CN110747336A - Photovoltaic cell recovery method - Google Patents
Photovoltaic cell recovery method Download PDFInfo
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- CN110747336A CN110747336A CN201810813175.2A CN201810813175A CN110747336A CN 110747336 A CN110747336 A CN 110747336A CN 201810813175 A CN201810813175 A CN 201810813175A CN 110747336 A CN110747336 A CN 110747336A
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- Prior art keywords
- photovoltaic cell
- aluminum
- polycrystalline silicon
- acid
- mixed solution
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/037—Purification
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for recovering photovoltaic cells, which is implemented according to the following steps: step 1, corroding the surface of the pretreated photovoltaic cell piece by using mixed acid of hydrochloric acid and perchloric acid, then washing the surface of the photovoltaic cell piece, and crushing and screening to obtain photovoltaic cell piece powder; step 2, adding concentrated sulfuric acid into the photovoltaic cell powder obtained in the step 1 to obtain a mixed solution of aluminum sulfate and silver sulfate and polycrystalline silicon; step 3, adjusting the pH value of the mixed solution obtained in the step 2, and filtering to obtain silver sulfate precipitate and an aluminum sulfate solution, so as to complete the recovery of polycrystalline silicon, aluminum ions and silver ions in the photovoltaic cell; according to the invention, the recovery of polysilicon, aluminum ions and silver ions in the photovoltaic cell is completed by adding concentrated sulfuric acid and reasonably adjusting the pH value.
Description
Technical Field
The invention belongs to the technical field of waste photovoltaic battery pack recovery, and particularly relates to a recovery method of photovoltaic battery pieces.
Background
As a new clean energy, the solar photovoltaic industry develops rapidly in recent years, and the recovery and treatment of waste photovoltaic modules become an inevitable problem while solar photovoltaic power generation brings clean energy to human beings.
Solar cells produced in commercial scale at present are mainly monocrystalline silicon and polycrystalline silicon series, the monocrystalline silicon and the polycrystalline silicon are used as base materials, silver paste, silver-aluminum paste and aluminum paste are used as conductive materials, light energy and heat energy are converted into electric energy, certain leftover waste and unqualified products exist in the manufacturing and mounting processes of solar photovoltaic cells, the solar photovoltaic cells need to be scrapped after the solar photovoltaic cells reach the service life, and the cells contain a large amount of valuable elements such as silicon, silver, aluminum and the like, so that how to recycle the cells efficiently can reduce environmental pollution, change waste into valuable and save resources.
Disclosure of Invention
The invention aims to provide a method for recovering a photovoltaic cell, which is characterized in that concentrated sulfuric acid is added, the pH value is reasonably adjusted, the recovery of polycrystalline silicon, aluminum ions and silver ions in the photovoltaic cell is completed, and then the recovery and the reutilization of the photovoltaic cell are completed through a reduction process.
The technical scheme adopted by the invention is that the method for recovering the photovoltaic cell is implemented according to the following steps:
step 1, corroding the surface of the pretreated photovoltaic cell piece by using mixed acid of hydrochloric acid and perchloric acid, then washing the surface of the photovoltaic cell piece, and crushing and screening to obtain photovoltaic cell piece powder;
step 2, adding concentrated sulfuric acid into the photovoltaic cell powder obtained in the step 1 to obtain a mixed solution of aluminum sulfate and silver sulfate and polycrystalline silicon;
step 3, adjusting the pH value of the mixed solution obtained in the step 2, and filtering to obtain silver sulfate precipitate and an aluminum sulfate solution, so as to complete the recovery of polycrystalline silicon, aluminum ions and silver ions in the photovoltaic cell;
and 4, reducing the silver sulfate precipitate and the aluminum sulfate solution obtained in the step 3 to obtain simple substance aluminum and simple substance silver, and recycling the photovoltaic cell.
The present invention is also characterized in that,
the pretreatment in the step 1 comprises the following steps: and disassembling the aluminum frame for external protection of the photovoltaic cell, connecting the box, burning to remove the EVA adhesive film, and then removing the upper glass plate and the bottom TPT back plate to obtain the polycrystalline silicon cell.
In the step 1, the hydrochloric acid concentration is 0.5-3mol/l, the perchloric acid concentration is 0.1-1mol/l, and the corrosion time is 1-60 minutes.
The temperature of the concentrated sulfuric acid in the step 2 is 70-90 ℃.
The molar concentration of the concentrated sulfuric acid in the step 2 is 12-18.4 mol/L.
