CN102887603B - Method for recycling and utilizing CdS waste liquor produced in production process of copper indium gallium selenide (CIGS) film solar cell - Google Patents
Method for recycling and utilizing CdS waste liquor produced in production process of copper indium gallium selenide (CIGS) film solar cell Download PDFInfo
- Publication number
- CN102887603B CN102887603B CN201210378807.XA CN201210378807A CN102887603B CN 102887603 B CN102887603 B CN 102887603B CN 201210378807 A CN201210378807 A CN 201210378807A CN 102887603 B CN102887603 B CN 102887603B
- Authority
- CN
- China
- Prior art keywords
- cds
- waste liquid
- solar cell
- filter
- film solar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Sorption (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention discloses a method for recycling and utilizing CdS waste liquor produced in the production process of a copper indium gallium selenide (CIGS) film solar cell, wherein the method comprises the following steps of: (1) filtering the cadmium sulphide in the waste liquor; (2) performing oxidation treatment; (3) adsorbing the waste liquor with an active carbon filter; (4) carrying out ion exchange adsorption; (5) monitoring the waste liquor subjected to the ion exchange adsorption; and (6) vaporizing and concentrating the waste liquor. The method provided by the invention has the beneficial effects that a large number of industrial wastewater comprising CdS particles produced in the production process of the CIGS film solar cell is subject to a multi-stage continuous waste liquor treatment processes such as secondary filtering, oxidation treatment, activated carbon adsorption, ion exchange, back penetration and concentration evaporation, thereby realizing the zero discharge of the cadmium-containing industrial wastewater and effectively saving the industrial water; the filtering membrane and the ion exchanging agent in the treatment device are periodically recycled and exchanged to effectively reduce the energy consumption in the treatment of the waste liquor.
Description
Technical field
The present invention relates to the recoverying and utilizing method of industrial effluent in a kind of solar energy generation technology field, be specifically related to the CdS waste liquid recoverying and utilizing method producing in a kind of copper-indium-galliun-selenium CIGS thin film solar cell production process.
Background technology
Copper-indium-galliun-selenium CIGS thin film solar cell because its specific absorption is high, band gap is adjustable, with low cost, turnover ratio is high, the low light level is good, stable performance and the advantage such as capability of resistance to radiation is strong, and become current industrial community and emphasis that research institution falls over each other exploitation.In recent years under its premium properties and great demand background, comprise that global numerous corporate facilitys such as U.S.'s renewable energy source laboratory NREL, Solar Frontier, Miasole, Global solar, Wurth Solar drop into huge financial resources and manpower is researched and developed and produced, 2011 annual capacities reach GW level, demonstrate good growth momentum.
In copper-indium-galliun-selenium CIGS solar battery structure; in order to realize the coupling of band gap between P type CIGS absorption layer and N-type Window layer film ZnO; simultaneously for effective protection absorption layer material when the sputter Window layer, thereby the Cadmium Sulfide CdS film of introducing 50nm between the two is as cushioning layer material.Laboratory and industry member all adopt chemical bath deposition CdS film at present, thereby relate to the problem of environmental pollution of cadmium, and the widespread use that contains cadmium material certainly will cause the pollution to soil and water.Harmful because of cadmium, it can be accumulated at human body by food chain, or directly acts on human body and cause acute and chronic cadmium poisoning, and a plurality of countries comprise that the situation of zone of pollution cadmium poisoning also once appearred in China in the world.Cadmium has caused the great attention of countries in the world to the harm of human body, all formulated corresponding standard.The maximal emission of China's regulation cadmium in industrial wastewater is 0.1mgL
-1.For fear of the generation of cadmium poisoning event, protect our ecotope, thereby cadmium wastewater must process before discharge, the trade effluent after up to standard just can discharge or recycle.
At present, the method for processing cadmium wastewater mainly contains physics, chemical method and microbial method.On State Intellectual Property Office of the People's Republic of China's patent website, disclose a kind of zinc, cadmium sewage water treatment method, added alkaline neutraliser and vulcanizing agent, form cadmium hydroxide and Cadmium Sulfide, then separation has been removed.But above-mentioned treatment process need to add vulcanizing agent, excessive vulcanizing agent also needs to add ferrous sulfate to remove, and has caused the pollution of environment.
