is easy to crack due to stress and gas release generated by EVA decomposition in the treatment process, and the silicon wafer is difficult to be completely stripped and recycled due to simple heat treatment along with the thinning and development of the silicon wafer; the chemical method needs to use a large amount of high-concentration chemical agent, the swelling period is as long as 10 days, and the silicon wafer is easy to crack due to severe corrosion or swelling, so that the recycling value is reduced.
Disclosure of Invention
The technical problem mainly solved by the application is to provide a recovery method and a recovery device of a photovoltaic module, and the problems that in the prior art, the reaction time is long and materials cannot be completely recovered can be solved.
In order to solve the above technical problem, a first technical solution adopted in the present application is to provide a method for recovering a photovoltaic module, including: preprocessing the photovoltaic module to obtain a photovoltaic laminated part; the photovoltaic laminating piece comprises a glass substrate, a first organic film layer, a battery sheet layer, a second organic film layer and a back plate which are sequentially laminated; placing the photovoltaic laminated part in a closed container, adding an organic cosolvent and an organic solvent, injecting carbon dioxide through pumping pressure, and swelling the first organic film layer and the second organic film layer after the carbon dioxide reaches a supercritical state; wherein the time required for swelling is not more than 30 min; and after the swelling is finished, taking out the photovoltaic laminated part to obtain the glass substrate, the cell sheet layer and the back plate which are separated from each other.
Wherein the solid-liquid ratio of the first organic film layer to the second organic film layer to the organic cosolvent and the organic solvent is controlled to be 1: 12.
wherein the swelling reaction temperature is controlled to be 150-180 ℃, and the swelling reaction pressure is controlled to be 74-210 bar.
The first organic film layer and the second organic film layer are made of ethylene-vinyl acetate copolymer.
Wherein the organic cosolvent comprises toluene, and the organic solvent comprises ethyl acetate, acetone, ethanol, isopropanol, dichloromethane and hexane.
Wherein the injected carbon dioxide is high-purity carbon dioxide with the purity of not less than 99.9 percent.
Wherein, carry out the preliminary treatment to photovoltaic module, obtain the step of photovoltaic lamination spare, specifically include: and mechanically disassembling to remove the aluminum frame and the junction box of the photovoltaic module to obtain the photovoltaic laminated part.
The battery piece layer consists of a plurality of battery pieces; after the swelling is finished, the photovoltaic laminated part is taken out, and the glass substrate, the cell sheet layer and the back plate which are separated from each other are obtained, and the method comprises the following steps: and placing all the battery pieces included in the battery piece layer in a cleaning device, and extracting, separating and purifying the battery pieces to obtain the processed battery pieces.
The method comprises the following steps of placing all battery pieces included by a battery piece layer in a cleaning device, extracting, separating and purifying the battery pieces to obtain the processed battery pieces, and specifically comprises the following steps: soaking the cell in a hydrochloric acid solution to obtain an aluminum-removed cell and an aluminiferous acid solution; soaking the aluminum-removed cell in a nitric acid solution to obtain a silver-removed cell and a silver-containing acid solution; soaking the silver-removed cell in hot phosphoric acid solution to obtain a treated cell with silicon nitride removed and silicon nitride-containing acid solution; and recovering aluminum, silver and silicon nitride in the battery piece based on the aluminiferous acid solution, the silver-containing acid solution and the silicon nitride-containing acid solution.
In order to solve the technical problem, a second technical scheme adopted by the application is to provide a recovery device of a photovoltaic module, wherein the recovery device comprises a closed container, a carbon dioxide storage, a high-pressure pump and a heat exchanger; the high-pressure pump is respectively connected with the carbon dioxide storage and the closed container and is used for injecting the carbon dioxide in the carbon dioxide storage into the closed container; the heat exchanger is communicated with the high-pressure pump and the closed container and is used for heating the carbon dioxide so that the carbon dioxide enters the closed container after reaching a supercritical state; the closed container comprises a feed inlet and a discharge outlet, the feed inlet is used for adding the photovoltaic laminating part obtained after the photovoltaic assembly is pretreated, the organic cosolvent and the organic solvent, and the discharge outlet is used for collecting the photovoltaic laminating part so as to obtain the glass substrate, the battery sheet layer and the back plate which are separated from each other.
