CN102534656A - Process for recycling copper through electrodeposition by treating scrap copper materials by adopting cyclone electrolysis technology - Google Patents
Process for recycling copper through electrodeposition by treating scrap copper materials by adopting cyclone electrolysis technology Download PDFInfo
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- CN102534656A CN102534656A CN2012100296590A CN201210029659A CN102534656A CN 102534656 A CN102534656 A CN 102534656A CN 2012100296590 A CN2012100296590 A CN 2012100296590A CN 201210029659 A CN201210029659 A CN 201210029659A CN 102534656 A CN102534656 A CN 102534656A
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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
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Abstract
The invention provides a process for recycling copper through electrodeposition by treating scrap copper materials by adopting a cyclone electrolysis technology, belonging to the technical field of recycling copper from wastes containing copper. The process is characterized by taking various purchased wastes containing copper as raw materials, preliminarily screening and grinding the wastes, adding the materials to a dissolved copper leaching bath device to undergo continuous copper dissolving to obtain a copper sulfate solution, then filtering the solution with precision filter equipment, decoppering the obtained filtrate through cyclone electrolysis, scalding an obtained copper pipe with weak acid and then feeding the copper pipe into a product processing unit to process a standard copper plate. The process has the following beneficial effects: through portable or module assembly, the cyclone electrolysis bath and support equipment are convenient to install, dismantle and move; the solution circulates in a closed loop, thus avoiding emission of harmful gases; electrolytic deposition is carried out on the metals selectively and the copper can be better purified by applying the cyclone electrolysis technology; higher current density and current efficiency are ensured, fewer reagents are consumed, the production cost is lowered and the enterprise revenue is improved; and high efficiency and high purity electrolytic extraction is carried out on the solution, the recycled copper is the standard cathode copper and the total recycling rate is above 96%.
Description
Technical field
The invention belongs to copper-bearing waste material and reclaim the copper technology field, be specifically related to a kind of useless composition brass material electrodeposition of eddy flow electrolysis tech processing efficient, reliable, that technical process is simple, easy and simple to handle, with low cost and reclaim process for copper.
Background technology
Useless composition brass can be divided into new useless composition brass and old useless composition brass, respectively accounts for half the approximately.New useless composition brass is the waste material that produces in the industrial production, copper that goes out of use after old copper scrap is to use or the copper in article that go out of use or the waste material.The method of recycling copper scrap at present both at home and abroad is a lot, mainly is divided into two types, and the first kind is direct utilization, accounts for 2/3 of copper scrap total amount, is about to high-quality useless composition brass and is smelted directly into smart copper or copper alloy; Second type is indirect utilization, accounts for 1/3 of useless composition brass total amount, promptly removes the base metal impurity in the useless composition brass through smelting, and it is cast positive plate, and electrorefining becomes electrolytic copper.
The smelting technology of general useless composition brass, promptly indirect utilization technology is divided into one-stage process, two-phase method, three-stage process.One-stage process is handled the purple composition brass, brass of copper grade＞90% etc., directly it is added to be refined into anode in refining furnace, again the electrolysis production cathode copper.The useless composition brass of two-phase method Treatment of Copper＞70%, it is fusing earlier in smelting furnace or converting furnace, reduces or blows into blister copper, passes through refining furnace-electrorefining again, the output cathode copper.Three-stage process is that cupric is lower than 70% useless composition brass and copper-bearing waste material through blast furnace (or ISA stove, TBRC stove, the many stoves of Ka Er etc.) melting-bessemerize-anode refining-electrolysis, output cathode copper.