Summary of the invention
The present invention is directed to above-mentioned deficiency of the prior art, the multistage continuous process for treating waste liquor such as a kind of employing cascade filtration, oxide treatment, charcoal absorption, ion-exchange, back of the body infiltration and evaporative concn are provided, realize the zero release of the CdS waste liquid producing containing cadmium industrial production copper-indium-galliun-selenium CIGS thin film solar cell, and can effectively reduce production energy consumption, reach the CdS waste liquid recoverying and utilizing method producing in the copper-indium-galliun-selenium CIGS thin film solar cell production process of energy-saving and emission-reduction object.
Object of the present invention can realize by following technical proposal: the CdS waste liquid recoverying and utilizing method producing in a kind of copper-indium-galliun-selenium CIGS thin film solar cell production process, and the method comprises the following steps:
(1) the Cadmium Sulfide CdS in filtering waste liquid: the CdS waste liquid producing during copper-indium-galliun-selenium CIGS thin film solar cell is produced, after the even water quality of Buffer Pool, again through employing the secondary filter of two kinds of different pore size filter screens to filter, with the solid-state CdS powder in filtering waste liquid;
(2) oxide treatment: the waste liquid that filters out solid-state CdS dust is passed in reaction tank, add oxygenant in reaction tank, to carry out stirring reaction, utilize oxygenant respectively remaining thiocarbamide and Cadmium Sulfide in waste liquid to be oxidized to thiourea peroxide and solubility Cadmium Sulphate CdSO
4;
(3) activated charcoal filter absorption: the solution after oxide treatment in reaction tank is passed into pH regulator pond, add HCL and NaOH to regulate pH to neutrality, then filter to absorb by two-stage activated carbon filter and dispose oxygenant unnecessary in solution and micro-CdS;
(4) ion-exchange absorption: the solution after activated charcoal filter absorption is filtered by selective ion exchange resin, filter out the CdS of remaining less than 1% in solution;
(5) monitoring is through the attached waste liquid of ion-exchange absorption, and wherein qualified water is recycled to the recycle of chemical water bathing pool, and defective waste liquid is again after back of the body infiltration, and wherein qualified solution circulated is recycled;
(6) evaporation concentration: after back of the body infiltration, underproof residual waste solution is through evaporation concentration, and the qualified part of evaporation is recycled, and remains micro-concentrating spent liquor and is reclaimed by specialized company;
The separatory membrane that secondary filter in described step (1) comprises twice different pore size, described first is the filter membrane in 400-600nm aperture, second is the filter membrane in 250-500nm aperture.
The principle of the technical program: the CdS particle in the CdS waste liquid producing in copper-indium-galliun-selenium CIGS thin film solar cell production process is after the secondary filter of two kinds of different pore size filter screens filters, solid-state CdS powder in filtering waste liquid, after adding oxygenant to stir, utilize oxygenant respectively remaining thiocarbamide and Cadmium Sulfide in waste liquid to be oxidized to thiourea peroxide and solubility Cadmium Sulphate CdSO
4and adjust pH value to the solution after neutrality again through charcoal absorption, ion-exchange, back of the body infiltration and evaporation concentration, realize containing the zero release of cadmium industrial effluent, can effectively save process water, the filtering membrane in treatment unit and ion-exchanger Deng You producer regularly reclaim replacing.
Further, in described step (3), unnecessary hydrogen peroxide and micro-cadmium salt is to adsorb by two-stage activated carbon filter.
Further, in described step (4), utilize and select ion exchange resin to filter out cadmium ion a small amount of in waste liquid.
Further, in described step (5), the defective waste liquid of monitoring permeates purifying treatment through the back of the body.
Further, in described step (6), residual waste solution is processed through evaporation concentration.
The main equation relating in aforementioned techniques scheme is as follows:
SC(NH
2)
2+2H
2O
2→SC(NH
2)
2O
2+2H
2O
CdS+8H
2O
2→CdSO
4+8H
2O+2O
2
Adopt above-mentioned recoverying and utilizing method, the present invention compared with prior art, have the following advantages: after solar cell piece deposition CdS buffer layer in copper-indium-galliun-selenium CIGS thin film solar cell production process, through rinsing, produce a large amount of trade effluents containing CdS particle, through cascade filtration, oxide treatment, charcoal absorption, ion-exchange, the multistage continuous process for treating waste liquor such as back of the body infiltration and evaporative concn, realized containing the zero release of cadmium industrial effluent, can effectively save process water, filtering membrane in treatment unit and ion-exchanger etc. regularly reclaim and change, can effectively reduce the energy consumption in liquid waste disposal.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2-4 are for CdS waste liquid is through the colloidal solution Tyndall effect picture before and after secondary filter processing.