In the step 3, the pH value of the mixed solution is adjusted to 0.5-2.5 by aluminum hydroxide, and the temperature is reduced to 10-40 ℃.
The method has the beneficial effects that concentrated sulfuric acid is firstly added into the photovoltaic cell to obtain a mixed solution of aluminum sulfate and silver sulfate and polycrystalline silicon, then the pH value of the mixed solution is adjusted, and filtration is carried out to obtain silver sulfate precipitate and an aluminum sulfate solution, so that the recovery of polycrystalline silicon, aluminum ions and silver ions in the photovoltaic cell is completed.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a method for recovering a photovoltaic cell, which is implemented according to the following steps:
step 1, corroding the surface of the pretreated photovoltaic cell piece by using mixed acid of hydrochloric acid and perchloric acid, then washing the surface of the photovoltaic cell piece, and crushing and screening to obtain photovoltaic cell piece powder;
hydrochloric acid concentration of 0.5-3mol/l, perchloric acid concentration of 0.1-1mol/l, corrosion time of 1-60 min
The pretreatment comprises the following steps: disassembling an aluminum frame for external protection of the photovoltaic cell, connecting the box, burning to remove an EVA (ethylene vinyl acetate) adhesive film, and then removing an upper glass plate and a bottom TPT (thermoplastic vulcanizate) back plate to obtain a polycrystalline silicon cell; the crushing and screening adopt a screen with 180 meshes and 220 meshes;
therefore, the photovoltaic cell is often provided with the aluminum metal frame, the aluminum metal frame needs to be detached firstly before the back plate and the EVA adhesive film are separated, then the packaging material can be detached and recovered by adopting tools such as a blade, and the like, wherein the aluminum metal frame and the packaging material can be used for aging test after being recovered, and the aging performance of the aluminum metal frame and the packaging material is researched to make a contribution to the search of the service life of the photovoltaic cell.
Step 2, adding concentrated sulfuric acid into the photovoltaic cell powder obtained in the step 1 to obtain a mixed solution of aluminum sulfate and silver sulfate and polycrystalline silicon;
the temperature of the concentrated sulfuric acid is 70-90 ℃, and the molar concentration is 12-18.4 mol/L;
because of the small degree of solution of silver, only hot concentrated sulfuric acid can react with it.
Step 3, adjusting the pH value of the mixed solution obtained in the step 2 to 0.5-2.5 by using aluminum hydroxide, cooling to 10-40 ℃, and filtering to obtain silver sulfate precipitate and an aluminum sulfate solution, thereby completing the recovery of polycrystalline silicon, aluminum ions and silver ions in the photovoltaic cell;
thus, the pH value is skillfully adjusted, the silver sulfate in the mixed solution is precipitated, the precipitate is the silver sulfate after filtration, and the filtrate is the aluminum sulfate.
Compared with the existing preparation method, the invention mainly has the following technical advantages: according to the method, concentrated sulfuric acid is added into a photovoltaic cell to obtain a mixed solution of aluminum sulfate and silver sulfate and polycrystalline silicon, the pH value of the mixed solution is adjusted, filtering is performed to obtain silver sulfate precipitate and an aluminum sulfate solution, recovery of polycrystalline silicon, aluminum ions and silver ions in the photovoltaic cell is completed, and finally simple substance aluminum and simple substance silver are obtained through a reduction process, so that recycling is achieved.
Example 1
The embodiment 1 of the invention provides a method for recovering a photovoltaic cell, which is implemented according to the following specific steps: disassembling an aluminum frame for external protection of the photovoltaic cell, connecting the box, burning to remove an EVA (ethylene vinyl acetate) adhesive film, and then removing an upper glass plate and a bottom TPT (thermoplastic vulcanizate) back plate to obtain a polycrystalline silicon cell; corroding the surface silicon nitride and phosphorus pentoxide of the polycrystalline silicon cell piece for 60 minutes at 50 ℃ by using 0.5% mol/l hydrochloric acid and 1% mol/l perchloric acid mixed acid; filtering the solution, crushing the corroded polycrystalline silicon cell pieces, and screening by using a 210-mesh screen to obtain photovoltaic cell piece powder; crushing the polycrystalline silicon cell pieces and screening by adopting a 180-mesh screen to obtain photovoltaic cell piece powder; adding concentrated sulfuric acid with the temperature of 70 ℃ and the molar concentration of 12mol/L into the photovoltaic cell piece powder to obtain a mixed solution of aluminum sulfate and silver sulfate and polycrystalline silicon; and adjusting the pH value of the mixed solution to 0.5, cooling to 0.5 ℃, and filtering to obtain silver sulfate precipitate and an aluminum sulfate solution, thereby completing the recovery of polycrystalline silicon, aluminum ions and silver ions in the photovoltaic cell.