At present there is significant disadvantages in the smelting technology technology of the useless composition brass smelting enterprise of China: 1. to the bad adaptability of raw material, existing process intelligent is handled the useless composition brass of higher-grade; 2. owing to the scientific research insufficient investment, the comprehensive recovery degree of existing smeltery raw material is low, has increased the difficulty and the cost of recycling, the income that is difficult to obtain; 3. energy consumption height, environment difference are the more general problems in domestic useless composition brass smeltery; 4. in technology, production-scale selection outstanding " newly " and " greatly ", and ignored this core of benefit; 5. long, the less low-grade useless composition brass more hard to manage of Production Flow Chart.Therefore; In environmental protection demand more and more stricter today; Energy-saving and emission-reduction and develop a circular economy and become inevitable choice simultaneously when handling useless composition brass, cut down the consumption of energy, shortened process, reduction running cost, improve Working environment, improve problems such as comprehensive benefit; Need the processing of the new useless composition brass of research and reclaim process for copper, have crucial meaning.
Summary of the invention
To the problems referred to above that exist in the prior art, the object of the present invention is to provide a kind of eddy flow electrolysis tech efficient, reliable, that technical process is simple, easy and simple to handle, with low cost to handle useless composition brass material electrodeposition and reclaim process for copper.It effectively handles the useless composition brass and the shortened process of various grades through adopting go-on-go, fragmentation, leaching, a complete set of wet processing of eddy flow electrolysis, reaches the purpose of energy-saving and emission-reduction, high-efficiency environment friendly.
Described eddy flow electrolysis tech is handled useless composition brass material electrodeposition and is reclaimed process for copper, it is characterized in that comprising the steps:
1) letter sorting: the useless composition brass material of raw material is slightly gone on foot screening and classification through manual work, remove organic impuritys such as rubber, plastics, lacquer class;
2) fragmentation: step 1) is ground into 5-10mm single-size material through the useless composition brass that sorts with the metal kibbler, so that feed intake, accelerate the leaching yield of reaction efficiency, raising copper;
3) a useless composition brass material material that the molten copper of aeration air supporting: with step 2) obtains adds molten copper reactor drum; Air is blasted molten copper reactor drum through microporous membrane pipe and the micropore hollow sheeting aeration that dissolves the copper reactor drum; Fully emulsified with the sulfuric acid of 100-180g/L; Obtain useless composition brass leach liquor, described microporous membrane pipe and micropore hollow sheeting aperture are 5-10 μ m;
4) secondary filter: the useless composition brass leach liquor that step 3) is obtained carries out the secondary filter processing;
5) eddy flow electrolysis production cathode copper: the leach liquor after the precision is under the effect of recycle pump; Squeeze into the electrodeposition circulation groove with the flow velocity that is exceedingly fast; Get into again with eddy flow electrolyzer that the electrodeposition circulation groove is connected in carry out eddy flow electrolysis decopper(ing); The negative electrode copper pipe that generates is collected by collector, and the electrodeposition lean solution that obtains behind the eddy flow electrolysis decopper(ing) is returned aeration air supporting and dissolved the copper device as the useless composition brass material of reaction acid leaching, described current density 220-800A/m
2, electrolyte flow rate is 12000-18000L/h;
6) the negative electrode copper pipe that step 5) is obtained is put into and is scalded board slot and scald with what contain dilute sulphuric acid that liquid washs, drying treatment, obtains clean negative electrode copper pipe, and this negative electrode copper pipe is got into product processing unit, is processed into the standard copper coin.
Described eddy flow electrolysis tech is handled useless composition brass material electrodeposition and is reclaimed process for copper, it is characterized in that the stripping temperature described in the step 3) is controlled at 80 ℃-85 ℃, and dissolving copper speed is 300-500Kg/m
3.d.
Described eddy flow electrolysis tech is handled useless composition brass material electrodeposition and is reclaimed process for copper, it is characterized in that the copper ion concentration 20-70g/l in the useless composition brass leach liquor described in the step 3), and sulfuric acid concentration is the copper-bath of 60-100g/l.
Described eddy flow electrolysis tech is handled useless composition brass material electrodeposition and is reclaimed process for copper, it is characterized in that the filtration velocity described in the step 4) is 4.5-5.5 m
3/ h.
