CN102776527A - Novel clean, energy-saving and environment-friendly technology for extracting high-grade copper plate by utilizing waste containing copper - Google Patents
Novel clean, energy-saving and environment-friendly technology for extracting high-grade copper plate by utilizing waste containing copper Download PDFInfo
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- CN102776527A CN102776527A CN2012102687866A CN201210268786A CN102776527A CN 102776527 A CN102776527 A CN 102776527A CN 2012102687866 A CN2012102687866 A CN 2012102687866A CN 201210268786 A CN201210268786 A CN 201210268786A CN 102776527 A CN102776527 A CN 102776527A
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Abstract
The invention discloses a novel clean, energy-saving and environment-friendly technology for extracting a high-grade copper plate by utilizing waste containing copper, and relates to the technical field of resource recycling. The technology comprises the following steps of: firstly crashing waste containing copper, filling the curshed waste into an anode frame; putting the anode frames filled with raw materials into an electrolytic bath as an anode; arranging a cathode plate between each two anode frames as a cathode; and heating an electrolytic solution, wherein a solution containing an acidic copper sulfate solution and an additive with certain amount is taken as the electrolytic solution, and the electrolytic solution always flows in a circulating mode in the electrolytic bath through an electrolytic solution circulating system; carrying out electrochemical solution of copper on the anode when direct-current electricity passes by in the electrolytic bath, and meanwhile separating out pure copper on the cathode; cleaning the cathode plate containing the finished product electrolytic copper, calculating, detecting and putting in storage to obtain a finished product electrolytic copper for selling; and further recycling and treating anode mud, and recycling the precious metal therein. The technology provided by the invention is simple in step, can effectively recycle the resources effectively, can achieve the copper extraction ratio of 99.99%, has no discharge of waste, is environment-friendly, and is high in economic benefit.
Description
Technical field
The present invention relates to resource recycling technical field, be specifically related to a kind of cupric waste wet method of utilizing and extract higher-grade copper coin clean energy-saving environmental-protecting process.
Background technology
Copper is the human metal that uses the earliest, and as far back as prehistoric age, people just begin the open-air copper mine of digging, and with the flexible weapon that obtains, formula tool and other vessel.The use of copper has a far reaching influence to early stage human civilization advance.Copper is a kind of metal that is present in the earth's crust and the ocean, and the content of copper in the earth's crust is about 0.01%, and in indivedual copper deposits, the content of copper can reach 3%～5%.The copper of occurring in nature, most is that copper mineral exists with compound.Copper mineral becomes copper mine stone with other mineral associations, and the copper mine stone that exploitation is come out becomes the higher copper ore concentrates of cupric grade through ore dressing.Copper is the non-ferrous metal very close with mankind's relation, is widely used in fields such as electric, light industry, machinofacture, building industry, national defense industry, in the consumption of China YouSe metallic substance, is only second to aluminium.That copper is used in electric, electronic industry is the widest, consumption is maximum, and it is over half to account for aggregate consumption.Be used for various cables and lead, motor and X-former, the manufacturing of switch and PC board etc. in machinery and road vehicle manufacturing, is used for process industry valve and accessory, instrument, sliding surface bearing, mould, heat exchanger and pump etc.China's copper resource is more in short supply, all will spend a large amount of copper ore concentratess of a large amount of foreign exchange imports, composition brass and electrolytic copper every year.And for the extraction of copper in the cupric waste utilize again do not accomplish very perfect.As reclaiming main method physics method, chemical method and microbial method are arranged for the extraction of copper in cupric discarded clothes slide fastener, the printed circuit board etc.The physics method mainly is to adopt methods such as gravitational segregation, magnetic separation, electrostatic separation that the copper in the metal mixture is sorted out, and its shortcoming is that the recovery and the grade of copper is not high; Microbial method is ripe not enough, still is in the stage of fumbling; Main rinsing, smelting or the use chemical solution of adopting cements out cupric ion in chemical process, and it is not high that these methods all exist the recovery, and environmental pollution is big, waste gas, waste water intractable, and the copper grade that extracts is not high, is difficult to meet international standards.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method simple, and the cupric waste wet method of utilizing that dna purity is high is extracted higher-grade copper coin clean energy-saving environmental-protecting process.