Embodiment
Embodiment 1
Now the present invention is described in further detail by reference to the accompanying drawings, and with reference to Fig. 1,2, embodiment is:
Cadmium Sulfide CdS in filtering waste liquid: the CdS waste liquid producing during copper-indium-galliun-selenium CIGS thin film solar cell is produced, after the even water quality of Buffer Pool, through secondary filter, filter again, CdS particle in filtering waste liquid, the separatory membrane that wherein secondary filter comprises twice different pore size, first is the filter membrane in 400nm aperture, and second is the filter membrane in 250nm aperture.Wherein the yellow waste liquid of sulfur-bearing cadmium, as shown in Figure 2, after secondary filter filters, can obviously observe the peculiar Tyndall effect of colloidal solution.After first membrane filtration, solution becomes clarification, and Tyndall phenomenon is may be seen indistinctly, as shown in Figure 3.Pass through again second membrane filtration, obtain clear soln, do not observe Tyndall phenomenon, as shown in Figure 4 simultaneously.
Oxide treatment: the waste liquid that filters out solid-state CdS dust is passed in reaction tank, add oxygenant H
2o
2at reaction tank stirring reaction, utilize oxygenant respectively remaining thiocarbamide and Cadmium Sulfide in waste liquid to be oxidized to thiourea peroxide and solubility Cadmium Sulphate CdSO
4.
Activated charcoal filter absorption: the solution after oxide treatment in reaction tank is passed into pH regulator pond, add HCL and NaOH to regulate pH to neutrality, then filter to absorb by two-stage activated carbon filter and dispose oxygenant unnecessary in solution and micro-CdS.
Ion-exchange absorption: the solution after activated charcoal filter absorption is filtered by selective ion exchange resin, filter out the CdS of remaining less than 1% in solution.
Monitoring qualified water is recycled to the recycle of chemical water bathing pool, monitors defective waste water again through carrying on the back after infiltration, monitors qualified solution circulated and recycles.
Evaporation concentration: the underproof residual waste solution after back of the body infiltration is through evaporation concentration, and the qualified part of evaporation is recycled, and remains micro-concentrating spent liquor and is reclaimed by specialized company.
Press 100MWCIGS thin film solar cell production capacity, the CdS flushing waste water generation of 10000 tons/year calculates, after ion exchange resin exchange, 500 tons of the defective waste liquids of monitoring of annual generation 5%, after back of the body infiltration, general 80% qualified solution recycle and reuse, 20% approximately 100 ton of waste liquid is defective, need to pass through evaporation concentration, cause and recycling surpass 95% waste liquid, produce the waste liquid of approximately 5 tons/year of less thaies 5% simultaneously, every day, (by 1 year 300 days production calculations) only produced the waste liquid of about 16.7L, thereby real realization containing the zero release of cadmium industrial effluent, year backwater amount approaches 100%, can effectively save process water, filtering membrane in treatment unit and ion-exchanger regularly reclaim replacing by producer, and only 100 tons of the waste liquid amount of year evaporation concentration, can effectively reduce the energy consumption in liquid waste disposal.
