CN102534656B - 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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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 copper technology field, be specifically related to a kind of efficient, reliable, that technical process is simple, easy and simple to handle, with low cost cyclone electrolytic cell technical finesse copper scap material electrodeposition and reclaim process for copper.
Background technology
Copper scap can be divided into new copper scap and old copper scap, about respectively accounts for half.New copper scap is the waste material produced in industrial production, and old copper scrap is the copper in the copper or the article gone out of use or waste material gone out of use after using.The method recycling copper scrap at present is both at home and abroad a lot, and be mainly divided into two classes, the first kind is direct utilization, accounts for 2/3 of copper scrap total amount, is smelted directly into smart copper or copper alloy by high-quality copper scap; Equations of The Second Kind is indirect utilization, accounts for 1/3 of copper scap total amount, and namely by smelting the base metal impurity in removing copper scap, and cast positive plate, electrorefining becomes electrolytic copper.
The smelting technology of general copper scap, i.e. indirect utilization technique, be divided into one-stage process, two-phase method, three-stage process.The recycled copper, brass etc. of one-stage process process copper grade > 90%, directly added in refining furnace and be refined into anode, then electrolysis production cathode copper.The copper scap of two-phase method Treatment of Copper > 70%, it first melts in smelting furnace or converting furnace, reduces or blows into blister copper, then through refining furnace-electrorefining, output cathode copper.Three-stage process be by cupric lower than 70% copper scap and copper-bearing waste material through blast furnace (or ISA stove, TBRC stove, Kaldo Furnace etc.) melting-bessemerize-anode refining-electrolysis, output cathode copper.
There is obvious shortcoming in the smelting technology technology of the copper scap smelting enterprise of current China: 1. to the bad adaptability of raw material, existing process intelligent process higher-grade copper scap; 2. because science research input is not enough, the synthetical recovery degree of existing smeltery raw material is low, adds difficulty and the cost of recycling, is difficult to the income obtained; 3. high, the environment of energy consumption is poor is the more general problem in domestic copper scap smeltery; 4. in technique, production-scale selection outstanding " newly " and " greatly ", have ignored this core of benefit; 5. Production Flow Chart length, less more difficult low-grade copper scap.Therefore, in today that ecological requirements is more and more stricter, energy-saving and emission-reduction and develop a circular economy and become inevitable choice, time simultaneously in order to process copper scap, reduce energy consumption, shortened process, reduction running cost, improve Working environment, improve the problems such as comprehensive benefit, need process and the recovery process for copper of studying new copper scap, tool is of great significance.
Summary of the invention
For the above-mentioned problems in the prior art, a kind of efficient, reliable, that technical process is simple, easy and simple to handle, with low cost cyclone electrolytic cell technical finesse copper scap material electrodeposition is the object of the present invention is to provide to reclaim process for copper.It, by adopting go-on-go, fragmentation, leaching, a complete set of wet processing of cyclone electrolytic cell, effectively processes copper scap and the shortened process of various grade, reaches the object of energy-saving and emission-reduction, high-efficiency environment friendly.
Described cyclone electrolytic cell technical finesse copper scap material electrodeposition reclaims process for copper, it is characterized in that comprising the steps:
1) sort: by raw material copper scap material through the screening of artificial thick step and classification, remove the organic impuritys such as rubber, plastics, paint class;
2) broken: step 1) is ground into 5-10mm single-size material through the copper scap metal pulverizer of sorting, so that the leaching yield feeding intake, accelerate reaction efficiency, improve copper;
3) the molten copper of aeration air supporting: by step 2) copper scap that obtains a material material adds molten copper reactor, air is blasted molten copper reactor by the microporous membrane pipe of molten copper reactor and micro porous hollow plate aeration, fully emulsified with the sulfuric acid of 100-180g/L, obtain copper scap leach liquor, described microporous membrane pipe and micro porous hollow panel aperture are 5-10 μm;
4) secondary filter: copper scap leach liquor step 3) obtained carries out secondary filter process;
5) cyclone electrolytic cell produces cathode copper: the leach liquor after precision is under the effect of recycle pump, electrodeposition circulation groove is squeezed into the flow velocity be exceedingly fast, enter again in the swirl electrolysis device that is connected with electrodeposition circulation groove and carry out cyclone electrolytic cell decopper(ing), the negative electrode copper pipe generated is collected by collector, the electrodeposition lean solution obtained after cyclone electrolytic cell decopper(ing) returns the molten copper device of aeration air supporting and leaches copper scap material as reaction acid, described current density 220-800A/m
2, electrolyte flow rate is 12000-18000L/h;
6) negative electrode copper pipe step 5) obtained is put into and is scalded board slot with scalding that liquid carries out washing, drying treatment containing dilute sulphuric acid, obtains clean negative electrode copper pipe, this negative electrode copper pipe is entered Product processing unit, is processed into standard copper coin.
