CN104278291A - Method of directly melting and molding scrap copper to extract copper by electrolysis - Google Patents
Method of directly melting and molding scrap copper to extract copper by electrolysis Download PDFInfo
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- CN104278291A CN104278291A CN201410573987.6A CN201410573987A CN104278291A CN 104278291 A CN104278291 A CN 104278291A CN 201410573987 A CN201410573987 A CN 201410573987A CN 104278291 A CN104278291 A CN 104278291A
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- copper
- scap
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a method of directly melting and molding scrap copper to extract copper by electrolysis. The method comprises the following steps: 1) directly melting and molding scrap copper with copper content of over 60% into an anode and taking a pure copper thin sheet as a cathode; 2) using copper sulfate, sulfuric acid and hydrochloric acid to prepare electrolyte adding the electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 45-60g/ L copper sulfate, 160-200g/L sulfuric acid, 0.04-0.08g/L hydrochloric acid and the balance of water; 3) switching on direct current for the electrolytic cell to perform electrolysis, wherein the process conditions for electrolysis are as follows: electrolyte temperature of 55-65 DEG C and cathode current density of 150-260A/m<2>. The scrap copper applicable to the method comprises the following components in percentage by weight: 60-99.5% of copper, 0-10% of lead, 0-5% of nickel, 0-3% of iron, 0-3% of iron, 0-3% of tin and 0-10% of zinc. The method disclosed by the invention can be used for solving the problem that the existing production process is long in process flow, low in recovery rate, high in energy consumption and low in utilization level and causes serious environmental pollution. The method abandons smelting processes such as oxidizing and reducing used in the existing process and has the advantages of a high recovery rate, low cost, a short production period, capacity of relieving environmental pollution, and the like.
Description
Technical field
The present invention relates to copper scap regeneration affinage metallurgy technique, particularly a kind of copper scap melt-forming Direct Electrolysis extracts the method for copper, utilizes present method using shaping for copper scap direct fusion as anode, can produce standard cathode copper by Direct Electrolysis.
Background technology
1, current, the copper ore resource shortage of China, needs a large amount of import copper ore concentrates to meet the needs of the national economic development.According to authoritative institution's statistics, within 2013, China produces copper amount 6,840,000 tons, but self-produced copper ore concentrates produces copper 159.6 ten thousand tons, the main dependence on import of copper ore concentrates needed for copper metallurgy.While import copper ore concentrates, China is a large amount of copper scap of import also.Copper scap in 2013 is recycled channel and is produced copper 1,750,000 tons, accounts for 25.6% of total product copper amount.Reclaimed copper produces more energy-conservation than primary copper more than 80%, and save production cost 60%-65%, saving copper habilitation 20,000 yuan/ton.Copper scap is gone out reclaimed copper as raw material production be conducive to expanding resources access, save energy, minimizing environmental pollution and increasing social synthesis's effect.
2, usually copper scap is divided into No. 1 composition brass according to copper content in industry, copper content is more than 96%; No. 2 composition brasses, copper content is more than 94%; No. 3 composition brasses, cupric is more than 90%; Cupric less than 90% the outer composition brass such as to be called.
3, the method recycling at present both at home and abroad copper scap is a lot, mainly can be divided into two large classes: the first kind be after the copper alloy by high-quality copper scap Direct Rolling copper bar or the corresponding trade mark of direct production for user, be called direct utilization; Equations of The Second Kind becomes for user after electrolytic copper through electrorefining after copper scap is smelted into positive plate, is called indirect utilization.Its indirect utilization can be divided into three kinds again: one-stage process, two-phase method and three-stage process.
4, No. 1 composition brass as above is used directly usually.No. 2 or part No. 3 composition brasses adopt one-stage processes and two-phase method process.One-stage process is directly added by copper scap after anode furnace is refined into positive plate, then become the method for electrolytic copper through electrorefining, and main drawback is that labour intensity is large, productivity is low, metal recovery rate is low.Two-phase method copper scap is added blast furnace or converter is smelted into blister copper, blister copper add again anode furnace be smelted into positive plate after again electrorefining become the method for electrolytic copper.Impure No. 3 high composition brasses and outer composition brass such as grade adopt three-stage process process usually, three-stage process be copper scap is added blast furnace smelting Cheng ?copper ?copper add converter and be smelt time blister copper, secondary blister copper add again anode furnace be smelt positive plate after electrorefining become the method for electrolytic copper.At present, use the widest or one-stage process, two-phase method gradually substitute by new two-phase method " bath smelting-anode furnace refining ".The factory adopting three-stage process seldom, only has foreign department point factory to use in continuation.
