CN115430692A - Novel method for separating and recycling retired photovoltaic module - Google Patents
Novel method for separating and recycling retired photovoltaic module Download PDFInfo
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- 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
- B09B3/40—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
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/35—Shredding, crushing or cutting
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- 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
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- 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
Abstract
The invention belongs to the field of harmless and recycling treatment of retired photovoltaic modules, and relates to a new method for separating and recycling photovoltaic modules. The invention provides a separation and recovery method of a retired photovoltaic module, which comprises the following steps: firstly, sequentially removing the additional structure, completely stripping the back plate and the glass layer by a heat treatment method to obtain a crystalline silicon cell sheet layer with the upper surface and the lower surface both stuck with sealing materials; and then, the obtained crystalline silicon cell sheet with the upper surface and the lower surface both adhered with the sealing material is subjected to cryogenic treatment at the temperature of-190 to-20 ℃ to split the crystalline silicon cell sheet, and metal is enriched on a splitting surface due to severe shrinkage of metal in the crystalline silicon cell sheet at low temperature, so that the metal is convenient to purify and recover subsequently. The method disclosed by the invention avoids the problems of difficult separation and difficult purification caused by crushing and mixing, can effectively shorten the recovery time of the solvent, and improves the metal separation purity.
Description
Technical Field
The invention relates to the field of retired photovoltaic module harmless and resource disposal; in particular to a novel process method for separating and recovering a photovoltaic module by heat treatment and deep cooling.
Background
The photovoltaic power generation is a new energy technology for converting solar energy into electric energy, the basic structure of a photovoltaic module comprises a crystalline silicon battery layer, an organic packaging layer, cover plate glass, a back plate, an outer frame and a junction box, wherein the cover plate glass, the back plate and a solar battery are bonded through the organic packaging layer.
According to the prediction of the international renewable energy agency, the worldwide rejection amount of photovoltaic modules reaches 7800 ten thousand tons by 2050, wherein the rejection amount of Chinese photovoltaic modules exceeds 2000 ten thousand tons. If the traditional waste treatment methods such as incineration, landfill and the like are adopted, not only can great resource waste be caused, but also the serious environmental pollution problem can be caused. Therefore, the retired photovoltaic module is recycled, so that the ecological environment pressure can be effectively relieved, and the resource recycling is realized.
The existing decomposition and recovery strategies of the photovoltaic module usually adopt the technical means of pyrolysis chemical methods (which can cause environmental pollution), crushing, low-temperature grinding, cryogenic cooling physics and the like to obtain the mixed particle (silicon particles, backboard polymer particles, EVA particles and the like) battery powder. However, the mixed particle battery powder is difficult to directly extract, and often needs to be subjected to a subsequent screening process (vibration, electrostatic screening method and the like), so that the purity of the recovered material is influenced.
In order to solve the problems, a method with stable process and simple equipment operation is urgently needed for separating various materials (silicon, aluminum, silver, polymers, glass and the like) of the photovoltaic module so as to realize value-added utilization.
Disclosure of Invention
Aiming at the defects, the invention provides a new method for separating and recovering the retired photovoltaic module material, which comprises the steps of removing a junction box and an aluminum frame through a series of heat treatment methods, and completely stripping a high-molecular back plate and glass to obtain a crystalline silicon battery piece with EVA adhesive films (EVA/Si/EVA three-layer structure) adhered to two sides; then, the battery piece with the EVA/Si/EVA laminated structure is subjected to cryogenic treatment by a cryogenic method (such as liquid nitrogen soaking), so that a metal silicon (Si) battery layer (containing various metals and mainly silicon) is effectively split, the metals (silicon, aluminum, silver, indium, gallium and the like) can be completely exposed, subsequent solvent purification and recovery (contact area is increased), the problems of difficult separation and difficult purification caused by crushing and mixing are avoided, the solvent recovery time can be effectively shortened, and the metal separation purity is improved.
The technical scheme of the invention is as follows:
the invention provides a separation and recovery method of a retired photovoltaic module, wherein the retired photovoltaic module comprises an additional structure and a laminated piece, the additional structure comprises a junction box and a frame, and the laminated piece comprises a glass layer, a first sealing material layer, a crystalline silicon battery piece layer, a second sealing material layer and a back plate;
the separation and recovery method comprises the following steps: sequentially removing the additional structure, completely stripping the back plate and the glass layer by a heat treatment method to obtain a crystalline silicon cell layer with the upper surface and the lower surface both adhered with sealing materials; and then, the obtained crystalline silicon battery sheet with the sealing materials adhered to the upper surface and the lower surface is subjected to cryogenic treatment at-190 to-20 ℃ to split the crystalline silicon battery sheet, and metal (mainly comprising silicon, and also comprising aluminum, silver, indium or gallium) is enriched on a splitting surface due to severe contraction of metal in the crystalline silicon battery sheet at low temperature, so that the subsequent purification and recovery of the metal are facilitated.