The beneficial effect of this application is: different from the prior art, the photovoltaic module recovery method and the photovoltaic module recovery device provided by the application have the advantages that the first organic film layer and the second organic film layer are swelled by injecting carbon dioxide and swelling the first organic film layer and the second organic film layer after the carbon dioxide reaches the supercritical state, so that the first organic film layer and the second organic film layer can be better permeated and swelled by utilizing the characteristics of high diffusivity, low viscosity and no surface tension of the supercritical fluid, and the dissolution rates of the first organic film layer and the second organic film layer are improved. Meanwhile, the polarity of the supercritical carbon dioxide can be enhanced by adding the organic cosolvent, the solubility of metal ions can be increased by the cosolvent formed by the organic cosolvent and the metal ions, and the layering of the first organic film layer and the second organic film layer with the glass substrate, the battery sheet layer and the back plate can be promoted by improving the extraction capacity of the metal ions, so that the falling of each component is accelerated, the glass substrate, the battery sheet layer and the back plate which are separated from each other can be obtained after a short swelling period, and the complete recovery of materials is realized.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow diagram of one embodiment of a method for recycling a photovoltaic module according to the present application;
FIG. 2 is a structural schematic of an embodiment of a photovoltaic module;
FIG. 3 is a schematic view illustrating a swelling process of the first organic glue film layer in FIG. 2;
FIG. 4 is a schematic structural view of an embodiment of a recycling apparatus for photovoltaic modules according to the present application;
fig. 5 is a microscopic image of a photovoltaic laminate during swelling taken in the recovery device of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise, the "plural" includes at least two in general, but does not exclude the presence of at least one.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
It should be understood that the terms "comprises," "comprising," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
In the existing method for recovering the photovoltaic module, a physical method cannot obtain a complete battery and a glass substrate, and subsequent screening and separation are difficult; the reaction time of the pyrolysis method is short, but the silicon wafer is easy to crack due to stress and gas release generated by EVA decomposition in the treatment process, and as the silicon wafer becomes thinner and develops, the integrity stripping and recycling of the silicon wafer are difficult to realize by simple heat treatment; the chemical method requires the use of a large amount of high concentration chemical agent, and the swelling device is as long as 10 days, and the severe corrosion or swelling also easily causes the silicon wafer to be cracked, thereby reducing the recycling value.
Based on the situation, the photovoltaic module recycling method and the photovoltaic module recycling device can solve the problems that in the prior art, the reaction time is long and materials cannot be completely recycled.
Referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a recycling method of a photovoltaic module according to the present application. In this embodiment, the preparation method comprises:
s11: preprocessing the photovoltaic module to obtain a photovoltaic laminated part; the photovoltaic laminating piece comprises a glass substrate, a first organic film layer, a battery sheet layer, a second organic film layer and a back plate which are sequentially laminated.
Specifically, referring to fig. 2, fig. 2 is a schematic structural diagram of an embodiment of a photovoltaic device. In this embodiment, the photovoltaic module 100 includes an aluminum frame 6, a junction box 7, and a glass substrate 1, a first organic adhesive film layer 2, a cell sheet layer 3, a second organic adhesive film layer 4, and a back sheet 5 stacked in sequence from top to bottom.
In this embodiment, the aluminum frame 6 and the junction box 7 of the photovoltaic module 100 are mechanically disassembled and removed to obtain the photovoltaic laminate which only includes the glass substrate 1, the first organic adhesive film layer 2, the cell sheet layer 3, the second organic adhesive film layer 4 and the back sheet 5.
The first organic adhesive film layer 2 and the second organic adhesive film layer 4 are made of ethylene-vinyl acetate copolymer.
