Photovoltaic module disassembling and recycling method

Abstract

The invention relates to a photovoltaic module disassembling and recycling method, a photovoltaic module comprises glass, a battery piece, a welding strip, an adhesive film, a frame and a junction box, and the disassembling and recycling method comprises the following steps: disassembling the frame and the junction box of the photovoltaic module to obtain the frame, the junction box and a to-be-processed module laminated part; carrying out mechanical crushing on glass on the surface of the to-be-treated assembly laminated piece to obtain the assembly laminated piece with the crushed surface glass; dividing the component laminated piece with the broken surface glass into a plurality of small component units; the small block assembly units are soaked in a decomposition treatment solution, a mixture of a battery piece and a welding strip and a bonding mixture of a glue film and glass are obtained after ultrasonic action is synchronously used, the battery piece, the welding strip, the glue film and the glass are obtained after sorting, and the decomposition treatment solution comprises alkali, a surface active agent, water and at least one of alcohol amine salt or alcohol. Compared with the prior art, the method has the advantages of high recovery efficiency, low cost, high recovery purity, complete material recovery and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photovoltaic module recycling, in particular to a photovoltaic module disassembly and recycling method. BACKGROUND

[0002] With the rapid development of the photovoltaic industry, the installed capacity of crystalline silicon photovoltaic modules is increasing, and by 2030, the capacity of discarded and disassembled photovoltaic modules will exceed 60 million tons, with an annual increase of 10 million tons of scrap recycling and processing. Photovoltaic modules use materials such as aluminum, silver, copper, glass, adhesive film, back plate, junction box, etc. which can be recycled and reused.

[0003] The existing disassembly and recycling process mainly has two types. The first type is a physical disassembly process, such as patents CN116550716A, CN116274283A, CN117505263A, which has the problem that the material is broken by mechanical crushing and ground into fine powder, the disassembly efficiency is high, the purity of the silicon powder is 60-80%, and the ethylene-vinyl acetate copolymer adhesive film (EVA adhesive film), co-extruded polyolefin adhesive film (EPE adhesive film) contains glass, silicon powder, silver powder, copper powder, etc. The purity of various substances is not high. The second type is a fire disassembly process, such as patent CN114505329A, which has the problem that the adhesive film material is burned and decomposed at high temperature, the battery piece, tinned copper solder strip, and glass are completely recycled, the adhesive film material is basically burned, and the organic residues that are not completely burned cover the surface of the battery piece, solder strip, and glass, affecting subsequent recycling and reuse. The process consumes a lot of energy at a high temperature of 200-500 degrees, and a fire disassembly equipment with a capacity of 10,000 tons per year on the market consumes about 12,000 degrees of electric power energy per day.

[0004] The existing two types of disassembly process recycling material reuse is not ideal. Patent CN114038940A discloses a method for separating the back plate of a photovoltaic module, which adds the photovoltaic laminate to an alkaline alcohol solution for reaction. After the reaction is complete, the fluorine layer in the back plate floats on the upper layer of the reaction solution, the PET layer in the fluorine-containing back plate is dissolved in the reaction solution, and the other parts of the photovoltaic laminate sink to the bottom of the solution. Thus, the back plate and other parts of the photovoltaic laminate are separated. However, this method can only separate the back plate from other parts, and cannot achieve complete separation of all components.

[0005] Therefore, there is an urgent need for a disassembly and recycling process method with high recovery efficiency, low cost, high recovery purity, and complete material recovery to meet the growing demand for material recycling and reuse of scrap components. SUMMARY

[0006] The present application aims to overcome the defects of the prior art and provides a photovoltaic module disassembly and recycling method.

[0007] The object of the present application can be achieved by the following technical solutions: A photovoltaic module disassembly and recycling method, the photovoltaic module comprising glass, cell pieces, solder strips, adhesive film, frame and junction box, the disassembly and recycling method comprising the following steps: S1, removing the frame and junction box of the photovoltaic module to obtain the frame, junction box and component laminates to be processed; S2, mechanically crushing the glass on the surface of the component laminates to be processed to obtain the component laminates with surface glass crushed; S3, dividing the component laminates with surface glass crushed into small component units; S4, immersing the small component units in a decomposition treatment solution, and synchronously using ultrasonic action to obtain a mixture of cell pieces and solder strips, and a bonding mixture of adhesive film and glass, wherein the decomposition treatment solution comprises alkali, surfactant and water, and at least one of alcohol amine salt or alcohol; S5, sorting the mixture of cell pieces and solder strips, and the bonding mixture of adhesive film and glass to obtain cell pieces, solder strips, adhesive film and glass.