Claims (6)
1. the CdS waste liquid recoverying and utilizing method producing in copper-indium-galliun-selenium CIGS thin film solar cell production process, is characterized in that, the method comprises the following steps:
(1) the Cadmium Sulfide CdS in filtering waste liquid: the CdS waste liquid producing during copper-indium-galliun-selenium CIGS thin film solar cell is produced, after the even water quality of Buffer Pool, again through employing the secondary filter of two kinds of different pore size filter screens to filter, with the solid-state CdS powder in filtering waste liquid;
(2) oxide treatment: the waste liquid that filters out solid-state CdS dust is passed in reaction tank, add oxygenant in reaction tank, to carry out stirring reaction, utilize oxygenant respectively remaining thiocarbamide and Cadmium Sulfide in waste liquid to be oxidized to thiourea peroxide and solubility Cadmium Sulphate CdSO
4;
(3) activated charcoal filter absorption: the solution after oxide treatment in reaction tank is passed into pH regulator pond, add HCl and NaOH to regulate pH to neutrality, then filter to absorb by two-stage activated carbon filter and dispose oxygenant unnecessary in solution and micro-CdS;
(4) ion-exchange absorption: the solution after activated charcoal filter absorption is filtered by selective ion exchange resin, filter out the CdS of remaining less than 1% in solution;
(5) monitoring is through the attached waste liquid of ion-exchange absorption, and wherein qualified water is recycled to the recycle of chemical water bathing pool, and defective waste liquid is again after back of the body infiltration, and wherein qualified solution circulated is recycled;
(6) evaporation concentration: underproof residual waste solution is through evaporation concentration after back of the body infiltration, and the qualified part of evaporation is recycled, and remains micro-concentrating spent liquor and is reclaimed by specialized company;
The separatory membrane that secondary filter in described step (1) comprises twice different pore size, described first is the filter membrane in 400-600nm aperture, second is the filter membrane in 250-500nm aperture.
2. the CdS waste liquid recoverying and utilizing method producing in copper-indium-galliun-selenium CIGS thin film solar cell production process according to claim 1, is characterized in that, the oxide treatment oxygenant used in described step (2) in reaction tank is oxydol H
2o
2.
3. the CdS waste liquid recoverying and utilizing method producing in copper-indium-galliun-selenium CIGS thin film solar cell production process according to claim 1, is characterized in that, hydrogen peroxide and micro-cadmium salt unnecessary in described step (3) are to adsorb by two-stage activated carbon filter.
4. the CdS waste liquid recoverying and utilizing method producing in copper-indium-galliun-selenium CIGS thin film solar cell production process according to claim 1, is characterized in that, utilizes and select ion exchange resin to filter out cadmium ion a small amount of in waste liquid in described step (4).
5. the CdS waste liquid recoverying and utilizing method producing in copper-indium-galliun-selenium CIGS thin film solar cell production process according to claim 1, is characterized in that, in described step (5), the defective waste liquid of monitoring is through back of the body infiltration purifying treatment.
6. the CdS waste liquid recoverying and utilizing method producing in copper-indium-galliun-selenium CIGS thin film solar cell production process according to claim 1, is characterized in that, in described step (6), residual waste solution is processed through evaporation concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210378807.XA CN102887603B (en) | 2012-10-08 | 2012-10-08 | Method for recycling and utilizing CdS waste liquor produced in production process of copper indium gallium selenide (CIGS) film solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210378807.XA CN102887603B (en) | 2012-10-08 | 2012-10-08 | Method for recycling and utilizing CdS waste liquor produced in production process of copper indium gallium selenide (CIGS) film solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102887603A CN102887603A (en) | 2013-01-23 |
| CN102887603B true CN102887603B (en) | 2014-09-10 |
Family
ID=47531309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210378807.XA Active CN102887603B (en) | 2012-10-08 | 2012-10-08 | Method for recycling and utilizing CdS waste liquor produced in production process of copper indium gallium selenide (CIGS) film solar cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102887603B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108048822A (en) * | 2017-12-20 | 2018-05-18 | 北京铂阳顶荣光伏科技有限公司 | Chemical bath deposition device and its deposition method, Mead-Bauer recovery system |
