CN101498009A - Method and equipment for recycling high purity copper block from low copper content waste liquor - Google Patents
Method and equipment for recycling high purity copper block from low copper content waste liquor Download PDFInfo
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- CN101498009A CN101498009A CNA2009100425049A CN200910042504A CN101498009A CN 101498009 A CN101498009 A CN 101498009A CN A2009100425049 A CNA2009100425049 A CN A2009100425049A CN 200910042504 A CN200910042504 A CN 200910042504A CN 101498009 A CN101498009 A CN 101498009A
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method and a device of recycling high-purity copper blocks from waste liquid with low copper content. Firstly, the waste liquid with low copper content is led by a pump resisting sour corrosion from a circulating slot to an electrowinning barrel, enters the bottom of the electrowinning barrel, flows out of the upper part of the electrowinning barrel and finally flows back to the circulating slot; at the same time, a variable-frequency motor drives a cathode barrel in the electrowinning barrel to make circumferential rotating movement, the cathode barrel and the anode electrowinning barrel are switched on to a direct current of a direct current power supply, high-purity, compact and block copper is precipitated on the cathode barrel, and the copper ion concentration of electrowinning liquid decreases to below 0.5 g/L; after the electrowinning process is finished, the cathode barrel is taken out, is soaked in a warm water tank and is cleaned in cold water, and then the cleaned cathode copper is stripped from the cathode barrel and is dried and cooled to finally obtain a block anode barrel produce with the purity of 99.8 percent to 99.95 percent. The invention has simple technological process, convenient and easily-controlled operation, small equipment investment, low movement cost, good environment-protecting performance and high economic value.
Description
Technical field
The present invention relates to a kind of from low copper containing, nickel or other low-metal content waste liquid, the extraction and reclaim method and apparatus high-purity, fine and close, block copper billet, belong to recycling metallurgical and trade waste.
Background technology
In recent years, along with the steady-state growth of world's electronic industry, the printed circuit board (pcb) manufacturing of China is also fast-developing, and its output and the output value have been listed as at the forefront in the world.Statistics according to authoritative institution, the printed circuit board output of China in 2006 is 13,000 ten thousand square metres, 10,000 square metres of circuit cards of every production will produce 50-100 tons of heavy metal waste liquids (based on contained waste liquid), mainly be divided into alkaline etching liquid, acidic etching liquid, the comprehensive waste liquid of low copper containing etc.Because alkaline etching liquid, acidic etching liquid content of copper ion restrain more than every liter, so the recovery value height up to 100.The comprehensive waste liquid of low copper containing is meant in the wiring board production process and changes cylinder liquid or change the cylinder rinse water with the copper bearing of operations generation such as chemical copper, melanism line, brown line, internal layer pre-treatment, anti-pre-welding treatment, change gold and silver line, the thin copper of erosion, sea line, OSP, general designation low copper containing waste liquid, main component is Cu
2+, HCl, H
2SO
4, oxygenant, stablizer and other additives etc., copper content is low by (2～45g/L), about average 9g/L, recycle with the waste liquid of the present technology that is had so low copper content, enterprise is profitless, and therefore present most of wiring board manufacturing enterprise can only transfer to the comprehensive waste liquid of low copper containing in the mode of paying and handle the merchant and handle.
Current, China remains the populous nation of a shortage of resources, environment fragility, and it is very necessary to make rational use of resources.Valuable metal copper in the low copper containing waste liquid is effectively reclaimed, make high-purity, fine and close, the blocky cathode copper of its output not only can realize the utilization again of resource, can also solve the awkward situation that value that current low copper containing waste liquid in the face of PCB institute output contained be nobody shows any interest in, make PCB manufacturing enterprise and wastewater treatment merchant obtain favorable economic benefit.Realize enterprise, society fully, the environmental protection win-win.
At present, the low copper containing Wastewater Recovery treatment technology that is produced in the PCB production process there is following several technology: neutralization precipitation method, extraction-electrodeposition method, common electrodeposition extraction method.The most general in the above-mentioned technology with the use of neutralization precipitation method, but owing to their limitation own, all fail the value that low copper containing waste water is contained is used to greatest extent.
