CN113564361A - Pyrogenic treatment and recovery process of cadmium telluride thin-film solar cell - Google Patents
Pyrogenic treatment and recovery process of cadmium telluride thin-film solar cell Download PDFInfo
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- CN113564361A CN113564361A CN202110547253.0A CN202110547253A CN113564361A CN 113564361 A CN113564361 A CN 113564361A CN 202110547253 A CN202110547253 A CN 202110547253A CN 113564361 A CN113564361 A CN 113564361A
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- 239000010409 thin film Substances 0.000 title claims abstract description 42
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000011084 recovery Methods 0.000 title claims abstract description 32
- 230000001698 pyrogenic effect Effects 0.000 title claims abstract description 10
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 39
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 37
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 33
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000428 dust Substances 0.000 claims abstract description 22
- 239000011521 glass Substances 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005357 flat glass Substances 0.000 claims abstract description 13
- 239000003546 flue gas Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims abstract description 8
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims abstract description 7
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 8
- 239000000779 smoke Substances 0.000 claims description 7
- 230000005484 gravity Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
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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
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/004—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G11/00—Compounds of cadmium
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B17/00—Obtaining cadmium
- C22B17/02—Obtaining cadmium by dry processes
-
- 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
- C22B7/02—Working-up flue dust
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
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Abstract
The invention relates to the technical field of valuable metal recovery of thin film photovoltaic materials, in particular to a pyrogenic process treatment and recovery process of a cadmium telluride thin film solar cell, which comprises the following steps: (1) stripping back plate glass of the cadmium telluride thin film solar cell in a mechanical knocking mode, directly recovering the back plate glass, and crushing the front glass and the EVA thin film into small pieces; (2) placing the crushed front glass and the EVA film in a roasting furnace for oxidizing roasting; (3) and recycling tellurium and cadmium entering the flue gas in the forms of tellurium oxide and cadmium oxide by using flue gas dust collection equipment. The method has the advantages of high recovery rate of valuable metals, short process flow, little environmental pollution, simple operation and the like.
Description
Technical Field
The invention relates to the technical field of valuable metal recovery of thin film photovoltaic materials, in particular to a pyrogenic process treatment and recovery process of a cadmium telluride thin film solar cell.
Background
With the exhaustion of conventional energy and the increase of environmental pollution, renewable energy is a focus of global attention. The photovoltaic power generation is a technology for directly converting light energy into electric energy by utilizing the photovoltaic effect of a semiconductor interface, and has the advantages of no need of fuel consumption, short construction period, cleanness, safety and the like. In recent years, photovoltaic power generation has been rapidly developed.
At present, cadmium telluride thin film solar cell materials are widely applied to the photovoltaic market, and with the rapid increase of the photovoltaic loading machine amount, the number of scrapped photovoltaic panels is increased rapidly and the scrapping period is in a dense period. The rare and dispersed metal tellurium and heavy metal cadmium contained in the cadmium telluride thin-film solar cell have the problems of few primary resources, high mining difficulty and the like, and can cause serious pollution when flowing into the nature. Therefore, the method has important economic and social significance for recycling tellurium and cadmium in the cadmium telluride thin film solar cell material.
At present, the method for recovering tellurium and cadmium from waste cadmium telluride thin film solar cells mainly comprises a gas phase method and a liquid phase method, wherein the gas phase method has higher operating conditions, and the equipment investment and the operating cost of the whole system are higher; the liquid phase method has relatively simple process flow, but has poor working conditions and produces cadmium-containing wastewater, which causes great environmental protection pressure.
Disclosure of Invention
In view of the above disadvantages and shortcomings of the prior art, the present invention provides a pyrometallurgical recovery process for cadmium telluride thin film solar cells.
In order to achieve the purpose, the invention adopts the main technical scheme that:
the invention provides a pyrogenic process treatment and recovery process of a cadmium telluride thin film solar cell, which comprises the following steps:
(1) stripping back plate glass of the cadmium telluride thin film solar cell in a mechanical knocking mode, directly recovering the back plate glass, and crushing the front glass and the EVA thin film into small pieces;
(2) placing the crushed front glass and the EVA film in a roasting furnace for oxidizing roasting;
(3) and recycling tellurium and cadmium entering the flue gas in the forms of tellurium oxide and cadmium oxide by using flue gas dust collection equipment.
Further, in the cadmium telluride thin film solar cell: the tellurium content is 920-1020 ppm, and the cadmium content is 420-500 ppm.
Further, in the step (1), the front glass and the EVA film are crushed into small pieces with the particle size of 2-4 cm.
Further, in the step (2), a roasting furnace used for roasting is electrically heated, the roasting temperature is 700-800 ℃, and the roasting time is 1-1.5 hours.
Furthermore, the atmosphere in the roasting furnace is an oxidizing atmosphere, and the furnace chamber ensures that the micro negative pressure is-15 to-5 Pa.
Further, in the step (2), the tellurium content in the roasted waste slag is lower than 60ppm, and the cadmium content is lower than 50 ppm.
Further, in the step (3), the process for recovering tellurium and cadmium in the smoke dust adopts the processes of gravity settling, cyclone dust collection and cloth bag dust collection.