[0008] Further, the photovoltaic module is a crystalline silicon photovoltaic module, and the adhesive film is an EVA adhesive film or an EPE adhesive film.

[0009] Further, the photovoltaic module is a double-glass photovoltaic module. Alternatively, the photovoltaic module is a single-glass photovoltaic module, which further comprises a back plate.

[0010] Further, in step S2, the size of the glass fragments in the component laminates with surface glass crushed is 1-10 mm.

[0011] Further, in step S2, a concave-convex interface roller press is used to mechanically crush the glass on the surface of the component laminates to be processed.

[0012] Further, the advancing speed of the component laminates to be processed is 0.1-5 m / min, and the gap between the upper and lower rollers of the roller press is 3-5 mm.

[0013] Further, in step S3, the component laminates with surface glass crushed are divided into small component units, which is beneficial to improving the processing efficiency in the decomposition process.

[0014] Further, the interval of the segmentation is 10-300mm, preferably according to the size of the battery piece, wherein the size of the battery piece is mostly 183*183mm, 210*210mm, 183mm*210mm, and can be adjusted according to the influence of laboratory conditions, such as 100mm*100mm in the embodiment.

[0015] Further, in step S4, the base includes one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium acetate, sodium bicarbonate, sodium methoxide or sodium ethoxide.

[0016] The alcohol includes one or more of methanol, ethanol, isopropanol, propylene glycol, ethylene glycol, diethylene glycol or glycerol.

[0017] Further, in step S4, the alcohol amine salt is formed by the reaction of alcohol amine and acid; the alcohol amine includes one or more of ethanolamine, diethanolamine, triethanolamine or isopropanolamine; The acid includes organic acid and inorganic acid, wherein the organic acid includes one or more of short-chain carboxylic acid, aromatic acid, fatty acid or substituted carboxylic acid; The short-chain carboxylic acid includes one or more of formic acid, acetic acid or propionic acid; The aromatic acid includes benzoic acid or salicylic acid; The fatty acid includes one or more of benzoic acid, oleic acid, linoleic acid, palmitoleic acid, palmitic acid, lauric acid, stearic acid, butyric acid or myristic acid, and the inorganic acid includes one or more of hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid; The substituted carboxylic acid includes one or more of lactic acid, citric acid or pyruvic acid.

[0018] Further, the acid is fatty acid, including one or more of oleic acid, linoleic acid, palmitoleic acid, palmitic acid, lauric acid, stearic acid, butyric acid or myristic acid.

[0019] Further, the alcohol amine salt includes one or more of triethanolamine oleate, triethanolamine stearate, triethanolamine laurate, triethanolamine palmitate, diethanolamine oleate, diethanolamine linoleate, ethanolamine oleate, ethanolamine stearate, isopropanolamine oleate, triethanolamine myristate, ethanolamine hydrochloride, diethanolamine hydrochloride, isopropanolamine hydrochloride, ethanolamine sulfate, diethanolamine nitrate or triethanolamine phosphate.

[0020] Further, in step S4, the surfactant includes one or more of sodium dodecyl benzene sulfonate, alkyl glycoside, block polyether, fatty alcohol polyoxyethylene ether or sorbitan fatty acid polyoxyethylene ether.

[0021] Further, in step S4, the mass concentration of the base is 40-500 g / L, preferably 120-240 g / L. When the decomposition treatment solution is a mixed solution of a base, a surfactant, water, and an alcohol amine salt, the sum of the mass concentrations of the alcohol amine salt and the surfactant is 20-240 g / L, preferably 50-80 g / L; and the mass ratio of the alcohol amine salt to the surfactant is 2-6:1. When the decomposition treatment solution is a mixed solution of a base, a surfactant, water, and an alcohol, the sum of the mass concentrations of the alcohol and the surfactant is 20-240 g / L, preferably 50-80 g / L; and the mass ratio of the alcohol to the surfactant is 2-6:1. When the decomposition treatment solution is a mixed solution of a base, a surfactant, water, an alcohol amine salt, and an alcohol, the sum of the mass concentrations of the alcohol amine salt, the alcohol, and the surfactant is 20-240 g / L, preferably 50-80 g / L; the mass ratio of the sum of the alcohol amine salt and the alcohol to the surfactant is 2-6:1; and the mass ratio of the alcohol amine salt to the alcohol is 1:1-2.