The ultimate principle of neutralization precipitation method technology is that the concentration of copper hydroxide in the aqueous solution is long-pending very little, by adjusting the pH value of solution, cupric ion is separated out with the form precipitation of copper hydroxide, add flocculation agent and filtering method again and reach the purpose that cupric ion in the low copper containing waste liquid is removed in recovery.The defective of this technology is the mud copper content only 2～5% of output, is unfavorable for next step efficient recovery to copper, and economic worth is not high, as the method that adopts pyrogenic process it is reclaimed and will cause secondary pollution to environment.Simultaneously, need to consume a large amount of alkali and flocculation agent in treating processes, processing cost is higher, and is disproportionate with the income that is obtained.
Summary of the invention:
Technical problem to be solved by this invention is: solve the problem that above-mentioned prior art exists, and provide reclaim a kind of waste liquid of, complex chemical composition low from content of copper ion that printed circuit board produced produce that high purity, densification, blocky copper coin, technical process are simple, convenient and easily-controlled operation, facility investment be few.Running cost is low, the method and apparatus that reclaims high-purity copper billet from the low copper containing waste liquid of good environmental protection.
The technical solution used in the present invention is: this method that reclaims the high purity copper billet from the low copper containing waste liquid is: at first with acid resistance corrosion pump the low copper containing waste liquid is imported the electrodeposition bucket from circulation groove, the low copper containing waste liquid enters from electrodeposition bucket bottom, flow out by electrodeposition bucket top, and finally flow back into circulation groove, meanwhile, the negative electrode bucket that variable-frequency motor drives in the electrodeposition bucket rotatablely moves as circumference, direct supply is connected direct current to negative electrode bucket and anode electrodeposition bucket, separate out high-purity on the negative electrode bucket, fine and close, blocky copper, below copper ion concentration in the electric effusion drops to 0.5 grams per liter, electrolytic deposition process finishes, close direct supply, negative electrode bucket rotating machine and acid resistance corrosion pump, taking-up negative electrode bucket is put into the warm water rinse bath and is soaked, use cold water flush again, then clean cathode copper is stripped down from the negative electrode bucket, again drying, cooling finally obtains purity and is 99.8-99.95% block cathode copper product.
In the described technical scheme, the variable-frequency motor rotating speed that drives the rotation of negative electrode bucket is 30-60 commentaries on classics/per minutes, and simultaneously, the negative electrode bucket is done the circumference rotation with 30-60 rev/mins speed under the drive of variable-frequency motor.
In the technique scheme, cathode current density be controlled at 300-800 the peace/every square metre, bath voltage be controlled at 2.5-3.5 the volt, cathode copper per ton comprehensive electric energy consumption in 3500-4000Kwh.
In the technique scheme, the negative electrode bucket after electrolytic deposition process finishes is put into the warm water rinse bath and is soaked 80 ℃ of water temperatures, soak time 30 minutes.
In the technique scheme, after cathode copper stripped down from the negative electrode bucket, exsiccant baking box temperature was 150-180 ℃, 30 minutes time.
In the technique scheme, the negative electrode bucket is made by the titanium plate or the stainless steel plate of 1.5-2.0 mm thick.
In the technique scheme, the anode bucket is made by the titanium plate of the graphite cake of insoluble or surface-coated noble ruthenium, iridium oxide.
In the technique scheme, the low copper containing waste liquid enters from electrodeposition bucket bottom, for the bottom tangentially enters, and is close to the cathode surface rotation and rises, and is flowed out by electrodeposition bucket top at last; Perhaps the low copper containing waste liquid is sprayed onto cathode surface by the mode of spray; Reduce the solution layer fluid layer thickness of cathode surface to greatest extent, cathode surface solution is in turbulence state.