The invention has the beneficial effects that:
1. the process has high recovery rate of tellurium and cadmium, the recovery rate of tellurium reaches 94.06%, and the recovery rate of cadmium reaches 89.60%.
2. The process flow is simple, the investment of process equipment is relatively low, the flue gas after tellurium and cadmium are recovered reaches the standard and is discharged, and the environmental protection pressure is low.
3. The method has the advantages of high recovery rate of valuable metals, short process flow, little environmental pollution, simple operation and the like.
Drawings
FIG. 1 is a schematic process flow diagram of a pyrogenic process treatment and recovery process of a cadmium telluride thin film solar cell of the present invention.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
According to the invention, the back plate glass of the cadmium telluride thin film solar cell is peeled in a mechanical knocking mode, the front glass substrate and the EVA thin film after the back plate is peeled are crushed into pieces with the size of 2-4 cm, the pieces are added into a roasting furnace for oxidizing roasting at 700-800 ℃, and tellurium and cadmium entering smoke in the form of tellurium oxide and cadmium oxide are recovered by smoke dust collection equipment. Finally, the recovery rate of tellurium reaches 94.06%, and the recovery rate of cadmium reaches 89.60%.
Example 1:
referring to fig. 1, the invention provides a pyrogenic process treatment and recovery process of a cadmium telluride thin film solar cell. In a treatable cadmium telluride thin film solar cell: the tellurium content was 960ppm and the cadmium content was 438 ppm.
The process comprises the following steps:
(1) the back plate glass is peeled off from the cadmium telluride thin film solar cell in a mechanical knocking mode, the back plate glass is directly recycled, and the front glass and the EVA thin film are crushed into small blocks with the particle size of 2 cm.
(2) Placing the crushed front glass and the EVA film in a roasting furnace for oxidizing roasting; the roasting furnace used for roasting adopts electric heating, the roasting temperature is 700 ℃, and the roasting time is 1 h. The atmosphere in the roasting furnace is an oxidizing atmosphere, and the hearth ensures the micro negative pressure of-15 Pa; the tellurium content in the roasted waste slag is 58ppm, and the cadmium content in the roasted waste slag is 47 ppm.
(3) And recycling tellurium and cadmium entering the flue gas in the forms of tellurium oxide and cadmium oxide by using flue gas dust collection equipment. The process for recovering tellurium and cadmium in the smoke dust adopts the processes of gravity settling, cyclone dust collection and cloth bag dust collection.
In the embodiment, the tellurium recovery rate reaches 93.96%, and the cadmium recovery rate reaches 89.27%.
Example 2:
referring to fig. 1, the invention provides a pyrogenic process treatment and recovery process of a cadmium telluride thin film solar cell. In a treatable cadmium telluride thin film solar cell: the tellurium content was 938ppm and the cadmium content was 425 ppm.
The process comprises the following steps:
(1) the back plate glass is peeled off from the cadmium telluride thin film solar cell in a mechanical knocking mode, the back plate glass is directly recycled, and the front glass and the EVA thin film are crushed into small blocks with the grain size of 4 cm.
(2) Placing the crushed front glass and the EVA film in a roasting furnace for oxidizing roasting; the roasting furnace used for roasting adopts electric heating, the roasting temperature is 800 ℃, and the roasting time is 1.5 h. The atmosphere in the roasting furnace is an oxidizing atmosphere, and the hearth ensures micro negative pressure of-5 Pa; the tellurium content in the roasted waste slag is 59ppm, and the cadmium content in the roasted waste slag is 48 ppm.
(3) And recycling tellurium and cadmium entering the flue gas in the forms of tellurium oxide and cadmium oxide by using flue gas dust collection equipment. The process for recovering tellurium and cadmium in the smoke dust adopts the processes of gravity settling, cyclone dust collection and cloth bag dust collection.
In the embodiment, the tellurium recovery rate reaches 93.71 percent, and the cadmium recovery rate reaches 88.71 percent.
Example 3:
referring to fig. 1, the invention provides a pyrogenic process treatment and recovery process of a cadmium telluride thin film solar cell. In a treatable cadmium telluride thin film solar cell: the tellurium content was 1010ppm and the cadmium content was 480 ppm.
The process comprises the following steps:
(1) the back plate glass is peeled off from the cadmium telluride thin film solar cell in a mechanical knocking mode, the back plate glass is directly recycled, and the front glass and the EVA thin film are crushed into small blocks with the grain size of 3 cm.
(2) Placing the crushed front glass and the EVA film in a roasting furnace for oxidizing roasting; the roasting furnace used for roasting adopts electric heating, the roasting temperature is 750 ℃, and the roasting time is 1.2 h. The atmosphere in the roasting furnace is an oxidizing atmosphere, and the hearth ensures the micro negative pressure of-10 Pa; the tellurium content in the roasted waste slag is 60ppm, and the cadmium content in the roasted waste slag is 50 ppm.
(3) And recycling tellurium and cadmium entering the flue gas in the forms of tellurium oxide and cadmium oxide by using flue gas dust collection equipment. The process for recovering tellurium and cadmium in the smoke dust adopts the processes of gravity settling, cyclone dust collection and cloth bag dust collection.
In the embodiment, the tellurium recovery rate reaches 94.06%, and the cadmium recovery rate reaches 89.60%.
Although embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are illustrative and not restrictive, and that those skilled in the art may make changes, modifications, substitutions and alterations to the above embodiments without departing from the scope of the present invention.
Claims (7)
1. A pyrogenic process treatment and recovery process of a cadmium telluride thin film solar cell is characterized in that: the method comprises the following steps:
(1) stripping back plate glass of the cadmium telluride thin film solar cell in a mechanical knocking mode, directly recovering the back plate glass, and crushing the front glass and the EVA thin film into small pieces;
(2) placing the crushed front glass and the EVA film in a roasting furnace for oxidizing roasting;
(3) and recycling tellurium and cadmium entering the flue gas in the forms of tellurium oxide and cadmium oxide by using flue gas dust collection equipment.
2. The pyrometallurgical recovery process of cadmium telluride thin film solar cells as in claim 1, wherein: in the cadmium telluride thin film solar cell: the tellurium content is 920-1020 ppm, and the cadmium content is 450-500 ppm.
3. The pyrometallurgical recovery process of cadmium telluride thin film solar cells as in claim 1, wherein: in the step (1), the front glass and the EVA film are crushed into small pieces with the particle size of 2-4 cm.
4. The pyrometallurgical recovery process of cadmium telluride thin film solar cells as in claim 1, wherein: in the step (2), a roasting furnace used for roasting is electrically heated, the roasting temperature is 700-800 ℃, and the roasting time is 1-1.5 h.
5. The pyrometallurgical recovery process of cadmium telluride thin film solar cells as in claim 4 wherein: the atmosphere in the roasting furnace is an oxidizing atmosphere, and the furnace chamber ensures the micro negative pressure of-15 to-5 Pa.
6. The pyrometallurgical recovery process of cadmium telluride thin film solar cells as in claim 1, wherein: in the step (2), the tellurium content in the roasted waste slag is lower than 60ppm, and the cadmium content is lower than 50 ppm.
7. The pyrometallurgical recovery process of cadmium telluride thin film solar cells as in claim 1, wherein: in the step (3), the process for recovering tellurium and cadmium in the smoke dust adopts the processes of gravity settling, cyclone dust collection and bag dust collection.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110547253.0A CN113564361A (en) | 2021-05-19 | 2021-05-19 | Pyrogenic treatment and recovery process of cadmium telluride thin-film solar cell |
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| CN202110547253.0A CN113564361A (en) | 2021-05-19 | 2021-05-19 | Pyrogenic treatment and recovery process of cadmium telluride thin-film solar cell |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2737935A1 (en) * | 1976-08-25 | 1978-03-02 | Cra Services | PROCESS FOR THE OBTAINMENT OF SELENIUM AND / OR CADMIUM |
| US20020030035A1 (en) * | 2000-09-11 | 2002-03-14 | Manuel Dieguez | Process for recycling CdTe/Cds thin film solar cell modules |
| CN101191158A (en) * | 2006-11-21 | 2008-06-04 | 比亚迪股份有限公司 | Method for reclaiming metal cadmium from cadmium-containing waste material |
| CN101613804A (en) * | 2009-07-28 | 2009-12-30 | 北京科技大学 | A kind of method of recovering cadmium from waste nickel-cadmium battery |
| TW201425594A (en) * | 2012-12-27 | 2014-07-01 | Univ Nat Cheng Kung | Recycling method of copper-indium-gallium-selenium residual target |
| CN108913902A (en) * | 2018-07-17 | 2018-11-30 | 成都中建材光电材料有限公司 | A kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly |
| CN108950213A (en) * | 2018-07-03 | 2018-12-07 | 昆明理工大学 | A method of recycling tellurium and bismuth from bismuth telluride material |
-
2021
- 2021-05-19 CN CN202110547253.0A patent/CN113564361A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2737935A1 (en) * | 1976-08-25 | 1978-03-02 | Cra Services | PROCESS FOR THE OBTAINMENT OF SELENIUM AND / OR CADMIUM |
| US20020030035A1 (en) * | 2000-09-11 | 2002-03-14 | Manuel Dieguez | Process for recycling CdTe/Cds thin film solar cell modules |
| CN101191158A (en) * | 2006-11-21 | 2008-06-04 | 比亚迪股份有限公司 | Method for reclaiming metal cadmium from cadmium-containing waste material |
| CN101613804A (en) * | 2009-07-28 | 2009-12-30 | 北京科技大学 | A kind of method of recovering cadmium from waste nickel-cadmium battery |
| TW201425594A (en) * | 2012-12-27 | 2014-07-01 | Univ Nat Cheng Kung | Recycling method of copper-indium-gallium-selenium residual target |
| CN108950213A (en) * | 2018-07-03 | 2018-12-07 | 昆明理工大学 | A method of recycling tellurium and bismuth from bismuth telluride material |
| CN108913902A (en) * | 2018-07-17 | 2018-11-30 | 成都中建材光电材料有限公司 | A kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly |
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Application publication date: 20211029 |