Wherein the cell sheet layer 3 is composed of a plurality of cell sheets (silicon wafers) 30.
The photovoltaic module 100 generally contains 70% of glass, 10% of aluminum, 10% of an organic film layer, 5% of a silicon wafer and 5% of a junction box, and in the embodiment, the aluminum frame 6 and the junction box 7 are firstly recycled through simple mechanical disassembly, and then the glass substrate 1, the back plate 5, the cell 30 and metals such as silver grid lines and copper solder strips in the cell 30 are recycled through subsequent steps.
S12: placing the photovoltaic laminated part in a closed container, adding an organic cosolvent and an organic solvent, injecting carbon dioxide through pumping pressure, and swelling the first organic film layer and the second organic film layer after the carbon dioxide reaches a supercritical state; wherein the time required for swelling does not exceed 30 min.
In the present embodiment, carbon dioxide (CO) is injected 2 ) The organic cosolvent is high purity carbon dioxide with purity not less than 99.9%, and the organic solvent comprises ethyl acetate, acetone, ethanol, isopropanol, dichloromethane and hexane.
In the embodiment, the swelling reaction temperature is controlled to be 150-180 ℃, and the swelling reaction pressure is controlled to be 74-210 bar.
Specifically, carbon dioxide becomes supercritical carbon dioxide (ScCO) at a temperature higher than the critical temperature Tc of 31.1 ℃ and a pressure higher than the critical pressure Pc of 73.8bar 2 ) Its properties change. Under supercritical state, ScCO 2 Density and liquid CO of 2 Has similar density and viscosity to that of gas CO 2 Similarly, the composite material has many excellent properties, such as large diffusion coefficient, low viscosity, no surface tension, and rapid change of mass transfer and dissolution capacity, dielectric constant and other properties along with pressure regulation, and has strong penetration and swelling capacity on natural polymers and synthetic polymers.
Wherein, when the pressure value is close to the near pressure and the temperature is increased, the ScCO is used for controlling the temperature of the sample 2 Diffusivity and gaseous CO 2 Similar diffusivity, high mass transfer power, and possibly increased ScCO at high temperature 2 For hydrocarbon diffusion and extraction, for most polymers, the viscosity is reduced due to the temperature increase, and ScCO is affected by the diffusivity 2 Enter the pores of the polymer to promote ScCO 2 Permeability to polymer. Since the viscosity of EVA will increase above 180 deg.C, in a preferred embodiment, the ScCO can be maximized at lower EVA viscosity by controlling the reaction temperature at 180 deg.C and the reaction pressure at 75bar 2 The optimal EVA dissolution rate is realized for the diffusion and extraction of EVA.
It can be understood that, injecting high-purity carbon dioxide into the closed container, and swelling the first organic adhesive film layer 1 and the second organic adhesive film layer 2 after the high-purity carbon dioxide becomes supercritical carbon dioxide can better permeate and swell the first organic adhesive film layer 2 and the second organic adhesive film layer 4 by utilizing the characteristics of high diffusivity, low viscosity and no surface tension of the supercritical fluid, thereby improving the dissolution rate of the first organic adhesive film layer 2 and the second organic adhesive film layer 4.
Due to ScCO 2 Is a non-polar solvent, and the metal complex has extremely strong polarity (is insoluble in ScCO) 2 ) By ScCO alone 2 Swelling EVA may cause low interaction in the extraction process, and EVA polymer is difficult to separate, and in order to solve the problem, ScCO is injected in the embodiment 2 At the same time, toluene is added to enhance ScCO 2 Of (c) is used.
The toluene molecules are polar molecules and can dissolve the EVA polymer, but the toluene molecules have small polarity and can be approximately considered as a non-polar solvent, so that the toluene molecules can be matched with ScCO 2 The cosolvent formed by the two is stronger in breaking capacity of chemical bonds in the metal complex, and can directly extract metal ions from the solid matrix, so that the solubility of the metal ions is increased, and the subsequent recovery of metal is facilitated.