[0022] Further, in step S4, the temperature of the decomposition treatment solution is 60-100℃, preferably 70-80℃.

[0023] Further, in step S4, the time of the immersion is 10-120 min, preferably 30-60 min.

[0024] Further, in step S4, the parameters of the ultrasonic are as follows: the frequency is 10-200 KHZ, preferably 20-40 KHZ; and the power is 0.1-10 W / cm 2 , preferably 0.5-1 W / cm 2 .

[0025] Compared with the prior art, the present application has the following advantages: In the decomposition treatment solution of the present application, the key adhesive material (adhesive film) in the photovoltaic laminated piece is efficiently decomposed through the synergistic effect of each component. The base is the main force of the hydrolysis reaction, and the surfactant, alcohol amine salt, and / or alcohol system assists in accelerating the hydrolysis reaction, thereby significantly improving the effect and efficiency of the reaction. By destroying the ester bond of the adhesive film, the industry problem of completely separating the adhesive film from the glass, solder strip, and cell piece is solved, and most of the adhesive film remains for recycling. This multi-reaction synergistic mechanism enables the adhesive film to be separated from the glass, solder strip, and cell piece under mild conditions, thereby realizing efficient, high-integrity, and high-purity recycling of the core components such as cell pieces, glass, solder strips, and adhesive films.

[0026] The present application forms uniform micro-cracks between the glass surface and different material layers, which opens a channel for the decomposition treatment solution to reach the internal reaction interface. This greatly increases the effective reaction area, so that the decomposition treatment solution can fully exert its decomposition efficiency. Compared with traditional physical methods or high-temperature pyrolysis processes, significant progress has been made in the value of recovered products, process green safety, and treatment efficiency.

[0027] (3) The present application introduces ultrasonic treatment, which realizes the synergistic strengthening of physical peeling and chemical reaction. The cavitation effect generated by ultrasonic waves can form high-pressure shock waves in the liquid, which can produce mechanical tearing effect on the EVA bonding interface weakened by chemical weakening, accelerating the physical separation of each layer of material. On the other hand, ultrasonic cavitation and the strong acoustic streaming effect accompanying it can greatly promote the diffusion and update of the decomposition treatment solution to the narrow interface under the broken glass, effectively destroy the boundary layer, ensure the full contact of reactants and timely removal of degradation products, thereby significantly shorten the overall treatment time and improve the separation cleanliness of the battery piece and the glass.

[0028] (4) The alcohol amine salt and / or alcohol and surfactant system of the present application greatly promotes the infiltration and penetration depth of the decomposition treatment solution between each material layer of the assembly. Under mild reaction conditions, the synergistic strengthening of chemical reaction and interfacial penetration is realized. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The flow chart of the photovoltaic module disassembly and recycling method of the present application; Figure 2 The pictures of each structure in the disassembly and recycling process of Example 3, (a) small assembly unit, (b) mixture of solder strip and battery piece, (c) bonding mixture of adhesive film and glass, (d) solder strip, (e) battery piece, (f) adhesive film, (g) broken glass; Figure 3 The pictures of the products obtained by disassembly and recycling of Example 3, (a) tin-plated copper strip, (b) glass, (c) battery piece, (d) adhesive film; Figure 4 The SEM pictures of the products obtained by disassembly and recycling of Example 3, (a) glass, (b) tin-plated copper strip, (c) battery piece; Figure 5 The pictures of the products obtained by disassembly and recycling of Example 4, (a) fluorine film, (b) PET, EVA adhesive film and glass without separation, (c) solder strip, battery piece; Figure 6 The pictures of the products obtained after 90 min of immersion of Comparative Example 1; Figure 7 The pictures of the products obtained after 600 min of immersion of Comparative Example 2; Figure 8 The pictures of the products obtained after 90 min of immersion of Comparative Example 3. Detailed Implementation

[0030] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments. All other embodiments obtained by those skilled in the art based on the given embodiments without creative effort are within the scope of protection of this application.