Example 2
The embodiment 2 of the invention provides a method for recovering a photovoltaic cell, which is implemented according to the following specific steps: disassembling an aluminum frame for external protection of the photovoltaic cell, connecting the box, burning to remove an EVA (ethylene vinyl acetate) adhesive film, and then removing an upper glass plate and a bottom TPT (thermoplastic vulcanizate) back plate to obtain a polycrystalline silicon cell; corroding the surface silicon nitride and phosphorus pentoxide of the polycrystalline silicon cell piece for 40 minutes at 40 ℃ by using mixed acid of 1.5% mol/l hydrochloric acid and 0.8% mol/l perchloric acid; filtering the solution, crushing the corroded polycrystalline silicon cell pieces, and screening by adopting a 190-mesh screen to obtain photovoltaic cell piece powder; crushing the polycrystalline silicon cell pieces and screening by adopting a 220-mesh screen to obtain photovoltaic cell piece powder; adding concentrated sulfuric acid with the temperature of 90 ℃ and the molar concentration of 18.4mol/L into the photovoltaic cell piece powder to obtain a mixed solution of aluminum sulfate and silver sulfate and polycrystalline silicon; and adjusting the pH value of the mixed solution to 2.5, cooling to 40 ℃, and filtering to obtain silver sulfate precipitate and an aluminum sulfate solution, thereby completing the recovery of polycrystalline silicon, aluminum ions and silver ions in the photovoltaic cell.
Example 3
The embodiment 3 of the invention provides a method for recovering a photovoltaic cell, which is implemented according to the following specific steps: disassembling an aluminum frame for external protection of the photovoltaic cell, connecting the box, burning to remove an EVA (ethylene vinyl acetate) adhesive film, and then removing an upper glass plate and a bottom TPT (thermoplastic vulcanizate) back plate to obtain a polycrystalline silicon cell; corroding the surface silicon nitride and phosphorus pentoxide of the polycrystalline silicon cell piece for 20 minutes at 60 ℃ by using 3.2% mol/l hydrochloric acid and 0.6% mol/l perchloric acid mixed acid; filtering the solution, crushing the corroded polycrystalline silicon cell pieces, and screening by using a 180-mesh screen to obtain photovoltaic cell piece powder; crushing the polycrystalline silicon cell pieces and screening by adopting a 200-mesh screen to obtain photovoltaic cell piece powder; adding concentrated sulfuric acid with the temperature of 80 ℃ and the molar concentration of 15mol/L into the photovoltaic cell piece powder to obtain a mixed solution of aluminum sulfate and silver sulfate and polycrystalline silicon; and adjusting the pH value of the mixed solution to 2, cooling to 20, filtering to obtain silver sulfate precipitate and an aluminum sulfate solution, and recovering polysilicon, aluminum ions and silver ions in the photovoltaic cell.
Example 4
The embodiment 4 of the invention provides a method for recovering a photovoltaic cell, which is implemented according to the following specific steps: disassembling an aluminum frame for external protection of the photovoltaic cell, connecting the box, burning to remove an EVA (ethylene vinyl acetate) adhesive film, and then removing an upper glass plate and a bottom TPT (thermoplastic vulcanizate) back plate to obtain a polycrystalline silicon cell; corroding the surface silicon nitride and phosphorus pentoxide of the polycrystalline silicon cell piece for 30 minutes at 30 ℃ by using 5.5% mol/l hydrochloric acid and 0.8% mol/l perchloric acid mixed acid; filtering the solution, crushing the corroded polycrystalline silicon cell pieces, and screening by adopting a 220-mesh screen to obtain photovoltaic cell piece powder; (ii) a Adding concentrated sulfuric acid with the temperature of 70 ℃ and the molar concentration of 17mol/L into the photovoltaic cell piece powder to obtain a mixed solution of aluminum sulfate and silver sulfate and polycrystalline silicon; and adjusting the pH value of the mixed solution to 2.5, cooling to 20 ℃, and filtering to obtain silver sulfate precipitate and an aluminum sulfate solution, thereby completing the recovery of polycrystalline silicon, aluminum ions and silver ions in the photovoltaic cell.
Example 5
The embodiment 5 of the invention provides a method for recovering a photovoltaic cell, which is implemented according to the following specific steps: disassembling an aluminum frame for external protection of the photovoltaic cell, connecting the box, burning to remove an EVA (ethylene vinyl acetate) adhesive film, and then removing an upper glass plate and a bottom TPT (thermoplastic vulcanizate) back plate to obtain a polycrystalline silicon cell; corroding silicon nitride and phosphorus pentoxide on the surface of the polycrystalline silicon cell piece for 10 minutes at 50 ℃ by using mixed acid of 6% mol/l hydrochloric acid and 0.21% mol/l perchloric acid; filtering the solution, crushing the corroded polycrystalline silicon cell pieces, and screening by using a 210-mesh screen to obtain photovoltaic cell piece powder; (ii) a Adding concentrated sulfuric acid with the temperature of 85 ℃ and the molar concentration of 13mol/L into the photovoltaic cell piece powder to obtain a mixed solution of aluminum sulfate and silver sulfate and polycrystalline silicon; and adjusting the pH value of the mixed solution to 1.5, cooling to 35 ℃, and filtering to obtain silver sulfate precipitate and an aluminum sulfate solution, thereby completing the recovery of polycrystalline silicon, aluminum ions and silver ions in the photovoltaic cell.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (6)
1. The method for recycling the photovoltaic cell is characterized by comprising the following steps:
step 1, corroding the surface of the pretreated photovoltaic cell piece by using mixed acid of hydrochloric acid and perchloric acid, then washing the surface of the photovoltaic cell piece, and crushing and screening to obtain photovoltaic cell piece powder;
step 2, adding concentrated sulfuric acid into the photovoltaic cell piece powder obtained in the step 1 to obtain a mixed solution of aluminum sulfate and silver sulfate and polycrystalline silicon;
and 3, adjusting the pH value of the mixed solution obtained in the step 2, and filtering to obtain silver sulfate precipitate and an aluminum sulfate solution.
2. The recycling method of photovoltaic cells as claimed in claim 1, wherein the pretreatment in step 1 is: and disassembling an aluminum frame and a junction box outside the photovoltaic cell, burning to remove the EVA adhesive film, and then removing the upper glass plate and the bottom TPT back plate to obtain the polycrystalline silicon cell.
3. The recycling method of the photovoltaic cell as claimed in claim 2, wherein the hydrochloric acid concentration in step 1 is 0.5-3mol/l, the perchloric acid concentration is 0.1-1mol/l, and the etching time is 1-60 minutes.
4. The recycling method of photovoltaic cell as claimed in claim 3, wherein the temperature of the concentrated sulfuric acid in step 2 is 70-90 ℃.
5. The recycling method of photovoltaic cell as claimed in claim 4, wherein the molar concentration of the concentrated sulfuric acid in the step 2 is 12-18.4 mol/L.
6. The recycling method of photovoltaic cell as claimed in claim 5, wherein the pH value of the mixed solution in step 3 is adjusted to 0.5-2.5 by aluminum hydroxide, and the temperature is reduced to 10-40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810813175.2A CN110747336A (en) | 2018-07-23 | 2018-07-23 | Photovoltaic cell recovery method |
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| CN201810813175.2A CN110747336A (en) | 2018-07-23 | 2018-07-23 | Photovoltaic cell recovery method |
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| CN110747336A true CN110747336A (en) | 2020-02-04 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475174A (en) * | 2009-01-23 | 2009-07-08 | 晶海洋半导体材料（东海）有限公司 | Method for purifying industrial silicon for preparing solar grade silicon |
| CN105618461A (en) * | 2015-12-31 | 2016-06-01 | 东莞珂洛赫慕电子材料科技有限公司 | Method for recycling crystalline silicon solar cell module |
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2018
- 2018-07-23 CN CN201810813175.2A patent/CN110747336A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475174A (en) * | 2009-01-23 | 2009-07-08 | 晶海洋半导体材料（东海）有限公司 | Method for purifying industrial silicon for preparing solar grade silicon |
| CN105618461A (en) * | 2015-12-31 | 2016-06-01 | 东莞珂洛赫慕电子材料科技有限公司 | Method for recycling crystalline silicon solar cell module |
Non-Patent Citations (2)
| Title |
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| 勤龙；KUNDA.W: "从含银物料中回收银的湿式冶金方法", 《矿产综合利用》 * |
| 王芃: "《无机及分析化学简明教程》", 30 October 2007 * |
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Application publication date: 20200204 |
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