5, the Production Flow Chart of existing traditional technology process copper scap: copper scap is added anode furnace melting, through charge melted, oxidation, reduction, casting output cupric more than 99%, foreign matter content controls the anode copper in lower scope, then through electrorefining output criteria cathode copper.The method also exists that the technological process of production is long, the rate of recovery is low, energy consumption is high, utilize the problems such as level is low, environmental pollution is large, causes production cost can not to be in any more.
6, China's most copper scap refinery plant small scale, technique falls behind, equipment is poor, environmental issue is serious, these plant sizes are generally 0.5-3 ten thousand tons, pyrorefining adopts anode furnace substantially, stove can differ in size at 25-110 ton, and thermo-efficiency is low, metal recovery rate is low, energy consumption is high, seriously polluted.
7, relevant statistics display, the refined matte of China about 1/3rd is from reclaimed copper, and about 60% raw material being used as reclaimed copper in copper scap, other about 40% is used directly.Therefore, the metal recovery rate of copper scap of the rate of recovery-particularly improving copper just becomes the problem that first will solve of industry.
8, along with the appearance successively of the relevant laws and regulations such as national related industries policy, Copper making industry standard condition, China's reclaimed copper industry will enter beyond example competition period.Therefore a kind of new technology of exigence accelerates the technical progress of reclaimed copper enterprise, cuts down finished cost, and improves Environmental Protection Level and valuable metal synthetical recovery ability.
9, for solving the above drawback existed in copper scap regeneration technique, the high-efficiency cleaning novel process of exploitation synthetical recovery copper scap, to China's copper scap secondary industry upgrading, the problem such as the environmental protection of puzzlement copper scap industry and the efficiency utilization of resource that solves has great importance.
Therefore a kind of new technology of exigence accelerates the technical progress of reclaimed copper enterprise, cuts down finished cost, and improves Environmental Protection Level and valuable metal synthetical recovery ability.This is contriver's problem to be solved just also.
Summary of the invention
The weak point that Production Flow Chart is long, metal recovery rate is low, environmental protection pressure is large, production cost is high is there is for existing copper scap regeneration industry, the object of invention is exactly for overcoming the deficiencies in the prior art, the difficult problem that, metal recovery rate high for production cost is low, a kind of method of copper scap melt-forming direct production standard cathode copper is provided, realize shortening the technological process of production, improve the rate of recovery, reduce energy consumption, raising utilizes level, reduce environmental pollution, and then reduce process plants cost.
The present invention is realized by such technical scheme: copper scap melt-forming Direct Electrolysis extracts the method for copper, and it is characterized in that, concrete steps are as follows:
(1) using the copper scap direct fusion casting mold of cupric more than 60% as anode, using copper sheet as negative electrode;
(2) add in electrolyzer with copper sulfate, sulfuric acid, hydrochloric acid preparation electrolytic solution, bath composition scope: concentration of copper sulfate 45-60 grams per liter, sulfuric acid concentration 160-200 grams per liter, concentration of hydrochloric acid 0.04-0.08 grams per liter, all the other are water;
(3) in electrolyzer, pass into direct current and carry out electrolysis, processing condition: electrolyte temperature 55-65 DEG C, cathode current density 150-260A/m
2; Copper raw material direct fusion is cast rectangular slab, and on rectangular slab, punching wears copper current conducting rod as anode or directly cast positive plate as anode; The composition range of the copper scap that present method is suitable for: copper 60-99.5%, plumbous 0-10%, nickel 0-5%, iron 0-3%, tin 0-3%, zinc 0-10%.
Beneficial effect of the present invention is:
1, use the present invention, eliminate oxidation, reduction refining operation owing to being processed in anodic process at copper scap, shorten technical process, improve metal recovery rate.Copper total yield, more than 99%, compares with existing traditional technology, and metal recovery rate improves 2-3 percentage point.
2, use the present invention to copper scap melt-forming Direct Electrolysis, compare with existing traditional technology, shorten the production time, improve production efficiency, reduce production comprehensive cost.
3, use the present invention to eliminate oxidation, reduction refining operation owing to being processed in anodic process at copper scap, alleviate environmental pollution, improve Environmental Protection Level.
4, use the present invention can the copper scap of Treatment of Copper amount more than 60%, output cathode copper purity can reach more than 99.96%, quality meets GB/T 467-1997 standard, and most of impurity element apart from copper with the form output of the anode sludge and enrichment reclaim again, improve valuable metal synthetical recovery ability.
Present method principal feature is in smelting process, eliminate this link of redox, energy decreasing pollution, and shortens technical process.The controling parameters of electrolysis link is just through that long period of experiments sums up out.
Solve that the technical process that existing production technique also exists is long, the rate of recovery is low, energy consumption is high, utilize the problems such as level is low, environmental pollution is large.Present method cancels the melting operation such as oxidation, reduction, has that the rate of recovery is high, cost is low, with short production cycle, the advantage that alleviates environmental pollution.
Accompanying drawing explanation
Fig. 1, production technological process.
Embodiment
For a more clear understanding of the present invention, by reference to the accompanying drawings 1 and embodiment describe the present invention in detail;
Embodiment one: raw material is the composition brass of 92%
1, rectangle punching is cast in composition brass fusing, wear copper current conducting rod as anode, scale copper is as negative electrode;
The anode components that founding becomes
2, add in electrolyzer with copper sulfate, sulfuric acid, hydrochloric acid preparation electrolytic solution, bath composition: concentration of copper sulfate 53 grams per liter, sulfuric acid concentration 170 grams per liter, concentration of hydrochloric acid 0.06 grams per liter, keeps bath composition to stablize;
3, electrolyte temperature controls at 62 DEG C;
4, cathode current density 200A/m3, keeps the concentration range of electrolytic solution cupric ion, chlorion, sulfuric acid in production process;
5, add 300 grams/ton, additive gelatine and separate out copper, thiocarbamide 30 grams/ton separates out copper.
After electrorefining, the physical appearance of output cathode copper is smooth fine and closely woven, and chemical composition is up to state standards the requirement of cathode copper, cupric 99.968%.Power consumption 360kwh/t Cu.The valuable metals such as precious metal are with the form enriching and recovering of the anode sludge.
Output cathode copper composition is:
Embodiment two: raw material is the composition brass copper rice of cupric 94%.
1, the fusing of composition brass copper rice is cast positive plate as anode, scale copper is as negative electrode.
The anode components that founding becomes is:
2, prepare bath composition: cupric ion 50 grams per liter, sulfuric acid 180 grams per liter, chlorion 0.05 grams per liter, add hydrochloric acid and keep chlorine ion concentration;
3, electrolyte temperature controls at 62 DEG C;
4, cathode current density 240A/m3, keeps the concentration range of electrolytic solution cupric ion, chlorion, sulfuric acid in production process;
5, add 200 grams/ton, additive gelatine and separate out copper, thiocarbamide 20 grams/ton separates out copper.
After electrorefining, the physical appearance of output cathode copper is smooth fine and closely woven, and chemical composition is up to state standards the requirement of cathode copper, cupric 99.972%, power consumption 350kwh/t Cu.The valuable metals such as precious metal are with the form enriching and recovering of the anode sludge.
Output cathode copper composition is:
To sum up embodiment, the concrete steps of present method are summarised as:
By copper raw material direct fusion casting mold, adopt smelting furnace or other type of heating direct fusion, cancel oxidation, reduction refining operation in current conventional process flow.
By copper raw material direct fusion casting mold rectangularity block, rectangular blocks is punched, wears copper current conducting rod as anode or directly cast positive plate as anode.
Using copper sheet or stainless steel plate as negative electrode.
Be mixed with the electrolytic solution meeting processing requirement add in electrolyzer with copper sulfate, sulfuric acid, hydrochloric acid, pass into direct current, control suitable processing condition and carry out electrolysis.
Need in electrolytic process to add additive: separate out copper for gelatine 200-400 gram/ton, separate out copper for thiocarbamide 20-60 gram/ton, improve copper and separate out quality.
Need in electrolytic process to add copper sulfate, the concentration of copper sulfate in maintenance electrolytic solution is within scope.
According to the above description, the solution of the present invention can be realized in conjunction with art technology.
Claims (5)
1. copper scap melt-forming Direct Electrolysis extracts the method for copper, and it is characterized in that, concrete steps are as follows:
(1) using the copper scap direct fusion casting mold of cupric more than 60% as anode, using copper sheet as negative electrode;
(2) add in electrolyzer with copper sulfate, sulfuric acid, hydrochloric acid preparation electrolytic solution, bath composition scope: concentration of copper sulfate 45-60 grams per liter, sulfuric acid concentration 160-200 grams per liter, concentration of hydrochloric acid 0.04-0.08 grams per liter, all the other are water;
(3) in electrolyzer, pass into direct current and carry out electrolysis, processing condition: electrolyte temperature 55-65 DEG C, cathode current density 150-260A/m
2; Copper raw material direct fusion is cast rectangular slab, and on rectangular slab, punching wears copper current conducting rod as anode or directly cast positive plate as anode; The composition range of the copper scap that present method is suitable for: copper 60-99.5%, plumbous 0-10%, nickel 0-5%, iron 0-3%, tin 0-3%, zinc 0-10%.