[0031] Unless otherwise specified, the reagents, methods, instruments and equipment used in this invention are conventional reagents, methods, instruments and equipment in the art.

[0032] Example 1 A method for dismantling and recycling photovoltaic modules, comprising the following steps: (1) Prepare waste crystalline silicon double-glass photovoltaic modules, mechanically remove the frame and junction box of the photovoltaic modules to obtain the frame, junction box and module laminate to be processed.

[0033] (2) The photovoltaic module to be processed is mechanically crushed using a roller press with a concave-convex interface to obtain a module laminate with broken glass on the surface. The forward speed of the photovoltaic module to be processed is 1m / min, the gap between the upper and lower rollers of the roller press is 5.0mm, and most of the broken glass is 1~10mm in size.

[0034] (3) Divide the broken surface glass of the module laminate into small strips along the edge of the cell at a spacing of 100mm, and divide the small strips into small module units along the edge of the cell at a spacing of 100mm.

[0035] (4) Immerse the weighed small component unit sample in the decomposition treatment solution, and simultaneously use 20KHZ, 0.5W / cm 2 Ultrasonic synergistic processing.

[0036] The decomposition treatment solution is a mixture of alkali, an alcoholic amine salt, a surfactant, and water, at a temperature of 80°C, and an immersion time of 60 minutes. The alkali is sodium hydroxide with a mass concentration of 160 g / L; the alcoholic amine salt is triethanolamine oleate; and the surfactant is an alkyl glycoside. The sum of the mass concentrations of the alcoholic amine salt and the surfactant is 60 g / L, and the mass ratio of triethanolamine oleate to alkyl glycoside is 5:1. After preparing the alkali, triethanolamine oleate and alkyl glycoside are added sequentially to the alkali solution, and then the mixture is heated to 80°C before proceeding with subsequent operations.

[0037] When the decomposition treatment solution is a mixture of alkali, alcoholamine salt, surfactant and water, the sample is completely decomposed after immersion for 60 minutes.

[0038] Example 2 A photovoltaic module disassembly recycling method, the disassembly recycling method comprising the following steps: (1) Prepare a waste crystalline silicon double-glass photovoltaic module, mechanically remove the frame and junction box of the photovoltaic module to obtain the frame, junction box and a component laminate to be processed.

[0039] (2) Use a roller press device with a concave-convex interface to mechanically crush the component laminate to be processed to obtain a component laminate with surface glass broken. The advance speed of the photovoltaic module to be processed is 1 m / min, the gap between the upper and lower rollers of the roller press is 5.0 mm, and most of the glass broken has a size of 1-10 mm.

[0040] (3) Divide the component laminate with surface glass broken into small strips along the edges of the cell pieces at an interval of 100 mm, and divide the small strips into small block component units along the edges of the cell pieces at an interval of 100 mm.

[0041] (4) Immersing the weighed small block component unit sample in a decomposition treatment solution, while using 20 KHZ, 0.5 W / cm 2 ultrasonic waves for cooperative treatment.

[0042] The decomposition treatment solution is a mixed solution of alkali, alcohol, surfactant and water, the temperature is 80°C, and the immersion time is 60 min. The alkali is sodium hydroxide, the mass concentration is 160 g / L; the alcohol is propylene glycol; the surfactant is alkyl glycoside, the sum of the mass concentrations of the alcohol and the surfactant is 60 g / L, and the mass ratio of propylene glycol to alkyl glycoside is 5:1. After the alkali is prepared, the propylene glycol and the alkyl glycoside are sequentially added to the alkali solution, and then heated to 80°C to start the subsequent operation.

[0043] In the case where the decomposition treatment solution is a mixed solution of alkali, alcohol, surfactant and water, the sample is completely decomposed after immersion for 60 min.

[0044] Example 3 A photovoltaic module disassembly recycling method, the photovoltaic module comprising glass, cell pieces, solder strips (tin-plated copper strips), EVA adhesive film, a frame and a junction box, the disassembly recycling method comprising the following steps, as shown in Figure 1 . (1) Prepare a waste crystalline silicon double-glass photovoltaic module, mechanically remove the frame and junction box of the photovoltaic module to obtain the frame, junction box and a component laminate to be processed.