Described eddy flow electrolysis tech is handled useless composition brass material electrodeposition and is reclaimed process for copper, it is characterized in that the pH value of the filtrating described in the step 4) is-1-5, and temperature is 20-60 ℃.
Described eddy flow electrolysis tech is handled useless composition brass material electrodeposition and is reclaimed process for copper, and the flow that it is characterized in that the recycle pump described in the step 5) is 120-200m
3/ h, copper ion concentration is 5-15g/l in the described electrodeposition lean solution, sulfuric acid concentration is 160-180g/l.
Described eddy flow electrolysis tech is handled various useless composition brasses and is reclaimed process for copper, it is characterized in that the described current density 300-800A/m of step 5)
2, electrolyte flow rate is 13000-17000L/h.
Described eddy flow electrolysis tech is handled various useless composition brasses and is reclaimed process for copper, it is characterized in that the described liquid of scalding of step 6) is the dilution heat of sulfuric acid of pH at 2.5-3.5, and the time of scalding is 20-30 minute, and the temperature of scalding board slot is >=90 ℃.
Through adopting above-mentioned technology, compared with prior art, beneficial effect of the present invention is following:
1) the present invention is for the useless better stripping of composition brass material; Raw material is carried out Rough Inspection and metal pulverizing crusher machine, get into the molten copper device of microvesicle and carry out the wet method leaching, reached the purpose of high-efficiency environment friendly; Do not produce any pollution, realize leaching efficiency height, sufficient reacting, free of contamination characteristics simultaneously;
2) the present invention adopts the useless composition brass leach liquor of eddy flow electrolysis process processing then to have higher current density and current efficiency;
3) electrodeposition of the present invention adopts the eddy flow electrolysis tech; And adopt automatic control current of PLC circulating pump system and feed liquor flow, effectively improve workload, in the eddy flow electrolysis; Adopt electrowinning intelligence to reclaim collecting device and gather copper pipe; This equipment has characteristics such as easy and simple to handle, safe, reliable, can be widely used in metallurgy industry, has stronger technology and cost advantage;
4) the present invention is through portable or module assembling, and eddy flow electrolyzer and support equipment make things convenient for installing/dismounting to relocate; The solution closed cycle does not have discharge of harmful gases; Optionally metal is carried out electrolytic deposition, use the eddy flow electrolysis tech copper of can better purifying; Higher current density and current efficiency, reagent consumption is few, reduces production costs, and improves the performance of enterprises;
5) the present invention is through above-mentioned technology; Can effectively substitute the useless composition brass technology of traditional pyrogenic attack; Directly carry out refining with wet method, process simplification, useless composition brass infusion solution is electrodeposition directly; Cut operating costs greatly, reduce technical risk and shortened technical process, reduced running cost, improved economic return; The copper coin purity that reclaims is 99.95%, and total yield is more than 96%;
6) the present invention is because the eddy flow electrolysis process adopts the sealing and circulating operation; Can be effectively the gas of separating out be absorbed to the absorption cleaning tower through negative pressure and handle; Reduce discharge of harmful gases, effectively improved Working environment, environmental pollution is little, technical process is short, processing cost is low, had the value of promoting the use aspect the processing of useless composition brass; Project investment is little, the construction period is short, risk is little, society and remarkable in economical benefits.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Eddy flow electrolysis tech of the present invention is handled useless composition brass material electrodeposition and is reclaimed process for copper, comprises the steps:
1) letter sorting: the useless composition brass material of raw material is slightly gone on foot screening and classification through manual work, remove organic impuritys such as rubber, plastics, lacquer class;