Further, the solid-to-liquid ratio (S/L) of the first organic glue film layer 2, the second organic glue film layer 4, the organic cosolvent and the organic solvent is controlled to be 1: 12. wherein, the solid-liquid ratio refers to the mass or volume ratio of the solid phase and the liquid phase in the suspension, the solid phase is the total mass of the EVA, and the liquid phase refers to the amount of all liquid characterization except the EVA. The total mass of the EVA may be determined based on the mass of the photovoltaic module 100 and the proportion of the first organic adhesive film layer 2 to the second organic adhesive film layer 2.
Specifically, the boiling point of toluene is 90 ℃, the boiling point of ethyl acetate is 63 ℃, the boiling point of acetone is 46 ℃, the boiling point of ethanol is 63 ℃, the boiling point of isopropanol is 67 ℃, the boiling point of dichloromethane is 32 ℃, the boiling point of hexane is 58 ℃, both the organic cosolvent and the organic solvent are vaporized at the temperature (150-180 ℃) required by swelling, the EVA can be subjected to steam-type swelling, and the dissolving rate of the EVA is further improved.
Referring to fig. 3 of the drawings, in which,fig. 3 is a schematic view illustrating a swelling process of the first organic glue film layer in fig. 2. In this embodiment, ScCO is injected into a closed vessel 2 After reacting with toluene, ScCO at the reaction temperature and reaction pressure required for swelling 2 And the EVA polymer gradually expands after nucleation and growth after permeating into the first organic adhesive film layer 2 until being layered with the glass substrate 1 and the cell sheet layer 3, wherein the cell sheet layer 3 forms a plurality of cell sheets 30 after falling off.
In this embodiment, ScCO is used 2 The cosolvent system formed by the organic solvent and the methylbenzene can improve the extraction capacity of metal ions and promote the layering of the first organic adhesive film layer 2, the second organic adhesive film layer 4 and the battery sheet layer 3, so that the falling of all components is accelerated, the glass substrate 1, the battery sheet layer 3 and the back plate 5 which are separated from one another can be obtained, and the complete recovery of materials is realized. Compared with the dissolving time of up to several days in the prior art, the EVA swelling and layering can be completed within 30min by the embodiment, so that the reaction time is greatly shortened, and the recovery efficiency of the photovoltaic module is improved.
S13: and after the swelling is finished, taking out the photovoltaic laminated part to obtain the glass substrate, the cell sheet layer and the back plate which are separated from each other.
In the embodiment, the photovoltaic laminated part is taken out after the organic cosolvent and the organic solvent are condensed, the first organic adhesive film layer 2 and the second organic adhesive film layer 4 in the photovoltaic laminated part are in a loose dispersion state, the glass substrate 1, the battery sheet layer 3 and the back plate 5 are completely separated, and the organic cosolvent and the organic solvent can be repeatedly used after being condensed.
Further, all the battery pieces 30 included in the battery piece layer 3 are placed in a cleaning device, and the battery pieces 30 are extracted, separated and purified to obtain the processed battery pieces 30.
Specifically, the battery piece 30 is first soaked in a hydrochloric acid solution to obtain an aluminum-removed battery piece and an aluminiferous acid solution. And then, placing the aluminum-removed cell in a nitric acid solution for soaking to obtain a silver-removed cell and a silver-containing acid solution. And then soaking the silver-removed cell in hot phosphoric acid solution to obtain the treated cell with silicon nitride removed and silicon nitride-containing acid solution. Finally, the aluminum, silver and silicon nitride in the cell 30 are recovered based on the aluminum-containing acid solution, the silver-containing acid solution and the silicon nitride-containing acid solution.
In this embodiment, lead-containing solder paste is printed on the main grid lines on the surface of the battery sheet 30, and lead wires can be recovered when the battery sheet 30 is processed. In other embodiments, a lead-free solder paste may be used, which is not limited in this application.