[0045] (2) Use a roller press device with a concave-convex interface to mechanically crush the component laminate to be processed to obtain a component laminate with surface glass broken. The advance speed of the photovoltaic module to be processed is 1 m / min, the gap between the upper and lower rollers of the roller press is 5.0 mm, and most of the glass broken has a size of 1-10 mm.

[0046] (3) The surface glass broken assembly laminates are cut into small strips along the edges of the cell sheet at an interval of 100 mm, and the small strips are cut into small block assembly units along the edges of the cell sheet at an interval of 100 mm, see Figure 2 (a). A small block assembly unit sample is weighed, with a mass of 67.4 grams.

[0047] (4) The weighed small block assembly unit sample is immersed in a decomposition treatment solution, while being treated with 20 KHZ, 0.5 W / cm 2 ultrasonic waves. The decomposition treatment solution is a mixed solution of alkali, alcohol amine salt, alcohol, surfactant and water, with a temperature of 80°C and an immersion time of 30 min. The alkali is sodium hydroxide, with a mass concentration of 160 g / L; the alcohol is propylene glycol; the alcohol amine salt is triethanolamine oleate, and the surfactant is alkyl polyglycoside. The sum of the mass concentrations of the alcohol amine salt, alcohol and surfactant is 60 g / L, and the mass ratio of triethanolamine oleate, propylene glycol and alkyl polyglycoside is 2:3:1. The alkali solution is prepared, and then triethanolamine oleate, propylene glycol and alkyl polyglycoside are sequentially added to the alkali solution, followed by heating to 80°C and starting the subsequent operation.

[0048] After immersion, the adhesive mixture of the adhesive film and the glass, and the mixture of the cell sheet and the solder strip can be separated, see Figure 2 (b), (c).

[0049] (5) The adhesive film and the glass are manually sorted to obtain the adhesive film and the glass, and the mixture of the cell sheet and the solder strip is manually sorted to obtain the cell sheet and the solder strip, see Figure 2 (d)-(g). This embodiment is carried out under laboratory conditions, so manual sorting is used. If it is applied to large-scale industrial production in the future, mechanical separation can be used.

[0050] (6) The mass of the glass is 54.8 grams, the mass of the EVA adhesive film is 7.7 grams, the mass of the tin-plated copper strip is 0.8 grams, the mass of the cell sheet is 3.1 grams, and the mass of the mixture of the cell sheet and the glass fine powder is 1.0 gram, with a total mass of 67.4 grams. The surface photos of the treated materials are shown in Figure 3 . The glass, tin-plated copper strip and cell sheet obtained are subjected to SEM testing, and the results are shown in Figure 4 . As can be seen from the figures, the surfaces of the glass, tin-plated copper strip and cell sheet are free of EVA residues, which is conducive to the recycling of the glass, tin-plated copper strip and cell sheet. However, the existing physical disassembly process and pyrometallurgical disassembly process leave EVA residues on the surfaces of the glass, tin-plated copper strip and cell sheet.

[0051] Example 4 A photovoltaic module disassembly and recycling method, the photovoltaic module comprising glass, cell sheet, solder strip (tin-plated copper strip), back plate, EVA adhesive film, frame and junction box, the disassembly and recycling method comprising the following steps: (1) Prepare the waste crystalline silicon single-glass photovoltaic module, mechanically remove the frame and junction box of the photovoltaic module to obtain the frame, junction box and the component laminated part to be treated.

[0052] (2) Use a roller press equipment with concave-convex interface to mechanically crush the component laminated part to be treated to obtain the component laminated part with surface glass crushed. The forward speed of the photovoltaic module to be treated is 1 m / min, the gap between the upper and lower rollers of the roller press is 4.0 mm, and the size of the glass crushed is mostly 1-10 mm.

[0053] (3) Divide the component laminated part with surface glass crushed into small strips along the cell edge at an interval of 100 mm, and divide the small strips into small block component units along the cell edge at an interval of 100 mm.