Technical problem to be solved by this invention adopts following technical scheme to realize:
A kind of cupric waste wet method of utilizing is extracted higher-grade copper coin clean energy-saving environmental-protecting process, and its process step is:
1. at first the cupric waste is carried out sorting, pulverizing, with the anode frame of packing into of the raw material after pulverizing;
2. the anode frame of charging feedstock is put into electrolyzer as anode; Between per two anode frames, be provided with a negative plate as negative electrode, the solution that will contain acid copper sulfate solution and some amount additive heats electrolytic solution as electrolytic solution; And it is mobile at the electrolyzer internal recycle all the time through electrolyte circulation system; When direct current in the electrolyzer passes through, the electrochemical solution of copper takes place on the anode, on negative electrode, separate out fine copper simultaneously;
3. in electrolytic process; Because noble metal gets into the earth of positive pole with other impurity of part, other impurity then mainly are transferred in the solution and separate with impurity, can obtain high-grade cathode copper through electrolytic refining; And the earth of positive pole that is enriched with noble metal; The minus plate that will contain the finished product cathode copper cleans, and through metering, detection, warehouse-in, sells as the finished product cathode copper;
4. antianode mud reclaims precious metal wherein through further handling;
5. the electrolyte that will contain more impurity is extracted a part out and is purified, and produces byproduct copper sulphate and nickelous sulfate from electrolyte circulation system; For guaranteeing the electrolysis ability of electrolyte; After purification, electrolyte is carried out sample examination, and add sulfuric acid and distilled water based on needs; Thereby the unlikely limit that allows that surpasses of impurity content in the electrolyte is to guarantee the normal operation of electrolytic refining;
6. sub product copper sulfate is carried out the electrodeposition decopper(ing), make electro deposited copper, and electro deposited copper is carried out electrolysis and absorbs with the raw material anode frame of packing into.
Should keep sufficiently high vitriolic concentration in the electrolytic solution, at the 120-180 grams per liter;
The temperature of electrolytic solution is too not high, is controlled at 50-56 ℃.
The invention has the beneficial effects as follows: process step of the present invention is simple, can effectively reclaim interest rate to resource, and the extraction yield of its copper can reach 99.99%, does not have the eliminating of waste, and is environmentally friendly, and economic benefit is high.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect and be easy to understand and understand, below in conjunction with concrete diagram, further set forth the present invention.
A kind of cupric waste wet method of utilizing is extracted higher-grade copper coin clean energy-saving environmental-protecting process, and its process step is:
1. at first the cupric waste is carried out sorting, pulverizing, with the anode frame of packing into of the raw material after pulverizing;
2. the anode frame of charging feedstock is put into electrolyzer as anode; Between per two anode frames, be provided with a negative plate as negative electrode, the solution that will contain acid copper sulfate solution and some amount additive heats electrolytic solution as electrolytic solution; And it is mobile at the electrolyzer internal recycle all the time through electrolyte circulation system; When direct current in the electrolyzer passes through, the electrochemical solution of copper takes place on the anode, on negative electrode, separate out fine copper simultaneously;
3. in electrolytic process; Because noble metal gets into the earth of positive pole with other impurity of part, other impurity then mainly are transferred in the solution and separate with impurity, can obtain high-grade cathode copper through electrolytic refining; And the earth of positive pole that is enriched with noble metal; The minus plate that will contain the finished product cathode copper cleans, and through metering, detection, warehouse-in, sells as the finished product cathode copper;
4. antianode mud reclaims precious metal wherein through further handling;
5. the electrolyte that will contain more impurity is extracted a part out and is purified, and produces byproduct copper sulphate and nickelous sulfate from electrolyte circulation system; For guaranteeing the electrolysis ability of electrolyte; After purification, electrolyte is carried out sample examination, and add sulfuric acid and distilled water based on needs; Thereby the unlikely limit that allows that surpasses of impurity content in the electrolyte is to guarantee the normal operation of electrolytic refining;
6. sub product copper sulfate is carried out the electrodeposition decopper(ing), make electro deposited copper, and electro deposited copper is carried out electrolysis and absorbs with the raw material anode frame of packing into.
Electrolytic refining can the following electrochemical systems of proximate usefulness be represented:
Cu is pure/CuSo
4H
2So
4H
2O/Cu is impure
Because ionized cause generates ion by following reaction in electrolytic solution:
When not switching on, owing to be in running balance, when direct supply was connected, under extraneous effect of electric field, various ions were done orientation movement, and the following formula reaction takes place on anode:
Under normal situation, become the bivalent cupric ion state, the standard potential of this reaction is: 0.344 volt.When having only copper ion concentration when electrolytic solution very big; Or the serious passivation of electrolyzer inner anode, when bath voltage rises to more than 2 volts; The discharge of hydroxide ion is just arranged, and precipitated oxygen on anode is as for the discharge of sulfate ion; Because of its current potential corrigendum, so can not carry out in the copper electrolytic process.
The following formula reaction takes place on negative electrode:
The standard potential of this reaction is: 0.344 volt; The standard potential of hydrogen is negative than copper; And the over voltage that hydrogen is separated out on cathode is planted and is bigger; Cupric ion can not separated out under the normal operation, only near the electrolytic solution negative electrode under the situation at the bottom of the concentration utmost point of cupric ion, the possibility of separating out hydrogen is arranged.
This shows, in the cupric electrolysis refinery practice, be that copper is dissolving and cupric ion separating out on negative electrode on the anode in the principal reaction on the two poles of the earth.
But when electrolysis, anode copper gets into the outer form dissolving that also has with 1 valency cupric ion of solution divided by the form of divalent cupric ion.
Positive 1 valency of Cu-e=Cu
The univalent copper ion that generates, column balancing under the situation that has metallic copper to exist and in the presence of the bivalent cupric ion:
Cu+Cu=2Cu
This equilibrium relationship has certain equilibrium constant at a certain temperature, and along with the rising of temperature, reaction is carried out to generating cupprous direction; But; Under general electrolytic condition, the equilibrium concentration of univalent copper ion is very little, and in the process of producing; Balance between monovalence copper and the cupric constantly is damaged, and its reason has two:
1, monovalence copper is oxidized to cupric
Cu
2SO
4+ H
2SO
4/ 2 an O
2=2CuSO
4+ H
2O
The speed of this reaction is accelerated along with the rising of temperature and with the increase of the exposure level of air, and the result increases the concentration of the cupric ion in the solution, and has consumed the sulfuric acid in the solution.
2, monovalence copper decomposes and separates out copper powder
The copper powder of separating out gets into the anode sludge, has diluted the content of precious metal wherein, and has caused the loss of copper.
Comprehensive above-mentioned can drawing to draw a conclusion: the cupric electrolysis refinery practice is under galvanic effect, and copper form with divalence on anode is dissolved; And the process that cupric is separated out with the form of metal on negative electrode; But in addition, the generation of univalent copper ion is arranged inevitably also, and therefore cause some disadvantageous side reactions; In order to make these disadvantageous side reactions reduce to minimum degree and to obtain good electrolysis effectiveness, should observe following condition during electrolysis:
1, should keep sufficiently high vitriolic concentration, 120-180 grams per liter in the electrolytic solution;
2, reduce contacting of electrolytic solution and air as far as possible;
3, the temperature of electrolytic solution is too not high, is controlled at 50-56 ℃;
4, keep sufficiently high current density.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (3)
1. utilize cupric waste wet method to extract higher-grade copper coin clean energy-saving environmental-protecting process, it is characterized in that: its process step is:
A. at first the cupric waste is carried out sorting, pulverizing, with the anode frame of packing into of the raw material after pulverizing;
B. the anode frame of charging feedstock is put into electrolyzer as anode; Between per two anode frames, be provided with a negative plate as negative electrode, the solution that will contain acid copper sulfate solution and some amount additive heats electrolytic solution as electrolytic solution; And it is mobile at the electrolyzer internal recycle all the time through electrolyte circulation system; When direct current in the electrolyzer passes through, the electrochemical solution of copper takes place on the anode, on negative electrode, separate out fine copper simultaneously;
C. in electrolytic process; Because noble metal gets into the earth of positive pole with other impurity of part, other impurity then mainly are transferred in the solution and separate with impurity, can obtain high-grade cathode copper through electrolytic refining; And the earth of positive pole that is enriched with noble metal; The minus plate that will contain the finished product cathode copper cleans, and through metering, detection, warehouse-in, sells as the finished product cathode copper;
D. antianode mud reclaims precious metal wherein through further handling;
The electrolyte that e. will contain more impurity is extracted a part out and is purified, and produces byproduct copper sulphate and nickelous sulfate from electrolyte circulation system; For guaranteeing the electrolysis ability of electrolyte; After purification, electrolyte is carried out sample examination, and add sulfuric acid and distilled water based on needs; Thereby the unlikely limit that allows that surpasses of impurity content in the electrolyte is to guarantee the normal operation of electrolytic refining;
F. sub product copper sulfate is carried out the electrodeposition decopper(ing), make electro deposited copper, and electro deposited copper is carried out electrolysis and absorbs with the raw material anode frame of packing into.
