CN102887603A - 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
- CN102887603A CN102887603A CN201210378807XA CN201210378807A CN102887603A CN 102887603 A CN102887603 A CN 102887603A CN 201210378807X A CN201210378807X A CN 201210378807XA CN 201210378807 A CN201210378807 A CN 201210378807A CN 102887603 A CN102887603 A CN 102887603A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- cds
- filter
- solar cell
- 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.)
- Granted
Links
Images
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 that produces 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 is because its specific absorption is high, band gap is adjustable, with low cost, the advantage such as turnover ratio is high, the low light level good, stable performance and capability of resistance to radiation are strong, and becomes the emphasis that current industrial community and research institution fall over each other to develop.In recent years under its premium properties and great demand background, comprise U.S. renewable energy source laboratory NREL, Solar Frontier, Miasole, global numerous corporate facilitys such as Global solar, Wurth Solar drop into huge financial resources and manpower is researched and developed and produced, 2011 annual capacities reach the 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 the 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.At present laboratory and industry member all adopt chemical bath deposition CdS film, 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, perhaps directly acts on human body and causes 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, has all formulated corresponding standard.The maximal emission of China's regulation cadmium in industrial wastewater is 0.1mgL
-1For fear of the generation of cadmium poisoning event, protect our ecotope, thereby cadmium wastewater must process before discharging, 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.Disclose a kind of zinc, cadmium sewage water treatment method on State Intellectual Property Office of the People's Republic of China's patent website, added alkaline neutraliser and vulcanizing agent, formed cadmium hydroxide and Cadmium Sulfide, separated again and remove.But above-mentioned treatment process need to add vulcanizing agent, and excessive vulcanizing agent also needs to add ferrous sulfate to be removed, 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, realization contains the zero release of the CdS waste liquid of cadmium industrial production copper-indium-galliun-selenium CIGS thin film solar cell generation, and can effectively reduce production energy consumption, reach the CdS waste liquid recoverying and utilizing method that produces in the copper-indium-galliun-selenium CIGS thin film solar cell production process of energy-saving and emission-reduction purpose.
Purpose of the present invention can realize by following technical proposal: the CdS waste liquid recoverying and utilizing method that produces in a kind of copper-indium-galliun-selenium CIGS thin film solar cell production process, and the method may further comprise the steps:
(1) the Cadmium Sulfide CdS in the filtering waste liquid: with the CdS waste liquid that produces in the production of copper-indium-galliun-selenium CIGS thin film solar cell, after the even water quality of Buffer Pool, filter through the secondary filter that adopts two kinds of different pore size filter screens again, with the solid-state CdS powder in the filtering waste liquid;
(2) oxide treatment: the waste liquid that will filter out solid-state CdS dust passes in the reaction tank, add oxygenant and in reaction tank, carry out stirring reaction, utilize oxygenant respectively remaining thiocarbamide and Cadmium Sulfide in the 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 the reaction tank is passed into the pH regulator pond, add HCL and NaOH and regulate pH to neutrality, filter to absorb by two-stage activated carbon filter again and dispose oxygenant unnecessary in the solution and micro-CdS;
(4) ion-exchange absorption: will filter by selective ion exchange resin through the solution after the activated charcoal filter absorption, filter out the CdS of remaining less than 1% in the 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 through back of the body infiltration after, wherein recycle again by qualified solution circulated for defective waste liquid;
(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 the concentrating spent liquor of residue trace is reclaimed by specialized company.
The principle of the technical program: the CdS particle in the CdS waste liquid that produces in the 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 the filtering waste liquid, after adding the oxygenant stirring, utilize oxygenant respectively remaining thiocarbamide and Cadmium Sulfide in the waste liquid to be oxidized to thiourea peroxide and solubility Cadmium Sulphate CdSO
4And adjust the solution of pH value to the neutrality again through charcoal absorption, ion-exchange, back of the body infiltration and evaporation concentration, realization contains the zero release of cadmium industrial effluent, can effectively save process water, and the filtering membrane in the treatment unit and ion-exchanger etc. regularly reclaim replacing by producer.
As preferably, the secondary filter in the described step (1) comprises the separatory membrane of twice different pore size, and described first is the filter membrane in 400-600 nm aperture, and second is the filter membrane in 250-500 nm aperture.
As preferably, the used oxygenant of oxide treatment in the described step (2) in the reaction tank is oxydol H
2O
2
Further, unnecessary hydrogen peroxide and micro-cadmium salt is to adsorb by two-stage activated carbon filter in the described step (3).