Further, the separation and recovery method comprises the following steps:
1) Removing the additional structure of the retired photovoltaic module through heat treatment to obtain a complete laminated part;
2) Softening the back plate by heat treatment of the obtained laminated piece, and completely stripping the softened back plate by using a tool to obtain a recycled polymer back plate material;
3) Continuously carrying out heat treatment on the rest assembly comprising the glass layer and the crystalline silicon cell sheet layer, stripping the crystalline silicon cell sheet layer from the surface of the glass to obtain a complete glass material and the crystalline silicon cell sheet layer with the upper and lower surfaces adhered with sealing materials;
4) Cutting the crystalline silicon cell sheet layer with the sealing materials adhered to the upper surface and the lower surface to obtain a regular cell sheet, then carrying out subzero treatment on the cell sheet with the regular shape at-190 to-20 ℃, splitting the crystalline silicon cell sheet after the subzero treatment, and completely exposing the metal in the crystalline silicon cell sheet due to the severe shrinkage of the metal in the crystalline silicon cell sheet at low temperature;
5) Recovering the metal material by a solvent dissolution recovery method.
Further, in the step 4), the cryogenic treatment adopts the following mode: liquid nitrogen quenching, liquid helium quenching, dry ice acetone quenching or dry ice acetonitrile quenching and the like.
Further, in step 5), the metal is aluminum, silicon, silver, indium, gallium or the like.
Further, in step 5), the solvent in the solvent dissolution recovery method includes: naOH, HF, HNO 3 、 H 2 SO 4 、H 3 PO 4 、H 2 SiF 6 、KOH、NH 3 Or Br 2 And the like.
Further, in the steps 1) to 3), the heat treatment temperature is 100-250 ℃, and the heat treatment time is 0.1-2 h.
Further, the recovery method further comprises: and (3) carrying out grading treatment on the polymer backboard material obtained in the step 2) for direct use or high value-added recycling.
Further, the above recovery method further comprises: and 3) carrying out grading treatment on the glass material obtained in the step 3) for direct use or recycling.
The second technical problem to be solved by the invention is to provide a method for improving the purity of the recovered metal obtained in the recovery treatment of the retired photovoltaic module, which comprises the following steps: firstly, sequentially removing the additional structure, completely stripping the back plate and the glass layer by a heat treatment method to obtain a crystalline silicon cell sheet layer with the upper surface and the lower surface both stuck with sealing materials; and then, carrying out cryogenic treatment on the obtained crystalline silicon battery sheet at-190 to-20 ℃ to split the metal silicon battery sheet, so that the metal can be completely exposed, and the purity of the recovered metal is improved by a subsequent solvent purification recovery method due to the increase of the contact area.
The invention has the beneficial effects that:
the invention adopts heat treatment to assist disassembly to obtain the battery laminating piece adhered with the sealing layer material (such as an EVA (ethylene vinyl acetate) adhesive film), and the battery pieces are effectively separated by direct cryogenic treatment (such as liquid nitrogen treatment) through cutting; the metal material (silicon, aluminum, silver, indium, gallium and other metals) can be completely exposed by utilizing the severe contraction of the metal at low temperature, so that the subsequent solvent purification and recovery (increasing the contact area) are facilitated, the problems of difficult separation and difficult purification caused by crushing and mixing are avoided, the solvent recovery time can be effectively shortened, and the metal separation purity is improved.
Description of the drawings:
FIG. 1 is a process flow diagram of an embodiment of the invention.
Fig. 2 is a scanning electron photograph (fig. 2a and 2 d) and energy spectrum analysis results (fig. 2b, c-upper sample, fig. 2e, f-lower sample) of a cross section of a cell in which a silicon layer is effectively separated after the cryogenic treatment according to example 1, step 5) of the present invention (two samples obtained after quenching are respectively referred to as upper sample and lower sample).
Fig. 3 is a scanning electron photograph (fig. 3 a) and energy spectrum analysis results (fig. 3 b-f) of the surface of an upper sample of a silicon layer effectively divided cell piece in example 1 of the present invention.