[0054] (4) Immersing the small block component unit sample weighed into the decomposition treatment solution, while using 20 KHZ, 0.5 W / cm 2 ultrasonic wave for cooperative treatment. The decomposition treatment solution is a mixed solution of alkali, alcohol amine salt, alcohol, surfactant and water, the temperature is 80℃, and the immersion time is 30 min. The alkali is sodium hydroxide, the mass concentration is 160 g / L; the alcohol is propylene glycol; the alcohol amine salt is triethanolamine oleate, the surfactant is alkyl polyglycoside, the sum of the mass concentrations of the alcohol amine salt, alcohol and surfactant is 60 g / L, and the mass ratio of triethanolamine oleate, propylene glycol and alkyl polyglycoside is 2:3:1. The alkali solution is prepared, then triethanolamine oleate, propylene glycol and alkyl polyglycoside are sequentially added into the alkali solution, then heated to 80℃, and the subsequent operation is started.

[0055] After immersion, the adhesive mixture of polyethylene terephthalate (PET), fluorine film, EVA adhesive film, cell, solder strip, adhesive film and glass can be separated.

[0056] (5) Separate the adhesive film and glass adhesive mixture to obtain the adhesive film and glass.

[0057] The disassembly and recycling method of the present application also has effect on single-glass photovoltaic modules, and can separate PET and fluorine film, which is beneficial to the subsequent environmental protection treatment of fluorine film, and the schematic diagram is shown in Figure 5 .

[0058] Comparative Example 1 A photovoltaic module disassembly and recycling method, compared with Example 3, is mostly the same, except that ultrasonic is not performed in step (4). The disassembly and recycling method comprises the following steps: (1) Prepare 600W crystalline silicon double-glass photovoltaic module, mechanically remove the frame and junction box of the photovoltaic module to obtain the frame, junction box and the component laminated part to be treated.

[0059] (2) The photovoltaic module to be processed is mechanically crushed using a roller press with a concave-convex interface to obtain a module laminate with broken glass on the surface. The forward speed of the photovoltaic module to be processed is 1m / min, the gap between the upper and lower rollers of the roller press is 5.0mm, and most of the broken glass is 1~10mm in size.

[0060] (3) Divide the broken surface glass of the module laminate into small strips along the edge of the cell at a spacing of 100mm, and divide the small strips into small module units along the edge of the cell at a spacing of 100mm.

[0061] (4) Immerse the weighed small component unit sample in the decomposition treatment solution. The decomposition treatment solution is a mixture of alkali, an alcoholic amine salt, an alcohol, a surfactant, and water, at a temperature of 80°C. The alkali is sodium hydroxide with a mass concentration of 160 g / L; the alcohol is propylene glycol; the alcoholic amine salt is triethanolamine oleate; and the surfactant is alkyl glycoside. The sum of the mass concentrations of the alcoholic amine salt, alcohol, and surfactant is 60 g / L, and the mass ratio of triethanolamine oleate, propylene glycol, and alkyl glycoside is 2:3:1. After preparing the alkali solution, add triethanolamine oleate, propylene glycol, and alkyl glycoside sequentially to the alkali solution, then heat to 80°C to begin subsequent operations.

[0062] When the immersion time is 90 minutes, the adhesive mixture of the film and glass, part of the battery cell, and the solder ribbon are separated. Figure 6 As shown, the small component units were not completely decomposed. Further immersion for 150 minutes resulted in complete decomposition of the small component units. This demonstrates the effectiveness of ultrasonic treatment in improving component separation efficiency.

[0063] Comparative Example 2 A method for dismantling and recycling photovoltaic modules is largely the same as that in Example 3, except that no alkali is added to the decomposition solution in step (4). This dismantling and recycling method includes the following steps: (1) Prepare waste crystalline silicon double-glass photovoltaic modules, mechanically remove the frame and junction box of the photovoltaic modules to obtain the frame, junction box and module laminate to be processed.

[0064] (2) The photovoltaic module to be processed is mechanically crushed using a roller press with a concave-convex interface to obtain a module laminate with broken glass on the surface. The forward speed of the photovoltaic module to be processed is 1m / min, the gap between the upper and lower rollers of the roller press is 5.0mm, and most of the broken glass is 1~10mm in size.