Further, utilize selection ion exchange resin to filter out cadmium ion a small amount of in the waste liquid in the described step (4).
Further, the defective waste liquid of monitoring permeates purifying treatment through the back of the body in the described step (5).
Further, residue pus waste liquid is processed through evaporation concentration in the described step (6).
The main equation that relates in the 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 the copper-indium-galliun-selenium CIGS thin film solar cell production process, through flushing, produce the trade effluent that contains in a large number the 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 the treatment unit and ion-exchanger etc. regularly reclaim and change, and can effectively reduce the energy consumption in the liquid waste disposal.
Description of drawings
Fig. 1 is process flow sheet of the present invention;
Fig. 2-4 processes the colloidal solution Tyndall effect picture of front and back through secondary filter for the CdS waste liquid.
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 the filtering waste liquid: with the CdS waste liquid that produces in the production of copper-indium-galliun-selenium CIGS thin film solar cell, after the even water quality of Buffer Pool, filter through secondary filter again, CdS particle in the filtering waste liquid, wherein secondary filter comprises the separatory membrane of twice different pore size, first is the filter membrane in 400 nm apertures, and second is the filter membrane in 250 nm apertures.Wherein the yellow waste liquid of Containing Sulfur cadmium as shown in Figure 2, after the secondary filter filtration, can obviously be observed the peculiar Tyndall effect of colloidal solution.Behind the first membrane filtration, solution becomes clarification, and Tyndall phenomenon is may be seen indistinctly, as shown in Figure 3.Pass through again the second membrane filtration, then obtain clear soln, do not observe simultaneously Tyndall phenomenon, as shown in Figure 4.
Oxide treatment: the waste liquid that will filter out solid-state CdS dust passes in the reaction tank, adds oxygenant H
2O
2At the reaction tank stirring reaction, utilize oxygenant respectively remaining thiocarbamide and Cadmium Sulfide in the waste liquid to be oxidized to thiourea peroxide and solubility Cadmium Sulphate CdSO
4
Activated charcoal filter absorption: the solution after oxide treatment in the reaction tank is passed into the pH regulator pond, add HCL and NaOH and regulate pH to neutrality, filter to absorb by two-stage activated carbon filter again and dispose oxygenant unnecessary in the solution and micro-CdS.
Ion-exchange absorption: will filter by selective ion exchange resin through the solution after the activated charcoal filter absorption, filter out the CdS of remaining less than 1% in the solution.
The monitoring qualified water is recycled to the recycle of chemical water bathing pool, monitors defective waste water again through after the back of the body infiltration, monitors qualified solution circulated and recycles.
Evaporation concentration: the underproof residue pus waste liquid after back of the body infiltration is through evaporation concentration, and the qualified part of evaporation is recycled, and the concentrating spent liquor of residue trace is reclaimed by specialized company.
By 100 MW CIGS thin film solar cell production capacities, 10,000 ton/years CdS flushing waste water generation calculates, after the 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% about 100 tons of waste liquids are defective, need through evaporation concentration, thereby recycle to surpass again 95% waste liquid, and produce simultaneously the about 5 ton/years waste liquid of less than 5%, only produce the waste liquid of about 16.7L every day (produce calculate by 1 year 300 days), thereby real realization contains the zero release of cadmium industrial effluent, year backwater amount can effectively be saved process water near 100%, and the filtering membrane in the 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 the liquid waste disposal.
Claims (7)
1. the CdS waste liquid recoverying and utilizing method that produces in the copper-indium-galliun-selenium CIGS thin film solar cell production process is characterized in that the method may further comprise the steps:
(1) the Cadmium Sulfide CdS in the filtering waste liquid: with the CdS waste liquid that produces in the production of copper-indium-galliun-selenium CIGS thin film solar cell, after the even water quality of Buffer Pool, filter through the secondary filter that adopts two kinds of different pore size filter screens again, with the solid-state CdS powder in the filtering waste liquid;
(2) oxide treatment: the waste liquid that will filter out solid-state CdS dust passes in the reaction tank, add oxygenant and in reaction tank, carry out stirring reaction, utilize oxygenant respectively remaining thiocarbamide and Cadmium Sulfide in the 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 the reaction tank is passed into the pH regulator pond, add HCL and NaOH and regulate pH to neutrality, filter to absorb by two-stage activated carbon filter again and dispose oxygenant unnecessary in the solution and micro-CdS;
(4) ion-exchange absorption: will filter by selective ion exchange resin through the solution after the activated charcoal filter absorption, filter out the CdS of remaining less than 1% in the 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 through back of the body infiltration after, wherein recycle again by qualified solution circulated for defective waste liquid;
(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 the concentrating spent liquor of residue trace is reclaimed by specialized company.
2. the CdS waste liquid recoverying and utilizing method that produces in the copper-indium-galliun-selenium CIGS thin film solar cell production process according to claim 1, it is characterized in that, secondary filter in the described step (1) comprises the separatory membrane of twice different pore size, described first is the filter membrane in 400-600 nm aperture, and second is the filter membrane in 250-500 nm aperture.
3. the CdS waste liquid recoverying and utilizing method that produces in the copper-indium-galliun-selenium CIGS thin film solar cell production process according to claim 1 is characterized in that, the used oxygenant of oxide treatment in the described step (2) in the reaction tank is oxydol H
2O
2
4. the CdS waste liquid recoverying and utilizing method that produces in the 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 the described step (3) are to adsorb by two-stage activated carbon filter.
5. the CdS waste liquid recoverying and utilizing method that produces in the copper-indium-galliun-selenium CIGS thin film solar cell production process according to claim 1 is characterized in that, utilizes in the described step (4) and selects ion exchange resin to filter out cadmium ion a small amount of in the waste liquid.
6. the CdS waste liquid recoverying and utilizing method that produces in the copper-indium-galliun-selenium CIGS thin film solar cell production process according to claim 1 is characterized in that, the defective waste liquid of monitoring is through back of the body infiltration purifying treatment in the described step (5).
7. the CdS waste liquid recoverying and utilizing method that produces in the copper-indium-galliun-selenium CIGS thin film solar cell production process according to claim 1 is characterized in that, residue pus waste liquid is processed through evaporation concentration in the described step (6).
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 true CN102887603A (en) | 2013-01-23 |
| CN102887603B 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) |
Cited By (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 (1)
| Title |
|---|
| 杨睿: "实验废料中镉的循环利用", 《中国资源综合利用》 * |
Cited By (5)
| 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 |
| WO2019119902A1 (en) * | 2017-12-20 | 2019-06-27 | 北京铂阳顶荣光伏科技有限公司 | Waste liquid recovery system, chemical bath deposition device and deposition method therefor |
| CN110177900A (en) * | 2017-12-20 | 2019-08-27 | 北京铂阳顶荣光伏科技有限公司 | Mead-Bauer recovery system, chemical bath deposition device and its deposition method |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102887603B (en) | 2014-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106277513B (en) | High ammonia nitrogen contains cadmium photovoltaic wastewater containing thiocarbamide processing method and system | |
| CN101759158B (en) | Method for regenerating and recovering sulfuric acid from waste acid | |
| CN102603097A (en) | Advanced treatment and recycling process for wastewater containing heavy metal ions | |
| CN102941065A (en) | Carbon-based material adsorbent for removing heavy metals in waste water, its preparation method and application | |
| CN104787928A (en) | Recovery processing method of stainless steel acid pickling waste liquid containing iron, chromium and nickel | |
| 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 | |
| CN102476836A (en) | Method for treating arsenic-containing wastewater | |
| CN102897885B (en) | The method of sulfuric acid industry Two-way Cycle jet-type arsenic removal | |
| CN103011464A (en) | Treatment method of stibium-containing wastewater | |
| CN103373776B (en) | Photovoltaic industry fluoride waste qualified discharge technique | |
| CN206179892U (en) | Solar cell processing procedure chemical liquid recycling apparatus | |
| CN104211239A (en) | Treatment method for aniline and nitrobenzene containing wastewater | |
| CN203715400U (en) | Low-concentration lead-containing wastewater treatment equipment | |
| CN103449623A (en) | Method for preparing metal nanometer material by recovering from industrial waste water | |
| CN110407359A (en) | One kind adopting beneficiation wastewater treatment method | |
| CN106745676A (en) | A kind of ecological many negative electrode urine processing devices and method | |
| 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 | |
| CN102838254A (en) | Treatment process for acidic heavy metal wastewater | |
| 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 | |
| CN206089111U (en) | Automatic water purifier of lake water | |
| CN110304753A (en) | A kind of processing method of chemical nickeling ageing waste liquid | |
| CN102476860B (en) | Mercury removal agent for treating waste water containing mercury |
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 |