Detailed Description
The junction box and the aluminum frame in the retired photovoltaic module are effectively removed through a series of heat treatment methods, and then the back plate and the glass material are completely stripped; finally, the cell piece with the EVA/Si/EVA laminated structure is subjected to direct cryogenic treatment (such as liquid nitrogen treatment) to effectively separate the cell piece from the silicon layer; by utilizing the split battery piece, metal materials (such as silicon, aluminum, silver, indium, gallium and the like) can be completely exposed, so that subsequent solvent purification and recovery (increase of contact area) are facilitated, the problems of difficult separation and difficult purification caused by crushing and mixing are avoided, the solvent recovery time can be effectively shortened, and the metal separation purity is improved.
The following examples are presented to further illustrate the invention and are not intended to limit the invention to the embodiments described.
Example 1
A method for efficiently recycling a retired photovoltaic module by heat treatment and deep cooling double-auxiliary separation comprises the following specific steps:
1) Placing the complete photovoltaic module on a heating platform, setting the temperature of the platform at 100 ℃, processing for 1 hour, and removing an aluminum frame and a junction box to obtain a complete photovoltaic laminating piece;
2) Adjusting the temperature of the heating platform to 200 ℃, treating for 0.5 hour, stripping the softened back plate layer by using a cutter, and grading the stripped back plate for treatment or recycling high value;
3) Adjusting the temperature of the heating platform to 180 ℃, treating for 1 hour, stripping the crystalline silicon battery layer from the surface of the glass, and performing grading treatment or recycling on the obtained complete glass, and performing subsequent treatment on the obtained battery layer adhered with the EVA adhesive film;
4) Taking the cell layer adhered with the EVA adhesive film from the heating platform, and cutting along the cell array to obtain 24 blocks of 20 × 10cm 2 A battery piece;
5) All the battery pieces are soaked in liquid nitrogen together and are soaked for 5 minutes in a cryogenic manner, the metals in the battery pieces are effectively separated due to severe low-temperature shrinkage, the step can completely expose the metals (such as silicon, aluminum, silver, indium or gallium and the like) (as shown in figures 2-3) so as to facilitate subsequent solvent purification and recovery (increase the contact area), and therefore the problems of difficult separation and difficult purification caused by crushing and mixing in the prior art are solved, the solvent recovery time can be effectively shortened, and the metal separation purity is improved;
6) Immersing the battery piece subjected to the cryogenic treatment in the step 5) in high-concentration oxidizing acid (concentrated hydrochloric acid and concentrated nitric acid are mixed according to the volume ratio of 3:1) for recovery and release, so that a metal silicon material with higher purity (about 85%) can be obtained, and the obtained metal silicon can be subjected to grading treatment or can be recycled for high-value utilization;
7) Or dissolving, recovering and releasing aluminum (Al) by using a solvent NaOH solution to obtain the metallic aluminum material with high purity (90%), and performing grading treatment and high-value utilization or recovery.
Comparative example 1
The method for recycling the retired photovoltaic module without adopting a cryogenic treatment method comprises the following specific steps:
1) Placing the complete photovoltaic module on a heating platform, setting the temperature of the platform at 100 ℃, treating for 1 hour, and removing an aluminum frame and a junction box to obtain a complete photovoltaic laminated piece;
2) Adjusting the temperature of the heating platform to 200 ℃, treating for 0.5 hour, stripping the softened back plate layer by using a cutter, and grading the stripped back plate for treatment or recycling high value;
3) Adjusting the temperature of the heating platform to 180 ℃, treating for 1 hour, stripping the crystalline silicon battery layer from the surface of the glass, and performing grading treatment or recycling on the obtained complete glass, and performing subsequent treatment on the obtained battery layer adhered with the EVA adhesive film;
4) Taking the battery layer adhered with the EVA adhesive film down from the heating platform, and directly crushing the battery layer to obtain metal and EVA mixed particles;
5) Treating the mixed particles by high-concentration oxidation acid leaching and the like to obtain a metallic silicon material with the purity of about 60 percent;
6) Or treating the mixed particles by a solvent NaOH solution or the like to obtain the metallic aluminum material with the purity of about 65 percent.