This equipment that reclaims high-purity copper billet from the low copper containing waste liquid comprises circulation groove, acid resistance corrosion pump, the electrodeposition bucket, direct supply, rinse bath, dry baking box, splendid attire low copper containing waste liquid in the circulation groove, the liquid feeding end of acid resistance corrosion pump connects circulation groove, the outlet end of acid resistance corrosion pump connects electrodeposition bucket bottom liquid feeding end, electrodeposition bucket top outlet end returns and connects to circulation groove, the negative electrode bucket is installed in the electrodeposition bucket, the negative electrode bucket is done the circumference rotation by the variable-frequency motor transmission, negative electrode bucket center conductive copper axle connects the direct supply negative terminal, electrodeposition bucket anode connects the direct supply anode, the negative electrode bucket after electrodeposition finishes and the cleaning and drying device of cathode copper are rinse bath and drying oven, and the waste gas that produces in the electrolytic deposition process all recycles through tail gas recovery tower.
In the technique scheme, the circulation groove top also is connected tail gas recovery tower by pipeline with vacuum fan.
In the technique scheme, the electrodeposition bucket can be for a plurality of, serial or parallel connection; During series connection, the outlet end of a last electrodeposition bucket connects the liquid feeding end of next electrodeposition bucket, and the outlet end of last electrodeposition bucket is connected to circulation groove; When in parallel, all electrodeposition bucket bottom liquid feeding ends connect acid resistance corrosion delivery side of pump, and the outlet end on all electrodeposition bucket tops all is connected to circulation groove.
The present invention compares with prior art, has outstanding substantive distinguishing features and obvious improvement:
1. the neutralization precipitation method of prior art
The ultimate principle of this technology is that the concentration of copper hydroxide in the aqueous solution is long-pending very little, by adjusting the pH value of solution, cupric ion is separated out with the form precipitation of copper hydroxide, add flocculation agent and filtering method again and reach the purpose that cupric ion in the low copper containing waste liquid is removed in recovery.The defective of this technology is the mud copper content only 2～5% of output, is unfavorable for next step efficient recovery to copper, and economic worth is not high, as the method that adopts pyrogenic process it is reclaimed and will cause secondary pollution to environment.Simultaneously, need to consume a large amount of alkali and flocculation agent in treating processes, processing cost is higher, and is disproportionate with the income that is obtained.
2. extraction-the electrodeposition process of prior art
The principle of this technology is by the selective adsorption of extraction agent to cupric ion, cupric ion in the low copper containing waste liquid is enriched in the extraction agent, again with sulfuric acid do reverse-extraction agent with the cupric ion back extraction in the extraction liquid to sulphuric acid soln, by flat Winning cell the copper bearing sulphuric acid soln of height is carried out electrodeposition at last and reclaim, obtain high purity, densification, blocky cathode copper product.This technology can finally obtain the high cathode copper product of economic worth, but it also has the following disadvantages: subject range is little, and to containing the low copper containing waste liquid of strong oxidized form material such as nitric acid, hydrogen peroxide, the work-ing life of extraction agent is short.The equipment one-time investment is big, is unsuitable for the little and dispersive characteristics of amount that the low copper containing waste liquid is had.Technical process is long, and is wayward.It is limited that extraction agent is reused number of times, and running cost is higher.
3. the flat electrodeposition treatment process of prior art
This technology is a kind of traditional electrodeposition process, and its principle is under galvanic effect, and anode and cathode is carried out redox reaction, mainly carries out cupric ion and the hydrionic electronic reduction reaction that gets on the negative electrode, separates out with the form of elemental copper and hydrogen.Carry out anionic betatopic oxidizing reactions such as hydroxide ion and chlorion on the anode, separate out with the form of other gases such as oxygen and chlorine.Utilize flat electrodeposition treatment process to handle the low copper containing waste liquid and mainly embody following shortcoming: at first, it can only output sponge copper powder, owing to there is not effective means that it is carried out Passivation Treatment, make the final copper content of sponge copper powder have only 80-95%, economic worth declines to a great extent.Secondly its current efficiency is only less than 65%, and then up to 6000-8000 degree electricity, processing cost is quite high for the energy consumption of cathode copper per ton.Another is exactly that its production capacity is little, if reach the purpose that increases production capacity by the method that improves cathode current density, its current efficiency will be lower so, and power consumption will further improve.