2. the cupric waste wet method of utilizing according to claim 1 is extracted higher-grade copper coin clean energy-saving environmental-protecting process, and it is characterized in that: vitriolic concentration remains on the 120-180 grams per liter in the said electrolytic solution.
3. the cupric waste wet method of utilizing according to claim 1 is extracted higher-grade copper coin clean energy-saving environmental-protecting process, and it is characterized in that: the temperature of said electrolytic solution is controlled at 50-56 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210268786.6A CN102776527B (en) | 2012-07-31 | 2012-07-31 | Utilize cupric waste wet underwater welding higher-grade copper coin clean energy-saving environmental-protecting process |
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| CN201210268786.6A CN102776527B (en) | 2012-07-31 | 2012-07-31 | Utilize cupric waste wet underwater welding higher-grade copper coin clean energy-saving environmental-protecting process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540956A (en) * | 2013-09-26 | 2014-01-29 | 界首市飞航铜业有限公司 | Wet separation technology for waste copper-tin alloy fitting soldering flakes |
| CN104694978A (en) * | 2013-12-05 | 2015-06-10 | 阳谷祥光铜业有限公司 | Waste electrolyte treatment method and device |
| CN105821443A (en) * | 2016-05-10 | 2016-08-03 | 胡桂生 | Production process of cathode copper |
| CN106676577A (en) * | 2017-02-06 | 2017-05-17 | 中国科学院过程工程研究所 | Method for recovering copper from used circuit board |
| CN107502920A (en) * | 2017-08-10 | 2017-12-22 | 云南龙蕴科技环保股份有限公司 | A kind of method of the hydrometallurgic recovery copper from circuit board |
| CN108754154A (en) * | 2018-06-29 | 2018-11-06 | 肇庆高新区国专科技有限公司 | A method of metal in classification recovery train plate |
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| CN1854346A (en) * | 2005-04-27 | 2006-11-01 | 范有志 | Rack-assembled anodic-basket non-residual electrode method of direct electrolytic fine stray copper |
| CN101168692A (en) * | 2005-10-26 | 2008-04-30 | 三星Sdi株式会社 | Desulfurization adsorbent for fuel cell and desulfurizing method using the same |
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Patent Citations (6)
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| CN1036805A (en) * | 1989-03-20 | 1989-11-01 | 重庆钢铁研究所 | Direct electrolytic refining of copper scrap by stainless steel anode frame |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540956A (en) * | 2013-09-26 | 2014-01-29 | 界首市飞航铜业有限公司 | Wet separation technology for waste copper-tin alloy fitting soldering flakes |
| CN104694978A (en) * | 2013-12-05 | 2015-06-10 | 阳谷祥光铜业有限公司 | Waste electrolyte treatment method and device |
| CN104694978B (en) * | 2013-12-05 | 2018-03-23 | 阳谷祥光铜业有限公司 | The processing method and processing unit of a kind of waste electrolyte |
| CN105821443A (en) * | 2016-05-10 | 2016-08-03 | 胡桂生 | Production process of cathode copper |
| CN106676577A (en) * | 2017-02-06 | 2017-05-17 | 中国科学院过程工程研究所 | Method for recovering copper from used circuit board |
| CN106676577B (en) * | 2017-02-06 | 2019-03-22 | 中国科学院过程工程研究所 | A method of recycling copper from waste and old circuit board |
| CN107502920A (en) * | 2017-08-10 | 2017-12-22 | 云南龙蕴科技环保股份有限公司 | A kind of method of the hydrometallurgic recovery copper from circuit board |
| CN108754154A (en) * | 2018-06-29 | 2018-11-06 | 肇庆高新区国专科技有限公司 | A method of metal in classification recovery train plate |
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| CN102776527B (en) | 2015-10-07 |
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Owner name: JIESHOU GELIN BRASS INDUSTRY CO., LTD. Free format text: FORMER OWNER: ANHUI JIAWEI RENEWABLE RESOURCES CO., LTD. Effective date: 20130116 |
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Effective date of registration: 20130116 Address after: 236502 Anhui city of Fuyang Province Jieshou City Xicheng Industrial Park Kaiyuan Road No. 56 Applicant after: Jieshou Green Copper Co.,Ltd. Address before: 236502 Anhui city of Fuyang Province Jieshou City Xicheng Industrial Park Kaiyuan Road No. 56 Applicant before: Anhui Jiawei Regeneration Resource Co.,Ltd. |
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