Example 2
A method for efficiently recycling a retired photovoltaic module by heat treatment and deep cooling double-auxiliary separation comprises the following specific steps:
1) Placing the complete photovoltaic module on a heating platform, setting the temperature of the platform at 200 ℃, processing for 0.1 hour, and removing an aluminum frame and a junction box to obtain a complete photovoltaic laminated piece;
2) Adjusting the temperature of the heating platform to 150 ℃, treating for 2 hours, stripping the softened back plate layer by using a cutter, and grading the stripped back plate for treatment or recycling high value;
3) Adjusting the temperature of the heating platform to 250 ℃, treating for 0.1 hour, stripping the crystalline silicon battery layer from the surface of the glass, and performing grading treatment or recycling on the obtained complete glass to obtain a battery layer adhered with an EVA adhesive film for subsequent treatment;
4) Taking the cell layer adhered with the EVA adhesive film from the heating platform, and cutting along the cell array to obtain 48 blocks of 10 × 10cm 2 A battery piece;
5) All the battery pieces are soaked in dry ice acetone together, deep cooling soaking is carried out for 30 minutes, metals are effectively separated due to severe low-temperature shrinkage, the metal materials can be completely exposed (shown in figures 2-3) in the step, so that subsequent solvent purification and recovery (contact area is increased) are facilitated, the problems of difficult separation and difficult purification caused by crushing and mixing are avoided, the solvent recovery time can be effectively shortened, and the metal separation purity is improved;
6) Dissolving, recovering and releasing silicon (Si) metal through high-concentration oxidation acid leaching and the like to obtain a metallic silicon material with higher purity (about 85 percent), and performing graded treatment and use or recovering high-value utilization;
7) By HNO 3 Dissolving, recovering and releasing the metal aluminum to obtain a metal aluminum material with higher purity (95%), and performing grading treatment or recycling high-value utilization;
8) The technical route of chlorination sedimentation, ammonia dissolution and hydrazine hydrate reduction is adopted, so that the high-efficiency separation and recovery of Ag are realized, and the recovery efficiency can reach more than 95%.
Example 3
A method for efficiently recycling a retired photovoltaic module by heat treatment and deep cooling double-auxiliary separation comprises the following specific steps:
1) Placing the complete photovoltaic module on a heating platform, setting the temperature of the platform at 100 ℃, treating for 2 hours, and removing an aluminum frame and a junction box to obtain a complete photovoltaic laminated piece;
2) Adjusting the temperature of the heating platform to 250 ℃, treating for 0.2 hour, stripping the softened back plate layer by using a cutter, and grading the stripped back plate for treatment or recycling high value;
3) Adjusting the temperature of the heating platform to 160 ℃, treating for 0.5 hour, stripping the crystalline silicon battery layer from the surface of the glass, and performing grading treatment or recycling on the obtained complete glass to obtain a battery layer adhered with an EVA adhesive film for subsequent treatment;
4) Taking the cell layer adhered with the EVA adhesive film from the heating platform, and cutting along the cell array to obtain 60 blocks of 8-10 cm 2 A battery piece;
5) All the battery pieces are soaked in dry ice acetonitrile together, deep-cold soaking is carried out for 90 minutes, the metal layers are effectively separated due to severe low-temperature shrinkage, metal materials (metals such as silicon, aluminum, silver, indium, gallium and the like) can be completely exposed (shown in figures 2-3) in the step, so that subsequent solvent purification and recovery (contact area is increased) are facilitated, the problems of difficult separation and difficult purification caused by crushing and mixing are avoided, the solvent recovery time can be effectively shortened, and the metal separation purity is improved;
6) Dissolving, recovering and releasing silicon (Si) metal through high-concentration oxidation acid leaching and the like to obtain a metallic silicon material with higher purity (about 85 percent), and performing graded treatment and use or recovering high-value utilization;
7) By HNO 3 Dissolving, recovering and releasing the metal aluminum to obtain a metal aluminum material with higher purity (95%), and performing grading treatment or recycling high-value utilization;
8) Through the technical route of NaOH, the Ag is efficiently separated and recovered, and the recovery efficiency can reach more than 95%. SEM sample preparation and characterization process:
in the step 5) of the embodiment 1, the battery piece is effectively separated from the silicon layer by adopting a deep cooling part, so that two parts of samples (respectively distinguished by an upper layer sample and a lower layer sample) are obtained; the cross-sectional characterization of the upper and lower layer samples was performed by SEM-EDS, and the SEM pictures are shown in fig. 2. It can be observed that the cell layers may be mainly of multilayer structure after the main treatment (see fig. 2a, d), the constituent elements of the layered structure may be further distinguished by EDS (energy spectrum analysis), the cross section mainly includes silicon (Si) and aluminum (Al) elements, and the cleavage plane mainly includes silicon (Si) elements (see fig. 2b, e), and aluminum (Al) elements are also observed in the cross section.
Subsequently, the microstructure and the elemental composition of the surface of the cleavage plane were observed by SEM-EDS, the results of the upper and lower surfaces were similar, and the results of the upper layer sample are shown and described as an example, and the specific results are shown in fig. 3. As shown In fig. 3a, the cracked surface has a fine linear ravine structure, and EDS analysis shows that the elements of the cracked surface are mainly Si (fig. 3 b), while a small amount of Al (fig. 3 c) and gallium (Ga) are observed (fig. 3 f), and the linear ravine structure is mainly silver (Ag) (fig. 3 d) and indium (In) (fig. 3 e); it can be seen that various metal materials can be effectively recovered by the method of the present invention.