| CN108793561A (en) * | 2018-06-26 | 2018-11-13 | 辽宁莱特莱德环境工程有限公司 | Cadmium ammonia waste water Zero discharging system and method applied to efficient film production line for manufacturing battery |
| CN110294560A (en) * | 2019-03-19 | 2019-10-01 | 中国电子系统工程第二建设有限公司 | A kind of thin-film solar cells producing wastewater treatment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686870A (en) * | 2005-03-31 | 2005-10-26 | 苏州市环境工程有限责任公司 | Technique for processing reclamation of industrial wastewater from printing electronic circuit board |
| JP2007313445A (en) * | 2006-05-26 | 2007-12-06 | Nippon Rensui Co Ltd | Wastewater treatment method, wastewater treatment apparatus, and wastewater recovery system |
| CN201141001Y (en) * | 2007-12-25 | 2008-10-29 | 苏州市环境工程有限责任公司 | Printing and dyeing wastewater recycling and processing equipment |
| CN101343125A (en) * | 2008-08-26 | 2009-01-14 | 昆山工研院华科生物高分子材料研究所有限公司 | Heavy metal waste water treatment process and apparatus |
-
2012
- 2012-10-08 CN CN201210378807.XA patent/CN102887603B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686870A (en) * | 2005-03-31 | 2005-10-26 | 苏州市环境工程有限责任公司 | Technique for processing reclamation of industrial wastewater from printing electronic circuit board |
| JP2007313445A (en) * | 2006-05-26 | 2007-12-06 | Nippon Rensui Co Ltd | Wastewater treatment method, wastewater treatment apparatus, and wastewater recovery system |
| CN201141001Y (en) * | 2007-12-25 | 2008-10-29 | 苏州市环境工程有限责任公司 | Printing and dyeing wastewater recycling and processing equipment |
| CN101343125A (en) * | 2008-08-26 | 2009-01-14 | 昆山工研院华科生物高分子材料研究所有限公司 | Heavy metal waste water treatment process and apparatus |
Non-Patent Citations (2)
| Title |
|---|
| 实验废料中镉的循环利用;杨睿;《中国资源综合利用》;20020228;第20-22页 * |
| 杨睿.实验废料中镉的循环利用.《中国资源综合利用》.2002,第20-22页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102887603A (en) | 2013-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103553249B (en) | In electroplating effluent, acid is separated and heavy metal collection method | |
| CN102603097A (en) | Advanced treatment and recycling process for wastewater containing heavy metal ions | |
| CN106277513B (en) | High ammonia nitrogen contains cadmium photovoltaic wastewater containing thiocarbamide processing method and system | |
| CN106587472B (en) | A kind of recycling recoverying and utilizing method of the electroplating wastewater containing palladium | |
| CN107285545A (en) | A kind of cadmium ammonia waste water technique of zero discharge of thin-film solar cells production line | |
| CN107973467A (en) | A kind of manufacture of solar cells waste water zero discharge treatment process | |
| CN102887603B (en) | Method for recycling and utilizing CdS waste liquor produced in production process of copper indium gallium selenide (CIGS) film solar cell | |
| CN102897885B (en) | The method of sulfuric acid industry Two-way Cycle jet-type arsenic removal | |
| CN203715400U (en) | Low-concentration lead-containing wastewater treatment equipment | |
| CN103449623A (en) | Method for preparing metal nanometer material by recovering from industrial waste water | |
| CN108314242A (en) | High ammonia nitrogen contains the fluorine-containing photovoltaic wastewater processing method of arsenic and system | |
| CN102642974B (en) | Method for treating high-acid high-chlorine waste water | |
| CN104211239A (en) | Treatment method for aniline and nitrobenzene containing wastewater | |
| CN110407359A (en) | One kind adopting beneficiation wastewater treatment method | |
| CN112607925B (en) | Silicon steel dilute acid wastewater zero-discharge treatment method and system | |
| Sun et al. | Research progress of arsenic removal from wastewater | |
| CN104005050A (en) | Method for treating and recycling divalent manganese in electrolytic manganese wastewater | |
| CN109052785A (en) | A kind of Zero-discharge treating process of thin-film solar cells production waste water | |
| CN218811144U (en) | Deep bed ion acid mine wastewater treatment system capable of recycling | |
| CN106277487A (en) | A kind of electrochemicial oxidation desulfurization wastewater device | |
| CN103373774A (en) | Membrane-method high-powered recycling process for fluoride-containing wastewater generated by photovoltaic industry and dedicated system of membrane-method high-powered recycling process | |
| CN103466871B (en) | Treatment method and recycling system for industrial wastewater of polycrystalline silicon batteries | |
| CN102092869A (en) | Processing method of waste acid in acid producing system | |
| Shen et al. | Advanced treatment process for papermaking wastewater by composite photoelectrocatalysis and heterogeneous photocatalysis of nano-TiO2 colloid and its pilot-scale system | |
| CN206089111U (en) | Automatic water purifier of lake water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |