CN117244920A - Method for green efficient separation and recovery of photovoltaic modules based on silicon-containing waste - Google Patents
Method for green efficient separation and recovery of photovoltaic modules based on silicon-containing waste Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 69
- 239000010703 silicon Substances 0.000 title claims abstract description 69
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 238000000926 separation method Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000011084 recovery Methods 0.000 title claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 54
- 239000004332 silver Substances 0.000 claims abstract description 52
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011521 glass Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000003466 welding Methods 0.000 claims abstract description 23
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 20
- 238000000197 pyrolysis Methods 0.000 claims abstract description 19
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 19
- 238000001291 vacuum drying Methods 0.000 claims abstract description 19
- 238000005530 etching Methods 0.000 claims abstract description 13
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000008358 core component Substances 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 238000004064 recycling Methods 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 238000002386 leaching Methods 0.000 claims description 36
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 239000002313 adhesive film Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 238000006479 redox reaction Methods 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002210 silicon-based material Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- WIUHYQBOXHNHLG-UHFFFAOYSA-N acetic acid hydrofluoride Chemical compound F.C(C)(=O)O WIUHYQBOXHNHLG-UHFFFAOYSA-N 0.000 claims description 4
- PEKIAHWVRGDDMN-UHFFFAOYSA-N oxalic acid;hydrofluoride Chemical compound F.OC(=O)C(O)=O PEKIAHWVRGDDMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000003487 electrochemical reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000002269 spontaneous effect Effects 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 41
- 239000007788 liquid Substances 0.000 abstract description 12
- -1 silver ions Chemical class 0.000 abstract description 10
- 238000012216 screening Methods 0.000 abstract description 6
- 239000000306 component Substances 0.000 abstract description 4
- 229910000679 solder Inorganic materials 0.000 abstract description 3
- 235000012431 wafers Nutrition 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 239000011449 brick Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 229910021422 solar-grade silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—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 NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/15—Electronic waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/15—Electronic waste
- B09B2101/16—Batteries
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Processing Of Solid Wastes (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to the technical field of wet separation and green recovery treatment, in particular to a green efficient separation and recovery photovoltaic module method based on silicon-containing waste, which comprises the following steps: dismantling a metal frame and a junction box at the periphery of the photovoltaic module to obtain a core module; screening and separating battery pieces, welding strips, glass and other residues after pyrolysis of the core component; then cleaning to obtain clean battery pieces; and soaking the clean battery piece in nitric acid, and then carrying out solid-liquid separation to obtain aluminum nitrate, silver nitrate solution and impurity-removing battery pieces, and cleaning the impurity-removing battery pieces, and then carrying out vacuum drying and recycling. And adding silicon-containing waste and etching solution into the solution, wherein silver can be deposited on the surface of silicon in the etching solution because the electronegativity of silver is greater than that of silicon, and accurately capturing silver ions in the solution by the silicon-containing waste. The method can separate and recycle Ag, si and Al elements, solder strips, glass and other valuable components in the photovoltaic module in a green and efficient way.
Description
Technical Field
The invention relates to the technical field of wet separation and green recovery treatment, in particular to a green efficient separation and recovery photovoltaic module method based on silicon-containing waste.
Background
The photovoltaic solar panel is rapidly developed as clean renewable energy, and the global photovoltaic industry in 2022 enters the tera era, and the accumulated installed quantity reaches 1053GW. The service life of the photovoltaic module is 20-25 years, the photovoltaic module is greatly retired at present, and the retirement amount of the photovoltaic module is exploded and increased in the future. The photovoltaic module contains valuable resources such as glass, silicon, silver, aluminum, copper-tin alloy and the like, and has important economic value and environmental significance in realizing comprehensive recovery.
At present, physical methods, chemical methods and pyrolysis methods exist for interlayer separation methods of retired photovoltaic modules. The physical method converts the photovoltaic module into particles through physical crushing, and then screens and classifies the particles, and respectively recovers the particles. The chemical method comprises the following steps: and swelling or dissolving the EVA adhesive film by adopting a solvent soaking component, and then separating other layers of structures. The pyrolysis method realizes the interlayer separation of the assembly by heating and gasifying and decomposing the backboard and the EVA adhesive film at high temperature. The glass after interlayer separation is cleaned and dried, and then is used as clinker to be mixed into photovoltaic glass preparation, and the mixing amount is generally lower than 30 percent. The battery piece after interlayer separation is subjected to impurity removal treatment, and the silver grid line and the aluminum back level are generally removed through nitric acid due to wide sources and low price of nitric acid, and the surface silicon nitride layer is removed through hydrofluoric acid or phosphoric acid. The silicon wafer after impurity removal can be used as a solar grade silicon preparation raw material, a lithium ion silicon-based negative electrode raw material or a complete silicon wafer to prepare the solar cell again. During impurity removal, silver ions are leached into the solution, and are usually separated from the solution by precipitation, solvent extraction, ion exchange, electrolysis and the like.
Precipitation processes form solid precipitates from anions by adding chemical agents, such as sodium borohydride, sodium sulfide or chloride, to the leachate, and then ammoniating the precipitates-hydrazine hydrate reduction (higher toxicity) or melt purification treatment (higher energy consumption);
the solvent extraction method utilizes the interaction between silver ions and a solvent to transfer the silver ions into the solvent, and then the silver is concentrated and recovered by evaporation and the like, but the concentration of the leached silver ions is low, the environment of strong nitric acid oxide is strong, and the selectivity of the extractant to the silver ions is low due to the difficulty in stabilizing the extractant;
ion exchange is a technique that uses resins or membranes to selectively adsorb silver ions from a leachate. The resin or film is then eluted with a solution containing high concentrations of silver ions, which are then recovered and converted into a usable form. Ion exchange is an effective method for recovering high-purity silver from low-capacity waste liquid, but has higher operation cost and needs to replace resin or membrane frequently;
electrolytic processes reduce silver ions to metallic silver and deposit on a cathode by applying an electric current to the leachate. The silver recovered afterwards is rinsed, dried and melted into ingots for reuse. Electrolytic processes are effective methods for recovering high purity silver from leaching solutions containing trace amounts of silver, but they require significant amounts of energy and are costly to operate.
Therefore, how to efficiently separate valuable metals of the waste photovoltaic modules at low cost becomes a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a green high-efficiency separation and recovery photovoltaic module method based on silicon-containing waste, which solves the technical problems of high toxicity of chemical reagents used in the existing separation method, low selectivity of extractant, high ion exchange cost and high energy consumption of electrolytic deposition.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
a green high-efficiency separation and recovery method for photovoltaic modules based on silicon-containing waste comprises the following steps:
s1, removing a metal frame and a junction box on the periphery of a photovoltaic module to obtain a core module; the core component sequentially comprises a glass plate, an EVA adhesive film, a battery piece, an EVA adhesive film and a TPT back plate from top to bottom;
s2, pyrolyzing and separating the core component to obtain glass, a welding belt, a battery piece and other residues;
s3, cleaning the glass and the welding strip, and recycling the glass and the welding strip after vacuum drying treatment;
s4, soaking the cleaned battery piece in a nitric acid solution to obtain a silver nitrate and aluminum nitrate mixed leaching solution and a impurity-removed battery piece, and cleaning and vacuum drying the impurity-removed battery piece;
s5, adding silicon-containing waste into the mixed leaching solution obtained in the step S4, wherein silver nitrate in the solution is used as catalytic nano metal, a silicon substrate and the catalytic metal silver nitrate form a primary cell, the catalytic metal contacts silicon to perform oxidation-reduction reaction, and spontaneous electrochemical reaction is formed on the surface of the catalytic metal;
s6, continuously performing oxidation-reduction reaction to cause oxidation of the silicon substrate, dissolving oxidized silicon by adding etching solution, continuously reacting the silicon material with silver nitrate, continuously replacing silicon-containing waste to obtain silver, filtering, and flushing to Ag particles and aluminum-containing solution.
Further, in the step S2, the periphery of the core component is fixed first, and then the core component is placed in a furnace for thermal separation.
Further, the pyrolysis temperature is 450-700 ℃, and the pyrolysis heat preservation time is 10-60 min.
Further, in the step S3, the temperature of the vacuum drying treatment is 60-80 ℃, and the time of the vacuum drying treatment is 60-180 min.
Further, in the step S4, the concentration of the nitric acid is 0.5-2.5 mol/L, the leaching time is 5-60 min, and the leaching temperature is 25-50 ℃. The mole ratio of hydrofluoric acid to acetic acid is 1:1 to 10, the mole ratio of hydrofluoric acid to oxalic acid is 1:1 to 10.
Further, in the step S4, the temperature of the vacuum drying treatment is 60-80 ℃, and the time of the vacuum drying treatment is 60-180 min.
Further, in the step S5, the mass ratio of capturing silver is required to be 1: 5-30 silicon-containing waste and etching agent, wherein the mass of the silicon-containing waste is 1-10 g, the reaction temperature is 25-65 ℃, and the reaction time is 1-20 min. Wherein the silicon-containing waste is selected from diamond wire cut silicon waste or waste silicon wafers;
further, in the step S6, the etchant is one of hydrofluoric acid, hydrofluoric acid-acetic acid, and hydrofluoric acid-oxalic acid solution; the concentration of hydrofluoric acid is 0.5-2 mol/L, the concentration of acetic acid is 0.5-2 mol/L, and the concentration of oxalic acid is 0.5-2 mol/L; the mole ratio of hydrofluoric acid to acetic acid is 1:1 to 10, the mole ratio of hydrofluoric acid to oxalic acid is 1:1 to 10.
The invention has the beneficial effects that:
wet separation green recovery treatment technology: the invention adopts a wet separation method and combines the processes of chemical leaching and pyrolysis separation, so that each interlayer material in the photovoltaic module can be effectively separated. Compared with the traditional physical method, the wet separation can separate all layers of the assembly more thoroughly, and the recovery efficiency is improved. Meanwhile, wet separation is more suitable for processing complex photovoltaic module structures. According to the invention, glass, a welding strip and a battery piece are separated through pyrolysis and then screening, and meanwhile, silver, aluminum and the like of the battery piece are leached to obtain impurity removal, and the purity of the leached battery piece is more than 99.9%.
The extractant has high selectivity: the nitric acid leaching method can effectively remove the silver grid line and the aluminum back level in the battery piece. Nitric acid has a higher selectivity than other chemical processes and can more effectively dissolve and extract valuable silver metal.
Oxidation-reduction reaction: the invention realizes the oxidation-reduction reaction by combining the silicon matrix with the catalytic metal silver nitrate. Because the electronegativity of silver is greater than that of silicon, silver can be deposited on the surface of silicon in etching solution, and silver ions in the solution are accurately captured by silicon-containing waste. The method can separate and recycle Ag, si and Al elements, solder strips, glass and other valuable components in the photovoltaic module in a green and efficient way. The reaction can effectively replace silicon and silver, and the silver can be recycled. Compared with the traditional ion exchange and electrolysis method, the invention provides a method for separating valuable metals in the leaching solution in a waste treatment mode, thereby effectively avoiding the use amount of high temperature, a large amount of electric energy and toxic reagents. The purity of the trapped silver particles reaches more than 99.9%, secondary treatment is not needed, and the method has the characteristics of low energy consumption and simplicity in operation.
And (3) selecting etching liquid: the etching liquid used in the invention comprises hydrofluoric acid, acetic acid, oxalic acid and the like, and the etching liquid can effectively dissolve oxidized silicon to realize continuous replacement of silver. The selection of the components and the concentration of the etching liquid has important influence on the reaction effect and the purity of the product, and the efficient separation and recovery can be realized through reasonable design and optimization.
In summary, the method for green and efficient separation and recovery of the photovoltaic modules based on the silicon-containing waste provided by the invention can improve the recovery and utilization efficiency of the waste photovoltaic modules, reduce the pollution to the environment and promote the sustainable development of the photovoltaic industry.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic overall flow chart of the present invention;
FIG. 2 is a photograph of the isolated product of the present invention, wherein glass, solder strips, edulcoration cell sheets, silver particles are sequentially left to right;
FIG. 3 shows the silicon-containing waste material required for capturing metal, wherein a is waste silicon wafer and b is waste silicon material;
FIG. 4 is a silver XRD pattern of the product captured in step S5 of example 2 of the present invention;
fig. 5a and b are SEM electron micrographs of the surfaces of silver particles of the products obtained by trapping in examples 2 and 5, respectively, according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
As shown in fig. 1-5
The method for green and efficient separation and recovery of the photovoltaic module based on the silicon-containing waste material comprises the following steps:
s1, removing a metal frame and a junction box on the periphery of a photovoltaic module to obtain a core module; the core component sequentially comprises a glass plate, an EVA adhesive film, a battery piece, an EVA adhesive film and a TPT back plate from top to bottom;
s2, pyrolyzing and separating the core component to obtain glass, a welding belt, a battery piece and other residues;
s3, cleaning the glass and the welding strip, and recycling the glass and the welding strip after vacuum drying treatment;
s4, soaking the cleaned battery piece in a nitric acid solution to obtain a silver nitrate and aluminum nitrate mixed leaching solution and a impurity-removed battery piece, and cleaning and vacuum drying the impurity-removed battery piece;
s5, adding silicon-containing waste into the mixed leaching solution, wherein silver nitrate in the solution is used as catalytic nano metal, and the silicon substrate and the catalytic metal silver nitrate form a primary cell. The catalytic metal contacts silicon to generate oxidation-reduction reaction, and spontaneous electrochemical reaction is formed on the surface.
S6, continuously carrying out oxidation-reduction reaction to cause oxidation of the silicon substrate, and adding etching liquid to dissolve the oxidized silicon to enable the silicon material to continuously react with silver nitrate. The waste silicon is continuously replaced to obtain silver, and the silver is filtered and washed to Ag particles and aluminum-containing solution.
In this embodiment, in the step S2, the periphery of the core component is fixed first, and then the core component is placed in a furnace for thermal separation.
In the embodiment, the pyrolysis temperature is 450-700 ℃, and the pyrolysis heat preservation time is 10-60 min.
In this embodiment, in the step S3, the temperature of the vacuum drying process is 60 to 80 ℃, and the time of the vacuum drying process is 60 to 180 minutes.
In this embodiment, in the step S4, the concentration of the nitric acid is 0.5-2.5 mol/L, the leaching time is 5-60 min, and the leaching temperature is 25-50 ℃.
In this embodiment, in the step S4, the temperature of the vacuum drying process is 60 to 80 ℃, and the time of the vacuum drying process is 60 to 180 minutes.
In this embodiment, in the step S5, the mass ratio of capturing silver is required to be 1: 5-30 silicon-containing waste and etching agent, wherein the mass of the silicon-containing waste is 1-10 g, the reaction temperature is 25-65 ℃, and the reaction time is 1-20 min.
In this embodiment, in the step S6, the etchant is one of hydrofluoric acid, hydrofluoric acid-acetic acid, and hydrofluoric acid-oxalic acid solution; the concentration of hydrofluoric acid is 0.5-2 mol/L, the concentration of acetic acid is 0.5-2 mol/L, and the concentration of oxalic acid is 0.5-2 mol/L; the mole ratio of hydrofluoric acid to acetic acid is 1:1 to 10, the mole ratio of hydrofluoric acid to oxalic acid is 1:1 to 10.
Example 2
And dismantling the metal frame and the junction box on the periphery of the photovoltaic module to obtain a core module, wherein the core module comprises glass, an EVA adhesive film, a battery piece, the EVA adhesive film and a TPT back plate from top to bottom. The core assembly was placed on refractory bricks in a muffle furnace for pyrolysis and incubated at 550 ℃ for 30min. And (5) screening after pyrolysis to obtain glass, welding strips, battery pieces and other white powder.
After the glass, the welding strip and the battery piece are ultrasonically cleaned, the glass and the welding strip can be reused. The cleaned battery piece is soaked in nitric acid solution, the concentration of nitric acid is 1.5mol/L, the leaching time is 30min, and the leaching temperature is 30 ℃. Filtering the reaction product by using a Buchner funnel after the reaction is finished, and obtaining the silver nitrate and aluminum nitrate mixed leaching solution and the impurity-removing battery piece after the filtration. The purity of the impurity-removed battery piece after removing silicon nitride by phosphoric acid can reach more than 99.9 percent, and the impurity-removed battery piece is recycled after being cleaned.
Placing a beaker for collecting the mixed leaching solution of silver nitrate and aluminum nitrate in a water bath, pouring 3g of waste silicon chips into the beaker, and completely immersing the waste silicon chips by the leaching solution. The water bath was heated to 50℃and then 15g of etchant (hydrofluoric acid) was added for 10min. Wherein, the mass ratio of the waste silicon wafer to the etchant is 1:5, the concentration of hydrofluoric acid is 1mol/L.
After the reaction is completed, solid-liquid separation is carried out through a Buchner funnel, and the silver particles can be obtained through water washing of the obtained solid phase.
Silver is trapped on the surface of the waste silicon wafer through detection.
FIG. 4 is a silver XRD pattern obtained after solid-liquid separation in this example; as can be seen from fig. 5a, a large amount of silver grows on the waste silicon wafer to form dendrite silver, while silver particles can be found to grow on the dendrite silver;
example 3
And dismantling the metal frame and the junction box on the periphery of the photovoltaic module to obtain a core module, wherein the core module comprises glass, an EVA adhesive film, a battery piece, the EVA adhesive film and a TPT back plate from top to bottom. The core assembly was placed on refractory bricks in a muffle furnace for pyrolysis and incubated at 650 ℃ for 10min. And (5) screening after pyrolysis to obtain glass, welding strips, battery pieces and other white powder.
After the glass, the welding strip and the battery piece are ultrasonically cleaned, the glass and the welding strip can be reused. The cleaned battery piece is soaked in nitric acid solution, the concentration of nitric acid is 2.5mol/L, the leaching time is 5min, and the leaching temperature is 25 ℃. Filtering the reaction product by using a Buchner funnel after the reaction is finished, and obtaining the silver nitrate and aluminum nitrate mixed leaching solution and the impurity-removing battery piece after the filtration. The purity of the impurity-removed battery piece after removing silicon nitride by phosphoric acid can reach more than 99.9 percent, and the impurity-removed battery piece is recycled after being cleaned.
Placing a beaker for collecting the mixed leaching solution of silver nitrate and aluminum nitrate in a water bath, pouring 10g of waste silicon slices into the beaker, and completely immersing the waste silicon slices by the leaching solution. The water bath was heated to 65℃and 200g of etchant (hydrofluoric acid-acetic acid) was then added for 2min. Wherein, the mass ratio of the waste silicon wafer to the etchant is 1:20, the concentration of hydrofluoric acid is 0.5mol/L, the concentration of acetic acid is 1.0mol/L, and the mass ratio of hydrofluoric acid to acetic acid is 2:1.
after the reaction is completed, solid-liquid separation is carried out through a Buchner funnel, and the silver particles can be obtained through water washing of the obtained solid phase.
Silver is trapped on the surface of the waste silicon wafer through detection.
Example 4
And dismantling the metal frame and the junction box on the periphery of the photovoltaic module to obtain a core module, wherein the core module comprises glass, an EVA adhesive film, a battery piece, the EVA adhesive film and a TPT back plate from top to bottom. The core assembly was placed on refractory bricks in a muffle furnace for pyrolysis and incubated at 450 ℃ for 60min. And (5) screening after pyrolysis to obtain glass, welding strips, battery pieces and other white powder.
After the glass, the welding strip and the battery piece are ultrasonically cleaned, the glass and the welding strip can be reused. The cleaned battery piece is soaked in nitric acid solution, the concentration of nitric acid is 1.0mol/L, the leaching time is 10min, and the leaching temperature is 40 ℃. Filtering the reaction product by using a Buchner funnel after the reaction is finished, and obtaining the silver nitrate and aluminum nitrate mixed leaching solution and the impurity-removing battery piece after the filtration. The purity of the impurity-removed battery piece after removing silicon nitride by phosphoric acid can reach more than 99.9 percent, and the impurity-removed battery piece is recycled after being cleaned.
Placing a beaker for collecting the mixed leaching solution of silver nitrate and aluminum nitrate in a water bath, pouring 5g of waste silicon materials into the beaker, and completely immersing the waste silicon chips by the leaching solution. The water bath was heated to 40 ℃ and then 75g of etchant (hydrofluoric acid) was added for 10min. Wherein, the mass ratio of the waste silicon wafer to the etchant is 1:15, the concentration of hydrofluoric acid is 1.5mol/L.
After the reaction is completed, solid-liquid separation is carried out through a Buchner funnel, and the silver particles can be obtained through water washing of the obtained solid phase.
Silver is trapped on the surface of the waste silicon wafer through detection.
Example 5
And dismantling the metal frame and the junction box on the periphery of the photovoltaic module to obtain a core module, wherein the core module comprises glass, an EVA adhesive film, a battery piece, the EVA adhesive film and a TPT back plate from top to bottom. The core assembly was placed on refractory bricks in a muffle furnace for pyrolysis and incubated at 550℃for 35min. And (5) screening after pyrolysis to obtain glass, welding strips, battery pieces and other white powder.
After the glass, the welding strip and the battery piece are ultrasonically cleaned, the glass and the welding strip can be reused. The cleaned battery piece is soaked in nitric acid solution, the concentration of nitric acid is 1.5mol/L, the leaching time is 30min, and the leaching temperature is 35 ℃. Filtering the reaction product by using a Buchner funnel after the reaction is finished, and obtaining the silver nitrate and aluminum nitrate mixed leaching solution and the impurity-removing battery piece after the filtration. The purity of the impurity-removed battery piece after removing silicon nitride by phosphoric acid can reach more than 99.9 percent, and the impurity-removed battery piece is recycled after being cleaned.