2. copper scap melt-forming Direct Electrolysis according to claim 1 extracts the method for copper, it is characterized in that: by copper raw material direct fusion casting mold, adopt smelting furnace or other type of heating direct fusion, cancel oxidation, reduction refining operation in current conventional process flow.
3. copper scap melt-forming Direct Electrolysis according to claim 1 extracts the method for copper, it is characterized in that: using copper sheet or stainless steel plate as negative electrode.
4. copper scap melt-forming Direct Electrolysis according to claim 1 extracts the method for copper, it is characterized in that: need in electrolytic process to add additive: separate out copper for gelatine 200-400 gram/ton, separates out copper for thiocarbamide 20-60 gram/ton, improves copper and separates out quality.
5. copper scap melt-forming Direct Electrolysis according to claim 1 extracts the method for copper, it is characterized in that: need in electrolytic process to add copper sulfate, and the concentration of copper sulfate in maintenance electrolytic solution is within scope.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410573987.6A CN104278291A (en) | 2014-10-24 | 2014-10-24 | Method of directly melting and molding scrap copper to extract copper by electrolysis |
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| CN201410573987.6A CN104278291A (en) | 2014-10-24 | 2014-10-24 | Method of directly melting and molding scrap copper to extract copper by electrolysis |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277359A (en) * | 2018-01-26 | 2018-07-13 | 宁波华成阀门有限公司 | The lead-free reflow and its manufacturing method extracted in a kind of copper scrap from valve |
| CN109055979A (en) * | 2018-09-04 | 2018-12-21 | 太原工业学院 | A kind of electrolysis unit and a kind of method of electrolysis copper processed |
| CN110042274A (en) * | 2019-05-05 | 2019-07-23 | 陶大海 | A kind of high elastic modulus, copper alloy of stress relaxation-resistant and preparation method thereof |
| CN110144604A (en) * | 2019-06-17 | 2019-08-20 | 阳谷祥光铜业有限公司 | A kind of preparation process of electrodeposition copper powder |
| CN111826684A (en) * | 2020-07-31 | 2020-10-27 | 中华全国供销合作总社天津再生资源研究所 | Electrolytic tank and electrolytic system for producing copper powder by using scrap copper material |
| CN113430580A (en) * | 2021-06-02 | 2021-09-24 | 清远市进田企业有限公司 | Preparation method of electrolytic copper for powder metallurgy |
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| CN102839390A (en) * | 2012-08-17 | 2012-12-26 | 致远控股集团有限公司 | Low-grade black scrap copper electrolysis process |
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Patent Citations (6)
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| CN1145958A (en) * | 1995-09-20 | 1997-03-26 | 李皆 | Direct electrolysis process of refining copper-bearing waste material |
| JPH11229171A (en) * | 1998-02-19 | 1999-08-24 | Sumitomo Metal Mining Co Ltd | Operation of decoppering electrolysis |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277359A (en) * | 2018-01-26 | 2018-07-13 | 宁波华成阀门有限公司 | The lead-free reflow and its manufacturing method extracted in a kind of copper scrap from valve |
| CN109055979A (en) * | 2018-09-04 | 2018-12-21 | 太原工业学院 | A kind of electrolysis unit and a kind of method of electrolysis copper processed |
| CN110042274A (en) * | 2019-05-05 | 2019-07-23 | 陶大海 | A kind of high elastic modulus, copper alloy of stress relaxation-resistant and preparation method thereof |
| CN110144604A (en) * | 2019-06-17 | 2019-08-20 | 阳谷祥光铜业有限公司 | A kind of preparation process of electrodeposition copper powder |
| CN111826684A (en) * | 2020-07-31 | 2020-10-27 | 中华全国供销合作总社天津再生资源研究所 | Electrolytic tank and electrolytic system for producing copper powder by using scrap copper material |
| CN113430580A (en) * | 2021-06-02 | 2021-09-24 | 清远市进田企业有限公司 | Preparation method of electrolytic copper for powder metallurgy |
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Application publication date: 20150114 |