Through a large number of experiments, the inventor of the present application found that, at a reaction temperature of 160 ℃, the recovery rates of the battery piece 30, the glass substrate 1, the back plate 5 and the lead wires can reach 100%, and the purities of the glass substrate 1, the lead wires and the back plate 5 respectively reach 77.1 ± 0.85%, 89.15 ± 0.63% and 84.26 ± 1.04%. Within the set reaction temperature (150 ℃ -180 ℃), the recovery rates of the battery piece 30, the glass substrate 1, the back plate 5 and the lead wires are kept at 100% along with the continuous increase of the temperature, but the purities of the components are gradually improved, and when the reaction temperature reaches 180 ℃, the purities of the glass substrate 1, the lead wires and the back plate 5 reach 84.61 +/-1.29%, 92.07 +/-0.37% and 93.55 +/-2.65%, respectively.
It can be understood that the swelling reaction temperature is controlled to be 180 ℃, the swelling reaction pressure is controlled to be 75bar, the solid-to-liquid ratio (S/L) of the first organic film layer 2 to the second organic film layer 4 to the organic cosolvent and the organic solvent is controlled to be 1: 12, the optimal EVA dissolution rate and the recovery purity of the material can be realized.
Different from the prior art, in the embodiment, by injecting carbon dioxide and swelling the first organic adhesive film layer 2 and the second organic adhesive film layer 4 after the carbon dioxide reaches the supercritical state, the first organic adhesive film layer 2 and the second organic adhesive film layer 4 can be better permeated and swelled by utilizing the characteristics of high diffusivity, low viscosity and no surface tension of the supercritical fluid, so that the dissolution rates of the first organic adhesive film layer 2 and the second organic adhesive film layer 4 are improved. Meanwhile, the polarity of the supercritical carbon dioxide can be enhanced by adding the organic cosolvent, the solubility of metal ions can be increased by the cosolvent formed by the organic cosolvent and the metal ions, and the delamination of the first organic glue film layer 2 and the second organic glue film layer 4 with the glass substrate 1, the battery sheet layer 3 and the back plate 5 can be promoted by improving the extraction capacity of the metal ions, so that the falling-off of each component is accelerated, the glass substrate 1, the battery sheet layer 3 and the back plate 5 which are separated from each other can be obtained after a short swelling period, and the complete recovery of materials is realized.
Correspondingly, the application provides a photovoltaic module's recovery unit.
Specifically, please refer to fig. 4, fig. 4 is a schematic structural diagram of an embodiment of a recycling apparatus of a photovoltaic module according to the present application.
In the present embodiment, the recovery device 200 includes a closed casing 201, a carbon dioxide storage 202, a high-pressure pump 203, and a heat exchanger 204. The high-pressure pump 203 is connected to the carbon dioxide storage 202 and the closed vessel 201, respectively, and injects carbon dioxide in the carbon dioxide storage 202 into the closed vessel 201. The heat exchanger 204 communicates the high-pressure pump 203 with the closed vessel 201, and heats the carbon dioxide to a supercritical state, and then the carbon dioxide enters the closed vessel 201. The closed container 201 includes a feed inlet (not shown) and a discharge outlet 2011, the feed inlet is used for adding the photovoltaic laminate obtained after the photovoltaic module is pretreated, and the organic cosolvent and the organic solvent, and the discharge outlet 2011 is used for collecting the photovoltaic laminate to obtain the glass substrate, the cell layer and the back plate which are separated from each other.
Wherein, the closed container 201 comprises a reaction kettle.
Wherein the high-pressure pump 203 is equipped with a pressure regulation system, which regulates the pressure to the working pressure for a time of about 20 s. In one particular implementation scenario, the maximum flow of the high pressure pump 203 is 50g/min and the operating flow rate is set to 20 g/min.
In the present embodiment, the recovery apparatus 200 further includes a circulation cooling apparatus 205. A circulation cooling device 205 is connected to the high-pressure pump 203 for dissipating heat from the high-pressure pump 203.