4. rotating cathode treatment technology of the present invention
The generation of rotating cathode treatment technology of the present invention is to have carried out effective improvement and perfect on the technical foundation of flat electrodeposition treatment process, makes it form a kind of new technology that reclaims the low copper containing waste liquid of handling.Its main technical principle is, design by rotating cathode electrodeposition bucket and to the change of the control of internal circulating load and electric effusion in the cathode surface flow pattern, reach the circulating effect of strengthening electric effusion, make the solution of cathode surface be in turbulence state, the molten difference of cupric ion that reduces the cathode surface generation in electrolytic deposition process of low copper containing waste liquid to greatest extent polarizes, and reaches to remedy the low copper containing waste liquid because content of copper ion is crossed low disadvantageous effect to the electrodeposition removal process.Making it be more conducive to form compact crystal is blocky cathode copper product.
Utilize rotating cathode treatment technology processing recovery low copper containing waste liquid to compare with existing processing recovery technology and have following advantage: 1. the rotating cathode treatment technology can extract high-purity, fine and close, blocky cathode copper product by electrodeposition from the low copper containing waste liquid.2. the copper ion concentration of low copper containing waste liquid waste liquid after the rotating cathode electrodeposition is carried copper can be reduced to every liter of 0.5 gram, and the rate of recovery of copper reaches 95-99%.The purity of cathode copper product reaches 99.8%-99.95%.3. utilize the production cost of rotating cathode treatment technology processing low copper containing waste liquid low, the power consumption that extracts one ton of copper is in 3500-4000 degree electricity.4. rotating cathode device fabrication cost is low, and processing technological flow is short, is convenient to operation control.5. the entire treatment process is carried out in the system of a sealing, discharges the production process environmental protection in atmosphere without any toxic and harmful.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is the present device synoptic diagram;
Fig. 3 is an electrodeposition barrel structure synoptic diagram of the present invention.
The accompanying drawing marking explanation:
1---acid resistance corrosion pump 2---electrodeposition bucket 3---direct supply
4---circulation groove 5---waste water storage tank 6---negative electrode conductive copper axles
7---tail gas recovery tower 8---rinse bath 9---cathode copper baking boxes
10---anode conducting copper bar 11---anode 12---negative electrode buckets
13---fluid inlet 14---liquid outlet 15---bearings
16---sealing-ring 17---mercury cup 18---belts
19---variable-frequency motor 20---copper axle steel bushing
Embodiment
Referring to accompanying drawing, the present invention reclaims the high purity copper billet from the low copper containing waste liquid method is: at first with acid resistance corrosion pump 1 the low copper containing waste liquid is imported electrodeposition bucket 2 from circulation groove 4, the low copper containing waste liquid enters from electrodeposition bucket 2 bottoms, flow out by electrodeposition bucket 2 tops, and finally flow back into circulation groove 4, meanwhile, the negative electrode bucket 12 that variable-frequency motor 19 drives in the electrodeposition buckets 2 rotatablely moves as circumference, direct supply 3 is connected direct current to negative electrode bucket 12 and anode electrodeposition bucket 2, separate out high-purity on the negative electrode bucket 12, fine and close, blocky copper, below copper ion concentration in the electric effusion drops to 0.5 grams per liter, electrolytic deposition process finishes, close direct supply 3, negative electrode bucket rotation variable-frequency motor 19 and acid resistance corrosion pump 1, take out negative electrode bucket 12 and put into 8 immersions of warm water rinse bath, use cold water flush again, then clean cathode copper is stripped down from negative electrode bucket 12, drying again, cooling finally obtains purity and is 99.8-99.95% block cathode copper product.
Variable-frequency motor 19 rotating speeds of above-mentioned drive negative electrode bucket rotation are 30-60 commentaries on classics/per minutes.In the operation, cathode current density be controlled at 300-800 the peace/every square metre.After electrolytic deposition process finished, negative electrode bucket 12 was put into warm water rinse bath 8 and is soaked 80 ℃ of water temperatures, soak time 30 minutes.After cathode copper stripped down from negative electrode bucket 12, the exsiccant oven temperature was 150-180 ℃, 30 minutes time.Above-mentioned negative electrode bucket 12 is made by the titanium plate of 1.5-2.0 mm thick or 316 stainless steel plates or titanium coating material.Above-mentioned low copper containing waste liquid enters from electrodeposition bucket bottom, for the bottom tangentially enters, and is close to the cathode surface rotation and rises, and is flowed out by electrodeposition bucket top at last; Perhaps the low copper containing waste liquid is sprayed onto cathode surface by the mode of spray; Reduce the solution layer fluid layer thickness of cathode surface to greatest extent, cathode surface solution is in turbulence state.