Claims (9)
1. A method for separating and recycling a decommissioned photovoltaic module comprises an additional structure and a laminating piece, wherein the additional structure comprises a junction box and a frame, and the laminating piece comprises a glass layer, a first sealing material layer, a crystalline silicon battery sheet layer, a second sealing material layer and a back plate; the separation and recovery method is characterized by comprising the following steps: firstly, sequentially removing the additional structure, completely stripping the back plate and the glass layer by a heat treatment method to obtain a crystalline silicon cell sheet layer with the upper surface and the lower surface both stuck with sealing materials; and then, the obtained crystalline silicon battery sheet with the sealing materials adhered to the upper surface and the lower surface is subjected to cryogenic treatment at-190 to-20 ℃ to split the crystalline silicon battery sheet, and metal is enriched on a splitting surface due to the fact that metal in the crystalline silicon battery sheet shrinks at low temperature, so that the metal is convenient to purify and recycle subsequently.
2. The method for separating and recycling a decommissioned photovoltaic module according to claim 1, wherein the method for separating and recycling comprises the following steps:
1) Removing the additional structure of the retired photovoltaic module through heat treatment to obtain a complete laminated part;
2) Softening the back plate by heat treatment of the obtained laminated piece, and completely stripping the softened back plate by using a tool to obtain a recycled polymer back plate material;
3) Continuously carrying out heat treatment on the rest assembly comprising the glass layer and the crystalline silicon cell sheet layer, stripping the crystalline silicon cell sheet layer from the surface of the glass to obtain a complete glass material and the crystalline silicon cell sheet layer with the upper and lower surfaces adhered with sealing materials;
4) Cutting the crystalline silicon battery sheet layer with the upper surface and the lower surface both adhered with the sealing material to obtain regular battery sheets, then carrying out subzero treatment on the battery sheets with regular shapes at a temperature of between 190 ℃ below zero and 20 ℃ below zero, splitting the crystalline silicon battery sheets after the subzero treatment, and completely exposing the metal in the crystalline silicon battery sheets due to the fact that the metal in the crystalline silicon battery sheets shrinks at a low temperature;
5) Recovering the metal material by a solvent dissolution recovery method.
3. The method for separating and recovering the retired photovoltaic module according to claim 2, wherein the cryogenic treatment in the step 4) is performed in the following manner: liquid nitrogen quenching, liquid helium quenching, dry ice acetone quenching or dry ice acetonitrile quenching.
4. The method for separating and recycling a decommissioned photovoltaic module according to claim 2 or 3, wherein in the step 5), the metal is aluminum, silicon, silver, indium or gallium.
5. The method for separating and recycling a retired photovoltaic module according to any one of claims 2 to 4, wherein in the step 5), the solvent in the solvent dissolution recycling method comprises: naOH, HF, HNO 3 、H 2 SO 4 、H 3 PO 4 、H 2 SiF 6 、KOH、NH 3 Or Br 2 A solvent.
6. The method for separating and recovering the retired photovoltaic module according to any one of claims 2 to 5, wherein in the steps 1) to 3), the temperature of the heat treatment is 100 to 250 ℃, and the time of the heat treatment is 0.1 to 2 hours.
7. The method for separating and recycling a decommissioned photovoltaic module according to any one of claims 2 to 6, wherein the recycling method further comprises the following steps: and (3) carrying out grading treatment on the polymer backboard material obtained in the step 2) for direct use or high value-added recycling.
8. The method for separating and recycling a decommissioned photovoltaic module according to any one of claims 2 to 7, wherein the recycling method further comprises the following steps: and (4) carrying out grading treatment on the glass material obtained in the step 3) for direct use or recycling.
9. A method for improving the purity of recovered metal obtained in the recovery treatment of a retired photovoltaic module is characterized by comprising the following steps: firstly, sequentially removing the additional structure, completely stripping the back plate and the glass layer by a heat treatment method to obtain a crystalline silicon cell sheet layer with the upper surface and the lower surface both stuck with sealing materials; and then, carrying out cryogenic treatment on the obtained crystalline silicon battery sheet at-190 to-20 ℃ to split the metal silicon battery sheet, so that the metal is completely exposed, and due to the increase of the contact area, the purity of the recovered metal is improved by a subsequent solvent purification recovery method.
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