2) fragmentation: step 1) is ground into 5-10mm single-size material through the useless composition brass that sorts with the metal kibbler, so that feed intake, accelerate the leaching yield of reaction efficiency, raising copper; 4.2 tons of all kinds of irregular copper-bearing waste materials such as described metal kibbler day treating piece, bar, line; The pulverizing of copper-contained material has certain degree of difficulty; Degree-of-difficulty factor gets 1.8; 1 600 shaped metal of design Selection is pulverized unit: power 18.5-22KW, mechanical dimensions: 2.65 * 1.5 * 1.85m, processing power: 200-400kg/h;
3) a useless composition brass material material that the molten copper of aeration air supporting: with step 2) obtains adds molten copper reactor drum; Air is blasted molten copper reactor drum through microporous membrane pipe and the micropore hollow sheeting aeration that dissolves the copper reactor drum; The stripping temperature is controlled at 80 ℃-85 ℃; Specifically can be 80 ℃, 82 ℃ or 85 ℃, dissolving copper speed is 300-500Kg/m
3.d, be specially 300Kg/m
3.d, 350Kg/m
3.d, 400Kg/m
3.d, 450Kg/m
3.d, 500Kg/m
3.d; Fully emulsified with the sulfuric acid of 100-180g/L; Sulfuric acid concentration is 100 g/L, 120 g/L, 150 g/L or 180g/L, obtains useless composition brass leach liquor, wherein copper ion concentration 60-65g/l; Sulfuric acid concentration is the copper-bath of 60-80 g/l, and described microporous membrane pipe and micropore hollow sheeting aperture are 5 μ m, 7 μ m or 10 μ m; Day 4.2 tons of the Treatment of Copper materials of said molten copper reactor drum, every day, operation was 15 hours, and unit dissolves the copper amount and is: 280Kg/h, consider that part copper-bearing waste material result of extraction is not good, degree-of-difficulty factor gets 1.4, and microvesicle dissolves copper device unit and dissolves copper efficient and gets: 12 Kg/m
3.h, then need the molten copper effective volume of equipment to be: 280 ÷, 12 * 1.4=32.7 m
3, then need overlap (effective volume 23 m of single cover with molten copper device 2 in the microvesicle of 2.8 * 2.4 * 5.8m
3); Liquid glass reinforced plastic storage tank φ is 4000 * 3,000 1 behind the molten copper of design Selection microvesicle;
4) secondary filter: the useless composition brass leach liquor that step 3) is obtained carries out the secondary filter processing, and filtration velocity is 4.5-5.5 m
3/ h is specially 4.5 m
3/ h, 5 m
3/ h or 5.5 m
3The pH value of the filtrating that/h obtains after filtering is-1,1,2,3,4 or 5, and temperature is 20 ℃, 40 ℃ or 60 ℃; Copper-containing solution is 32m behind the molten copper of secondary filter day processing
3, because dissolution fluid partly contains organic matter or jelly, filtration existence is sometimes filtered slow or is filtered phenomenons such as motionless, for this reason, selects for use this equipment need increase value-at-risk 1.8, design Selection 5 m
3Essence filter equipment 1 cover of/h; Select 1 of smart filter back liquid storage tank (the new liquid bath of electrolysis) φ 3000 * 3000mm glass reinforced plastic storage tank for use;
5) eddy flow electrolysis production cathode copper: the leach liquor after the precision is under the effect of recycle pump; Squeeze into the electrodeposition circulation groove with the flow velocity that is exceedingly fast; Get into again with eddy flow electrolyzer that the electrodeposition circulation groove is connected in carry out eddy flow electrolysis decopper(ing); The negative electrode copper pipe that generates is collected by collector, and the electrodeposition lean solution that obtains behind the eddy flow electrolysis decopper(ing) is returned aeration air supporting and dissolved the copper device and leach useless composition brass material as reaction acid, also can be with wherein small portion electrodeposition lean solution after treatment among the embodiment; Carry out innoxious open circuit, described current density 220-800A/m
2, preferred current density is 300-800A/m
2, electrolyte flow rate is 12000-18000L/h, preferred electrolyte flow rate is 13000-17000L/h; The flow of described recycle pump is 120-200m
3/ h, copper ion concentration is 5-15g/l in the described electrodeposition lean solution, sulfuric acid concentration is 160-180g/l;
6) the negative electrode copper pipe that step 5) is obtained is put into and is scalded board slot and scald with what contain dilute sulphuric acid that liquid washs, drying treatment; Obtain clean negative electrode copper pipe; This negative electrode copper pipe is got into product processing unit, be processed into the standard copper coin, described to scald liquid be pH at 2.5,3.0 or 3.5 dilution heat of sulfuric acid; The time of scalding is 20 minutes, 25 minutes or 30 minutes, and the temperature of scalding board slot is 85 ℃, 120 ℃, 150 ℃ or 180 ℃.
Embodiment 1:
(1) the useless composition brass material of raw material is slightly gone on foot screening and classification through manual work, remove organic impuritys such as rubber, plastics, lacquer class, bulk (greater than 250mm), irregular copper billet material will cut; Be delivered to the metal kibbler through belt and be ground into 5 ~ 10mm single-size material; The charging opening of being delivered to the molten copper device of microvesicle by hopper is for use, the useless composition brass material of raw material is joined be equipped with in the molten copper device of sulfuric acid microvesicle then, and the stripping temperature is controlled at 82 ℃; Stripping obtains copper ion concentration 65g/l; Sulfuric acid concentration is the copper-bath of 70g/l, and is subsequent use, dissolves copper speed and reaches as high as 500Kg/m
3.d (mainly being pulverulent material), lumpy material also can reach 300Kg/m
3.d;
(2) copper-bath that step 1) is obtained filters through secondary filter equipment, and filtration velocity is 5 m
3/ h removes suspended substance, organic matter and particulate contamination, and filter residue returns in the step 1) and raw materials mix, and filtrating is carried out next step operation;
(3) with step 2) in the filtrating that obtains change in the reservoir, the pH value of filtrating is 2, temperature is 40 ℃, through recycle pump filtrating is squeezed in the electrodeposition circulation groove, the flow of recycle pump is 160m
3/ h, described electrodeposition circulation groove is connected with the eddy flow electrolyzer, in the eddy flow electrolyzer, carries out eddy flow electrolysis decopper(ing); Separate out copper pipe, when copper pipe grows to 25kg, reclaim the collecting device collection through electrowinning intelligence and get into the low-concentration sulfuric acid wash water and scald in the groove and wash; Taking-up is dried, and the copper coin purity of recovery is 99.95%, and total yield is more than 96%; Electrolytic solution behind the decopper(ing) subsequent use (this electrolytic solution copper ion concentration is 12g/l, and sulfuric acid concentration is 170g/l);
(4) copper pipe that obtains in the step 3) gets into product processing unit, is processed into standard electrodeposition cathode plate, and the electrolytic solution behind the decopper(ing) is back to the molten copper leaching vat device in the step (1);
(5) step 3) is reduced to 12g/l with the copper ion concentration in the copper-bath by 60g/l, current density 500A/m
2, the flow velocity of electrolytic solution is 15000 l/hr.