The equipment that reclaims high-purity copper billet from the low copper containing waste liquid of the present invention comprises circulation groove 4, acid resistance corrosion pump 1, electrodeposition bucket 2, direct supply 3, rinse bath 8, dry baking box 9, splendid attire low copper containing waste liquid in the circulation groove 4, the liquid feeding end of acid resistance corrosion pump 1 connects circulation groove 4, the outlet end of acid resistance corrosion pump 1 connects electrodeposition bucket 2 bottom liquid feeding ends, electrodeposition bucket 2 top outlet ends return and connect circulation groove 4, negative electrode bucket 12 is installed in the electrodeposition bucket 2, negative electrode bucket 12 is done the circumference rotation by variable-frequency motor 19 transmissions, negative electrode bucket 12 center conductive copper axles 6 connect direct supply 3 negative terminals, electrodeposition bucket 12 anodes connect direct supply 3 anodes, and the cleaning and drying device that electrodeposition finishes back negative electrode bucket 12 and cathode copper is rinse bath 8 and dry baking box 9.
Above-mentioned circulation groove 4 tops also are connected tail gas recovery tower 7 by pipeline with vacuum fan.
Above-mentioned electrodeposition bucket 2 can be for a plurality of, serial or parallel connection; During series connection, the outlet end of a last electrodeposition bucket connects the liquid feeding end of next electrodeposition bucket, and the outlet end of last electrodeposition bucket is connected to circulation groove 4; When in parallel, all electrodeposition bucket 2 bottom liquid feeding ends connect the output terminal of acid resistance corrosion pump 1, and the outlet end on all electrodeposition bucket 2 tops all is connected to circulation groove 4.
The invention will be further described below in conjunction with drawings and Examples:
Production method of the present invention is the valuable metal copper resource recovery at the low copper containing waste liquid, is that example describes with output microetch low copper containing waste liquid in the printed circuit board production process now.
At first, microetch low copper containing waste liquid is imported electrodeposition bucket 2 and circulation groove 4, open acid resistance corrosion pump 1 and carry out the circulation of electric effusion in whole circulation system.Open rotating cathode bucket power variable-frequency motor 19 is provided, and regulate frequency transformer according to processing requirement, the speed of rotation that makes negative electrode is at 60 rpms, and connection tail gas recovery tower 7 power supplys make it in running order.Finish after the above-mentioned work by direct supply 3 to electrodeposition bucket input dc power, the electrodeposition that begins to carry out printed circuit board microetch low copper containing waste liquid is carried copper.Can carry out the suitable adjustment of received current intensity according to the decline degree of cupric ion in the electric effusion in electrolytic deposition process, the adjustment foundation of strength of current is to guarantee that cathode copper forms densification, block crystallization, can not form the powdery crystallization.When the copper ion concentration of electric effusion dropped to every liter of 0.5 gram, whole electrolytic deposition process finished, deenergization.Discharging of waste liquid enters waste water station and handles to waste water storage tank 5 behind the electrodeposition.Will the negative electrode bucket 12 put into rinse bath 8 after taking out and clean, guarantee the cathode copper surface, and after cleaning up cathode copper be stripped down from the negative electrode bucket 12 fully and put into baking box 9 bakings, finally obtain qualified cathode copper product without any residual electric effusion.