Placing a beaker for collecting the mixed leaching solution of silver nitrate and aluminum nitrate in a water bath, pouring 3g of waste silicon materials into the beaker, and completely immersing the waste silicon chips by the leaching solution. The water bath was heated to 45℃and 45g of etchant (hydrofluoric acid-oxalic acid) was then added for 8min. Wherein, the mass ratio of the waste silicon wafer to the etchant is 1:15, the concentration of hydrofluoric acid is 1mol/L, the concentration of acetic acid is 1.0mol/L, and the mass ratio of hydrofluoric acid to acetic acid is 3:1.
after the reaction is completed, solid-liquid separation is carried out through a Buchner funnel, and the silver particles can be obtained through water washing of the obtained solid phase.
Silver is trapped on the surface of the waste silicon wafer through detection.
Fig. 5b is an effect diagram of example 5 of the present invention, in which silver particles are attached to the surface of the waste silicon material.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (7)
1. The green high-efficiency separation and recovery method for the photovoltaic module based on the silicon-containing waste is characterized by comprising the following steps of:
s1, removing a metal frame and a junction box on the periphery of a photovoltaic module to obtain a core module; the core component sequentially comprises a glass plate, an EVA adhesive film, a battery piece, an EVA adhesive film and a TPT back plate from top to bottom;
s2, pyrolyzing and separating the core component to obtain glass, a welding belt, a battery piece and other residues;
s3, cleaning the glass and the welding strip, and recycling the glass and the welding strip after vacuum drying treatment;
s4, soaking the cleaned battery piece in a nitric acid solution to obtain a silver nitrate and aluminum nitrate mixed leaching solution and a impurity-removed battery piece, and cleaning and vacuum drying the impurity-removed battery piece;
s5, adding silicon-containing waste into the mixed leaching solution obtained in the step S4, wherein silver nitrate in the solution is used as catalytic nano metal, a silicon substrate and the catalytic metal silver nitrate form a primary cell, the catalytic metal contacts silicon to perform oxidation-reduction reaction, and spontaneous electrochemical reaction is formed on the surface of the catalytic metal;
s6, continuously performing oxidation-reduction reaction to cause oxidation of the silicon substrate, dissolving oxidized silicon by adding etching solution, continuously reacting the silicon material with silver nitrate, continuously replacing silicon-containing waste to obtain silver, filtering, and flushing to Ag particles and aluminum-containing solution.
2. The green and efficient separation and recovery method for photovoltaic modules based on silicon-containing waste according to claim 1, wherein: in the step S2, the periphery of the core component is fixed first and then is put into a furnace for thermal separation; the pyrolysis temperature is 450-700 ℃, and the pyrolysis heat preservation time is 10-60 min.
3. The green and efficient separation and recovery method for photovoltaic modules based on silicon-containing waste according to claim 1, wherein: in the step S3, the temperature of the vacuum drying treatment is 60-80 ℃, and the time of the vacuum drying treatment is 60-180 min.
4. The green and efficient separation and recovery method for photovoltaic modules based on silicon-containing waste according to claim 1, wherein: in the step S4, the concentration of the nitric acid is 0.5-2.5 mol/L, the leaching time is 5-60 min, and the leaching temperature is 25-50 ℃.
5. The green and efficient separation and recovery method for photovoltaic modules based on silicon-containing waste according to claim 4, wherein: in the step S4, the temperature of the vacuum drying treatment is 60-80 ℃, and the time of the vacuum drying treatment is 60-180 min.
6. The green and efficient separation and recovery method for photovoltaic modules based on silicon-containing waste according to claim 1, wherein: in the step S5, the mass ratio of capturing silver is required to be 1: 5-30 silicon-containing waste and etching agent, wherein the mass of the silicon-containing waste is 1-10 g, the reaction temperature is 25-65 ℃, and the reaction time is 1-20 min.
7. The green and efficient separation and recovery method for photovoltaic modules based on silicon-containing waste according to claim 1, wherein: in the step S6, the etchant is one of hydrofluoric acid, hydrofluoric acid-acetic acid, and hydrofluoric acid-oxalic acid solution; the concentration of hydrofluoric acid is 0.5-2 mol/L, the concentration of acetic acid is 0.5-2 mol/L, and the concentration of oxalic acid is 0.5-2 mol/L; the mole ratio of hydrofluoric acid to acetic acid is 1:1 to 10, the mole ratio of hydrofluoric acid to oxalic acid is 1:1 to 10.
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