[0065] (3) Divide the broken surface glass of the module laminate into small strips along the edge of the cell at a spacing of 100mm, and divide the small strips into small module units along the edge of the cell at a spacing of 100mm.

[0066] (4) The weighed small block assembly unit sample is immersed in a decomposition treatment solution, and 20 KHZ, 0.5 W / cm 2 ultrasonic wave is used for cooperative treatment. The decomposition treatment solution is a mixed solution of alcohol amine salt, alcohol, and surfactant, and water, and the temperature is 80°C. The alcohol is propylene glycol; the alcohol amine salt is triethanolamine oleate, and the surfactant is alkyl glycoside. The mass concentration of the alcohol amine salt, the alcohol, and the surfactant is 60 g / L, and the mass ratio of triethanolamine oleate, propylene glycol, and alkyl glycoside is 2:3:1. Triethanolamine oleate, propylene glycol, and alkyl glycoside are sequentially added to water, and then heated to 80°C, and the subsequent operation is started.

[0067] After 120 min of immersion, the sample is not decomposed. Continue to immerse until 600 min as shown in Figure 7 The sample is still not decomposed, showing that there is no hydrolysis of the alkaline solution, and the adhesive film cannot be separated from the glass, the solder strip, and the battery piece.

[0068] Comparative Example 3 A photovoltaic module disassembly and recycling method is compared with Example 3, and most of them are the same, except that the decomposition treatment solution in step (4) is a sodium hydroxide aqueous solution. The disassembly and recycling method comprises the following steps, as shown in Figure 1 . (1) Prepare a waste crystalline silicon double-glass photovoltaic module, mechanically shovel off the frame and junction box of the photovoltaic module, and obtain the frame, junction box, and component laminated piece to be treated.

[0069] (2) Use a roller press equipment with concave-convex interface to mechanically crush the component laminated piece to be treated, and obtain a component laminated piece with surface glass crushed. The forward speed of the photovoltaic module to be treated is 1 m / min, the gap between the upper and lower rollers of the roller press is 5.0 mm, and the glass crushing size is mostly 1-10 mm.

[0070] (3) The component laminated piece with surface glass crushed is divided into small strips along the edge of the battery piece at an interval of 100 mm, and the small strips are divided into small block assembly units along the edge of the battery piece at an interval of 100 mm.

[0071] (4) The weighed small block assembly unit sample is immersed in a decomposition treatment solution, and 20 KHZ, 0.5 W / cm 2 ultrasonic wave is used for cooperative treatment. The decomposition treatment solution is a mixed solution of alcohol amine salt, alcohol, and surfactant, and water, and the temperature is 80°C. The alcohol is propylene glycol; the alcohol amine salt is triethanolamine oleate, and the surfactant is alkyl glycoside. The mass concentration of the alcohol amine salt, the alcohol, and the surfactant is 60 g / L, and the mass ratio of triethanolamine oleate, propylene glycol, and alkyl glycoside is 2:3:1. Triethanolamine oleate, propylene glycol, and alkyl glycoside are sequentially added to water, and then heated to 80°C, and the subsequent operation is started.

[0072] After 90 min of immersion, as shown in Figure 8As shown, the sample decomposition reaction did not complete within 90 min. Continued immersion to 300 min resulted in complete sample decomposition. This indicates that while alkaline solutions can be used to decompose, high efficiency decomposition is difficult to achieve and is not the optimal solution.

[0073] While the application has been described in detail with particular references to specific embodiments thereof, it will be understood by those skilled in the art that various modifications or changes in form and details can be made therein without departing from the spirit and scope thereof. It is therefore intended that the application be construed as including all such modifications and changes as fall within the scope of the appended claims.

Claims

1. A method for dismantling and recycling photovoltaic modules, characterized in that, Photovoltaic modules include glass, solar cells, solder ribbons, encapsulant film, frames, and junction boxes. This dismantling and recycling method includes the following steps: S1. Remove the frame and junction box of the photovoltaic module to obtain the frame, junction box and module laminate to be processed; S2. Mechanically break the glass on the surface of the component laminate to be processed to obtain a component laminate with broken surface glass; S3. Divide the component laminate with broken surface glass into several small component units; S4. The small component unit is immersed in the decomposition treatment solution and ultrasonic treatment is applied simultaneously to obtain a mixture of battery cell and solder ribbon, adhesive film and glass bonding mixture, wherein the decomposition treatment solution includes alkali, surfactant, water, and at least one of alcoholic amine salt or alcohol. S5. The mixture of battery cells and solder ribbon, and the adhesive mixture of film and glass are sorted to obtain battery cells, solder ribbon, film and glass.