The main electrode reaction of electrolytic deposition process:
Mainly carry out the betatopic reaction of hydroxide ion and chlorion on the anode:
4OH
--4e→O
2+2H
2O
2Cl
--2e→Cl
2
Mainly carry out on the negative electrode cupric ion electron reaction and side reaction hydrionic electron reaction:
Cu
2++2e→Cu
2H
++2e→H
2
Embodiment
1 implementation condition and processing parameter
Handle microetch liquid cupric content: 7 grams per liters
Electric effusion volume: 560 liters
Electric effusion speed of circulation: 80 liters/minute
Negative electrode speed of rotation: 60 rev/mins
Negative electrode useful area: 0.7 square metre
Cathode current density: 400 peaces/square metre
Bath voltage: 2.9-2.6 volt
2 results of implementation
Whole electrolytic deposition process has carried out 13.7 hours altogether, output densification, blocky cathode copper 3800 grams, and printed circuit board microetch low copper containing waste liquid copper ion concentration after the electrodeposition recycling drops to every liter of 0.5 gram.
As calculated, utilize the rotating cathode technical finesse to reclaim valuable metal copper in the printed circuit board microetch low copper containing waste liquid, the copper recoveries that its cathode efficiency is 80%, power consumption is 3500 degree cathode copper per ton, printed circuit board microetch low copper containing waste liquid are 97%, the purity of cathode copper reaches 99.828%.
Claims (4)
1, a kind of method that from the low copper containing waste liquid, reclaims the high purity copper billet, it is characterized in that: at first the low copper containing waste liquid is imported the electrodeposition bucket from circulation groove with acid resistance corrosion pump, the low copper containing waste liquid enters from electrodeposition bucket bottom, flow out by electrodeposition bucket top, and finally flow back into circulation groove, meanwhile, the negative electrode bucket that variable-frequency motor drives in the electrodeposition bucket rotatablely moves as circumference, direct supply is connected direct current to negative electrode bucket and anode electrodeposition bucket, separate out high-purity on the negative electrode bucket, fine and close, blocky copper, below copper ion concentration in the electric effusion drops to 0.5 grams per liter, electrolytic deposition process finishes, close direct supply, negative electrode bucket rotating machine and acid resistance corrosion pump, taking-up negative electrode bucket is put into the warm water rinse bath and is soaked, and uses cold water flush again, then clean cathode copper is stripped down from the negative electrode bucket, drying again, cooling finally obtains purity and is 99.8-99.95% block cathode copper product.
2, the method that reclaims the high purity copper billet from the low copper containing waste liquid according to claim 1 is characterized in that: cathode current density is controlled at 300-800 peaces/every square metre, bath voltage is controlled at the comprehensive electric energy consumption of 2.5-3.5 volts, cathode copper per ton in 3500-4000Kwh.
3, the method that reclaims the high purity copper billet from the low copper containing waste liquid according to claim 1 is characterized in that: the low copper containing waste liquid enters from electrodeposition bucket bottom, for the bottom tangentially enters, and is close to the cathode surface rotation and rises, and is flowed out by electrodeposition bucket top at last; Perhaps the low copper containing waste liquid is sprayed onto cathode surface by the mode of spray; Reduce the solution layer fluid layer thickness of cathode surface to greatest extent, cathode surface solution is in turbulence state.Simultaneously, the negative electrode bucket is done the circumference rotation with 30-60 rev/mins speed under the drive of variable-frequency motor.