Claims (8)
1. the eddy flow electrolysis tech is handled useless composition brass material electrodeposition and is reclaimed process for copper, it is characterized in that comprising the steps:
1) letter sorting: the useless composition brass material of raw material is slightly gone on foot screening and classification through manual work, remove organic impuritys such as rubber, plastics, lacquer class;
2) fragmentation: step 1) is ground into 5-10mm single-size material through the useless composition brass that sorts with the metal kibbler, so that feed intake, accelerate the leaching yield of reaction efficiency, raising copper;
3) a useless composition brass material material that the molten copper of aeration air supporting: with step 2) obtains adds molten copper reactor drum; Air is blasted molten copper reactor drum through microporous membrane pipe and the micropore hollow sheeting aeration that dissolves the copper reactor drum; Fully emulsified with the sulfuric acid of 100-180g/L; Obtain useless composition brass leach liquor, described microporous membrane pipe and micropore hollow sheeting aperture are 5-10 μ m;
4) secondary filter: the useless composition brass leach liquor that step 3) is obtained carries out the secondary filter processing;
5) eddy flow electrolysis production cathode copper: the leach liquor after the precision is under the effect of recycle pump; Squeeze into the electrodeposition circulation groove with the flow velocity that is exceedingly fast; Get into again with eddy flow electrolyzer that the electrodeposition circulation groove is connected in carry out eddy flow electrolysis decopper(ing); The negative electrode copper pipe that generates is collected by collector, and the electrodeposition lean solution that obtains behind the eddy flow electrolysis decopper(ing) is returned aeration air supporting and dissolved the copper device as the useless composition brass material of reaction acid leaching, described current density 220-800A/m
2, electrolyte flow rate is 12000-18000L/h;
6) the negative electrode copper pipe that step 5) is obtained is put into and is scalded board slot and scald with what contain dilute sulphuric acid that liquid washs, drying treatment, obtains clean negative electrode copper pipe, and this negative electrode copper pipe is got into product processing unit, is processed into the standard copper coin.
2. eddy flow electrolysis tech according to claim 1 is handled useless composition brass material electrodeposition and is reclaimed process for copper, it is characterized in that the stripping temperature described in the step 3) is controlled at 80 ℃-85 ℃, and dissolving copper speed is 300-500Kg/m
3.d.
3. eddy flow electrolysis tech according to claim 1 is handled useless composition brass material electrodeposition and is reclaimed process for copper, it is characterized in that the copper ion concentration 20-70g/l in the useless composition brass leach liquor described in the step 3), and sulfuric acid concentration is the copper-bath of 60-100g/l.
4. eddy flow electrolysis tech according to claim 1 is handled useless composition brass material electrodeposition and is reclaimed process for copper, it is characterized in that the filtration velocity described in the step 4) is 4.5-5.5 m
3/ h.
5. eddy flow electrolysis tech according to claim 1 is handled useless composition brass material electrodeposition and is reclaimed process for copper, it is characterized in that the pH value of the filtrating described in the step 4) is-1-5, and temperature is 20-60 ℃.
6. eddy flow electrolysis tech according to claim 1 is handled useless composition brass material electrodeposition and is reclaimed process for copper, and the flow that it is characterized in that the recycle pump described in the step 5) is 120-200m
3/ h, copper ion concentration is 5-15g/l in the described electrodeposition lean solution, sulfuric acid concentration is 160-180g/l.
7. eddy flow electrolysis tech according to claim 1 is handled various useless composition brasses and is reclaimed process for copper, it is characterized in that the described current density 300-800A/m of step 5)
2, electrolyte flow rate is 13000-17000L/h.
8. eddy flow electrolysis tech according to claim 1 is handled various useless composition brasses and is reclaimed process for copper, it is characterized in that the described liquid of scalding of step 6) is the dilution heat of sulfuric acid of pH at 2.5-3.5, and the time of scalding is 20-30 minute, and the temperature of scalding board slot is >=90 ℃.
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| CN201210029659.0A CN102534656B (en) | 2012-02-10 | 2012-02-10 | Process for recycling copper through electrodeposition by treating scrap copper materials by adopting cyclone electrolysis technology |
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| CN103556186A (en) * | 2013-11-05 | 2014-02-05 | 浙江科菲冶金科技股份有限公司 | Selective separation method for copper and beryllium in sulfuric acid system |
| CN103726071A (en) * | 2013-12-13 | 2014-04-16 | 金川集团股份有限公司 | Cathode used for tubular cathode copper production |
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| CN104724864A (en) * | 2015-03-31 | 2015-06-24 | 江苏地一环保科技有限公司 | Cyclone treatment technique of nickel-containing electroplating wastewater |
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| CN114717413A (en) * | 2022-05-09 | 2022-07-08 | 惠州市华盈科技有限公司 | Copper smelting process for soaking waste copper material by high-pressure oxygen |
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