In this embodiment, the recovery device further includes a controller 206. A controller 206 is connected to the closed vessel 201 for controlling the reaction pressure in the closed vessel 201. The controller 206 controls the time for the reaction pressure in the closed vessel 201 to reach the operating pressure to be 20 seconds.
In this embodiment, the recycling device 200 further includes an illumination device 207 and a camera module 208.
Wherein, the lighting device 207 is arranged at one side of the closed container 201 and is used for lighting the sample reacted in the closed container 201. In one specific implementation scenario, the illumination device 207 is an LED ring lamp (81 mm outer diameter, 60 ° illumination cone) capable of illuminating the sample in a uniform manner.
Wherein the camera assembly 208 is disposed on a side of the illumination device 207 away from the hermetic container 201. The camera assembly 208 includes a high magnification lens 2081, with the high magnification lens 2081 disposed proximate to the illumination device 207. In one particular implementation scenario, the high magnification lens 2081 is a zero distortion macro lens with a magnification of 9.8 μm per pixel method.
In this embodiment, the recovery apparatus 200 further includes an external control apparatus 209. The external control device 209 includes a computer.
The camera module 208 and the controller 206 are electrically connected to the external control device 209, respectively, and when the controller 206 controls the pressure in the closed container 201 to decrease to 8bar, the external control device 209 controls the camera module 208 to photograph the sample in the closed container 201, and transmits the photographed image to the external control device 209, and then the external control device 209 is used to display the image.
Specifically, referring to fig. 5, fig. 5 is a microscopic image of the photovoltaic laminate during swelling taken in the recovery device of the present application. In this embodiment, the swelling reaction temperature is controlled to be 180 ℃, the swelling reaction pressure is controlled to be 75bar, and the solid-to-liquid ratio (S/L) of the first organic glue film layer 2, the second organic glue film layer 4 and the organic cosolvent is controlled to be 1: 12, at a reaction time of 50s, the first organic glue film layer 2 and the second organic glue film layer 4 in the photovoltaic laminate have expanded significantly, and at a reaction time of 70s, the first organic glue film layer 2 and the second organic glue film layer 4 have begun to delaminate from the glass substrate 3, the cell sheet layer 3, and the backsheet 5, indicating that the recycling device 200 is capable of rapidly swelling the EVA layer and delaminating from the remaining components.
Unlike the prior art, the recovery apparatus 200 according to the present embodiment adds the carbon dioxide storage 202, and injects the carbon dioxide stored in the carbon dioxide storage 202 into the closed container by using the high-pressure pump 203, so that the first organic film layer and the second organic film layer can be better permeated and swollen by using the characteristics of the supercritical carbon dioxide, such as high diffusivity, low viscosity, and no surface tension, thereby improving the dissolution rates of the first organic film layer and the second organic film layer. Meanwhile, the polarity of the supercritical carbon dioxide can be enhanced by adding the organic cosolvent, the solubility of metal ions can be increased by the cosolvent formed by the organic cosolvent and the metal ions, and the layering of the first organic film layer and the second organic film layer with the glass substrate, the battery sheet layer and the back plate can be promoted by improving the extraction capacity of the metal ions, so that the falling of each component is accelerated, the glass substrate, the battery sheet layer and the back plate which are separated from each other can be obtained after a short swelling period, and the complete recovery of materials is realized.
The above description is only an embodiment of the present application, and not intended to limit the scope of the present application, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the specification and the drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present application.
Claims (10)
1. A method for recycling a photovoltaic module, comprising:
preprocessing the photovoltaic module to obtain a photovoltaic laminated part; the photovoltaic laminating piece comprises a glass substrate, a first organic film layer, a battery sheet layer, a second organic film layer and a back plate which are sequentially laminated;
placing the photovoltaic laminated piece into a closed container, adding an organic cosolvent and an organic solvent, injecting carbon dioxide through pumping pressure, and swelling the first organic glue film layer and the second organic glue film layer after the carbon dioxide reaches a supercritical state; wherein the time required for the swelling does not exceed 30 min;
and after the swelling is finished, taking out the photovoltaic laminated part to obtain the glass substrate, the cell sheet layer and the back plate which are separated from each other.