4, a kind of equipment that from the low copper containing waste liquid, reclaims high-purity copper billet, it is characterized in that comprising circulation groove, acid resistance corrosion pump, the electrodeposition bucket, direct supply, rinse bath, dry baking box, splendid attire low copper containing waste liquid in the circulation groove, the liquid feeding end of acid resistance corrosion pump connects circulation groove, the outlet end of acid resistance corrosion pump connects electrodeposition bucket bottom liquid feeding end, electrodeposition bucket top outlet end returns and connects to circulation groove, the negative electrode bucket is installed in the electrodeposition bucket, the negative electrode bucket is done the circumference rotation by the variable-frequency motor transmission, negative electrode bucket center conductive copper axle connects the direct supply negative terminal, electrodeposition bucket anode connects the direct supply anode, the back negative electrode bucket that electrodeposition finishes and the cleaning and drying device of cathode copper are rinse bath and drying oven, and the waste gas that produces in the electrolytic deposition process all recycles through tail gas recovery tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100425049A CN101498009A (en) | 2009-01-15 | 2009-01-15 | Method and equipment for recycling high purity copper block from low copper content waste liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100425049A CN101498009A (en) | 2009-01-15 | 2009-01-15 | Method and equipment for recycling high purity copper block from low copper content waste liquor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101498009A true CN101498009A (en) | 2009-08-05 |
Family
ID=40945276
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100425049A Pending CN101498009A (en) | 2009-01-15 | 2009-01-15 | Method and equipment for recycling high purity copper block from low copper content waste liquor |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260879A (en) * | 2011-07-27 | 2011-11-30 | 金川集团有限公司 | Treatment method of waste copper sulfate electrolyte |
| CN102531106A (en) * | 2011-12-16 | 2012-07-04 | 深圳市祐林环保有限公司 | Device for removing ammonia nitrogen in waste liquor and extracting high-purity copper and method therefor |
| CN103276412A (en) * | 2013-05-29 | 2013-09-04 | 辽宁科技大学 | Method for preparing copper or nickel powder and electrolysis device based on same |
| CN106521552A (en) * | 2016-10-18 | 2017-03-22 | 河海大学 | Hydrogen peroxide-sulfuric acid micro-etching waste liquid copper recovery and electric waste liquid regeneration two-segment type platform rotational flow electrolysis device and method |
| CN107192660A (en) * | 2017-05-27 | 2017-09-22 | 中国科学院上海技术物理研究所 | It is a kind of to be used for the apparatus and method that dynamic observes Cdl-x_Znx_Te chemical attack hole |
| CN114622247A (en) * | 2021-04-23 | 2022-06-14 | 东莞市盛德电解设备科技有限公司 | Copper extraction process for low-concentration acid leaching solution of ore |
| CN114622247B (en) * | 2021-04-23 | 2024-04-26 | 东莞市盛德电解设备科技有限公司 | Copper extraction process of ore low-concentration acid leaching solution |
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2009
- 2009-01-15 CN CNA2009100425049A patent/CN101498009A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260879A (en) * | 2011-07-27 | 2011-11-30 | 金川集团有限公司 | Treatment method of waste copper sulfate electrolyte |
| CN102531106A (en) * | 2011-12-16 | 2012-07-04 | 深圳市祐林环保有限公司 | Device for removing ammonia nitrogen in waste liquor and extracting high-purity copper and method therefor |
| CN103276412A (en) * | 2013-05-29 | 2013-09-04 | 辽宁科技大学 | Method for preparing copper or nickel powder and electrolysis device based on same |
| CN103276412B (en) * | 2013-05-29 | 2015-10-21 | 辽宁科技大学 | A kind of method and electrolyzer thereof preparing copper powder or nickel powder |
| CN106521552A (en) * | 2016-10-18 | 2017-03-22 | 河海大学 | Hydrogen peroxide-sulfuric acid micro-etching waste liquid copper recovery and electric waste liquid regeneration two-segment type platform rotational flow electrolysis device and method |
| CN106521552B (en) * | 2016-10-18 | 2018-05-18 | 河海大学 | A kind of hydrogen peroxide-sulfuric acid micro-etched waste liquid copper recycling two-part platform swirl electrolysis device regenerated with electric extraction raffinate and electrolytic method |
| CN107192660A (en) * | 2017-05-27 | 2017-09-22 | 中国科学院上海技术物理研究所 | It is a kind of to be used for the apparatus and method that dynamic observes Cdl-x_Znx_Te chemical attack hole |
| CN107192660B (en) * | 2017-05-27 | 2023-09-12 | 中国科学院上海技术物理研究所 | Device and method for dynamically observing tellurium-zinc-cadmium material chemical corrosion pits |
| CN114622247A (en) * | 2021-04-23 | 2022-06-14 | 东莞市盛德电解设备科技有限公司 | Copper extraction process for low-concentration acid leaching solution of ore |
| CN114622247B (en) * | 2021-04-23 | 2024-04-26 | 东莞市盛德电解设备科技有限公司 | Copper extraction process of ore low-concentration acid leaching solution |
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