2. The method for dismantling and recycling photovoltaic modules according to claim 1, characterized in that, In step S2, the glass fragments in the laminated component with broken surface glass have a size of 1~10mm.

3. The method for dismantling and recycling photovoltaic modules according to claim 1, characterized in that, In step S4, the alkali includes one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, sodium methoxide, or sodium ethoxide.

4. The method for dismantling and recycling photovoltaic modules according to claim 1, characterized in that, In step S4, the alcohols include one or more of methanol, ethanol, isopropanol, propylene glycol, ethylene glycol, diethylene glycol, or glycerol.

5. A method for dismantling and recycling photovoltaic modules according to claim 1, characterized in that, In step S4, the alkanolamine salt is formed by the reaction of an alkanolamine with an acid; The alkanolamine includes one or more of ethanolamine, diethanolamine, triethanolamine, or isopropanolamine; The acid includes organic acids and inorganic acids, wherein the organic acid includes one or more of short-chain carboxylic acids, aromatic acids, fatty acids or substituted carboxylic acids; The short-chain carboxylic acids include one or more of formic acid, acetic acid, or propionic acid; The aromatic acid includes benzoic acid or salicylic acid; The fatty acids include one or more of benzoic acid, oleic acid, linoleic acid, palmitoleic acid, palmitic acid, lauric acid, stearic acid, butyric acid, or myristic acid; and the inorganic acids include one or more of hydrochloric acid, phosphoric acid, sulfuric acid, or nitric acid. The substituted carboxylic acids include one or more of lactic acid, citric acid, or pyruvic acid.

6. A method for dismantling and recycling photovoltaic modules according to claim 5, characterized in that, The alcoholamine salts include one or more of the following: triethanolamine oleate, triethanolamine stearate, triethanolamine laurate, triethanolamine palmitate, diethanolamine oleate, diethanolamine linoleate, ethanolamine oleate, ethanolamine stearate, isopropanolamine oleate, triethanolamine myristate, ethanolamine hydrochloride, diethanolamine hydrochloride, isopropanolamine hydrochloride, ethanolamine sulfate, diethanolamine nitrate, or triethanolamine phosphate.

7. A method for dismantling and recycling photovoltaic modules according to claim 1, characterized in that, In step S4, the surfactant includes one or more of sodium dodecylbenzenesulfonate, alkyl glycoside, block polyether, fatty alcohol polyoxyethylene ether, or dehydrated sorbitol fatty acid polyoxyethylene ether.

8. A method for dismantling and recycling photovoltaic modules according to claim 1, characterized in that, In step S4, the mass concentration of the alkali is 40~500g / L; When the decomposition treatment solution is a mixed solution of alkali, surfactant, water, and alcohol amine salt, the sum of the mass concentrations of the alcohol amine salt and the surfactant is 20~240 g / L, and the mass ratio of the alcohol amine salt to the surfactant is 2~6:1; When the decomposition treatment solution is a mixed solution of alkali, surfactant, water, and alcohol, the sum of the mass concentrations of the alcohol and surfactant is 20~240g / L, and the mass ratio of the alcohol to the surfactant is 2~6:

1. When the decomposition treatment solution is a mixed solution of alkali, surfactant, water, alcoholic amine salt, and alcohol, the sum of the mass concentrations of the alcoholic amine salt, alcohol, and surfactant is 20~240 g / L, the mass ratio of the sum of the alcoholic amine salt and alcohol to the surfactant is 2~6:1, and the mass ratio of the alcoholic amine salt to alcohol is 1:1~2.

9. A method for dismantling and recycling photovoltaic modules according to claim 1, characterized in that, In step S4, the temperature of the decomposition treatment solution is 60~100℃.

10. A method for dismantling and recycling photovoltaic modules according to claim 1, characterized in that, In step S4, the parameters of the ultrasound are: frequency 10~200kHz, power 0.1~10W / cm. 2 .

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