2. The recycling method according to claim 1, wherein the solid-to-liquid ratio of the first organic film layer to the second organic film layer to the organic cosolvent and the organic solvent is controlled to be 1: 12.
3. the recycling method according to claim 2, wherein the swelling reaction temperature is controlled to 150 to 180 ℃ and the swelling reaction pressure is controlled to 74 to 210 bar.
4. The recycling method according to any one of claims 1 to 3, wherein the first organic adhesive layer and the second organic adhesive layer are made of ethylene-vinyl acetate copolymer.
5. The recovery method according to any one of claims 1 to 3, wherein the organic cosolvent comprises toluene and the organic solvent comprises ethyl acetate, acetone, ethanol, isopropanol, dichloromethane, and hexane.
6. A recovery method according to any one of claims 1 to 3, wherein the carbon dioxide injected is high purity carbon dioxide having a purity of not less than 99.9%.
7. The recycling method according to claim 1, wherein the step of pretreating the photovoltaic module to obtain a photovoltaic laminate comprises:
and mechanically disassembling and removing the aluminum frame and the junction box of the photovoltaic module to obtain the photovoltaic laminated part.
8. The recycling method according to claim 1, wherein the cell sheet layer is composed of a plurality of cell sheets;
after the swelling is finished, the step of taking out the photovoltaic laminate to obtain the glass substrate, the cell sheet layer and the back sheet which are separated from each other comprises the following steps:
and placing all the battery pieces included in the battery piece layer in a cleaning device, and extracting, separating and purifying the battery pieces to obtain the processed battery pieces.
9. The recycling method according to claim 8, wherein the step of placing all the battery pieces included in the battery piece layer in a cleaning device, and extracting, separating and purifying the battery pieces to obtain the processed battery pieces specifically comprises:
soaking the battery piece in a hydrochloric acid solution to obtain an aluminum-removed battery piece and an aluminiferous acid solution;
soaking the aluminum-removed cell in a nitric acid solution to obtain a silver-removed cell and a silver-containing acid solution;
soaking the silver-removed cell in hot phosphoric acid solution to obtain the treated cell with silicon nitride removed and silicon nitride-containing acid solution;
and recovering aluminum, silver and silicon nitride in the battery piece based on the aluminum-containing acid solution, the silver-containing acid solution and the silicon nitride-containing acid solution.
10. The recovery device of the photovoltaic module is characterized by comprising a closed container, a carbon dioxide storage, a high-pressure pump and a heat exchanger;
the high-pressure pump is respectively connected with the carbon dioxide storage and the closed container and is used for injecting the carbon dioxide in the carbon dioxide storage into the closed container;
the heat exchanger is communicated with the high-pressure pump and the closed container and is used for heating the carbon dioxide so that the carbon dioxide enters the closed container after reaching a supercritical state;
the closed container comprises a feeding hole and a discharging hole, the feeding hole is used for adding the photovoltaic laminating piece obtained after the photovoltaic assembly is pretreated, and an organic cosolvent and an organic solvent, and the discharging hole is used for collecting the photovoltaic laminating piece to obtain a glass substrate, a battery sheet layer and a back plate which are separated from each other.
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| CN202210566221.XA CN115090645A (en) | 2022-05-23 | 2022-05-23 | Photovoltaic module recycling method and device |
| PCT/CN2022/137811 WO2023226373A1 (en) | 2022-05-23 | 2022-12-09 | Photovoltaic module recovery method and recovery device |
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| WO2023226373A1 (en) * | 2022-05-23 | 2023-11-30 | 深圳先进技术研究院 | Photovoltaic module recovery method and recovery device |
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