Described cyclone electrolytic cell technical finesse copper scap material electrodeposition reclaims process for copper, and it is characterized in that the leaching temperature described in step 3) controls at 80 DEG C-85 DEG C, molten copper speed is 300-500Kg/m
3.d.
Described cyclone electrolytic cell technical finesse copper scap material electrodeposition reclaims process for copper, and it is characterized in that the copper ion concentration 20-70g/l in the copper scap leach liquor described in step 3), sulfuric acid concentration is the copper-bath of 60-100g/l.
Described cyclone electrolytic cell technical finesse copper scap material electrodeposition reclaims process for copper, it is characterized in that the filtration velocity described in step 4) is 4.5-5.5 m
3/ h.
Described cyclone electrolytic cell technical finesse copper scap material electrodeposition reclaims process for copper, and it is characterized in that the pH value of the filtrate described in step 4) is-1-5, temperature is 20-60 DEG C.
Described cyclone electrolytic cell technical finesse copper scap material electrodeposition reclaims process for copper, it is characterized in that the flow of the recycle pump described in step 5) is 120-200m
3/ h, in described electrodeposition lean solution, copper ion concentration is 5-15g/l, and sulfuric acid concentration is 160-180g/l.
The various copper scap of described cyclone electrolytic cell technical finesse reclaims process for copper, it is characterized in that the current density 300-800A/m described in step 5)
2, electrolyte flow rate is 13000-17000L/h.
The various copper scap of described cyclone electrolytic cell technical finesse reclaims process for copper, and it is characterized in that the liquid of scalding described in step 6) is the dilution heat of sulfuric acid of pH at 2.5-3.5, the time of scalding is 20-30 minute, and the temperature of scalding board slot is >=90 DEG C.
By adopting above-mentioned technology, compared with prior art, beneficial effect of the present invention is as follows:
1) the present invention is in order to the better stripping of copper scap material, raw material is carried out Rough Inspection and metal pulverizer fragmentation, enter the molten copper device of microvesicle and carry out wet-leaching, reach the object of high-efficiency environment friendly, do not produce any pollution, realize that leaching efficiency is high, sufficient reacting, free of contamination feature simultaneously;
2) the present invention adopts cyclone electrolytic cell art breading copper scap leach liquor then to have higher current density and current efficiency;
3) electrodeposition of the present invention adopts cyclone electrolytic cell technology, and adopt PLC circulating pump system automatic control electric stream and feed liquor flow, effective raising workload, in cyclone electrolytic cell, adopt electrowinning intelligence to reclaim collecting device and gather copper pipe, this equipment has the features such as easy and simple to handle, safe, reliable, can be widely used in metallurgy industry, have stronger technology and cost advantage;
4) the present invention is by portable or module assembled, and swirl electrolysis device and support equipment facilitate installing/dismounting to relocate; Solution closed cycle, does not have the discharge of obnoxious flavour; Optionally carry out electrolytic deposition to metal, application cyclone electrolytic cell technology can better be purified copper; Higher current density and current efficiency, reagent consumption is few, reduces production cost, improves the performance of enterprises;
5) the present invention is by above-mentioned technology, effectively can substitute traditional pyrogenic attack copper scap technique, direct wet method carries out refining, process simplification, copper scap infusion solution can direct electrowinning, greatly cut operating costs, reduce technical risk and shorten technical process, reduce running cost, improve economic return; The copper coin purity reclaimed is 99.95%, and total yield is more than 96%;
6) the present invention is due to the operation of cyclone electrolytic cell technique employing sealing and circulating, can effectively by separate out gas through negative pressure absorbing to type absorption purification tower process, decrease the discharge of obnoxious flavour, effectively improve Working environment, environmental pollution is little, technical process is short, processing cost is low, have in the process of copper scap and promote the use value, project investment is little, the construction period is short, risk is little, and Social and economic benef@is remarkable.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Cyclone electrolytic cell technical finesse copper scap material electrodeposition of the present invention reclaims process for copper, comprises the steps:
1) sort: by raw material copper scap material through the screening of artificial thick step and classification, remove the organic impuritys such as rubber, plastics, paint class;
2) broken: step 1) is ground into 5-10mm single-size material through the copper scap metal pulverizer of sorting, so that the leaching yield feeding intake, accelerate reaction efficiency, improve copper; The described all kinds of irregular copper-bearing waste material 4.2 tons such as metal pulverizer day treating piece, bar, line, the pulverizing of copper-contained material has certain difficulty, degree-of-difficulty factor gets 1.8, design selects 1 600 shaped metal to pulverize unit: power 18.5-22KW, mechanical dimensions: 2.65 × 1.5 × 1.85m, processing power: 200-400kg/h;
3) the molten copper of aeration air supporting: by step 2) copper scap that obtains a material material adds molten copper reactor, air is blasted molten copper reactor by the microporous membrane pipe of molten copper reactor and micro porous hollow plate aeration, leaching temperature controls at 80 DEG C-85 DEG C, be specifically as follows 80 DEG C, 82 DEG C or 85 DEG C, molten copper speed is 300-500Kg/m
3.d, 300Kg/m is specially
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, obtain copper scap 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 micro porous hollow panel aperture are 5 μm, 7 μm or 10 μm; The day Treatment of Copper material 4.2 tons of described molten copper reactor, operation 15 hours every day, the molten copper amount of unit is: 280Kg/h, and consider that part copper-bearing waste material result of extraction is not good, degree-of-difficulty factor gets 1.4, and the molten copper efficiency of microvesicle Rong Tong device unit is got: 12 Kg/m
3.h, then the molten copper effective volume of equipment is needed to be: 280 ÷ 12 × 1.4=32.7 m
3, then need in the microvesicle of 2.8 × 2.4 × 5.8m, to overlap (single cover useful volume 23 m with molten copper device 2
3); Liquid glass reinforced plastic storage tank φ 4000 × 3,000 1 after the molten copper of microvesicle is selected in design;
4) secondary filter: copper scap leach liquor step 3) obtained carries out secondary filter process, 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 filtrate that/h obtains after filtering is-1,1,2,3,4 or 5, and temperature is 20 DEG C, 40 DEG C or 60 DEG C; After processing molten copper secondary filter day, copper-containing solution is 32m
3, because dissolution fluid part contains organic matter or jelly, filter sometimes to exist and filter slow or filter the phenomenons such as motionless, for this reason, select this equipment need increase value-at-risk 1.8,5 m are selected in design
3the essence filter equipment 1 of/h overlaps; Select rear liquid storage tank (the new liquid bath of the electrolysis) φ 3000 × 3000mm glass reinforced plastic storage tank 1 of essence filter;
5) cyclone electrolytic cell produces cathode copper: the leach liquor after precision is under the effect of recycle pump, electrodeposition circulation groove is squeezed into the flow velocity be exceedingly fast, enter again in the swirl electrolysis device that is connected with electrodeposition circulation groove and carry out cyclone electrolytic cell decopper(ing), the negative electrode copper pipe generated is collected by collector, the electrodeposition lean solution obtained after cyclone electrolytic cell decopper(ing) returns the molten copper device of aeration air supporting and leaches copper scap material as reaction acid, also can by small portion electrodeposition lean solution wherein after treatment in 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, and preferred electrolyte flow rate is 13000-17000L/h; The flow of described recycle pump is 120-200m
3/ h, in described electrodeposition lean solution, copper ion concentration is 5-15g/l, and sulfuric acid concentration is 160-180g/l;
6) negative electrode copper pipe step 5) obtained is put into and is scalded board slot with scalding that liquid carries out washing, drying treatment containing dilute sulphuric acid, obtain clean negative electrode copper pipe, this negative electrode copper pipe is entered Product processing unit, be processed into standard copper coin, described to scald liquid be pH 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 DEG C, 120 DEG C, 150 DEG C or 180 DEG C.
Embodiment 1:
(1) raw material copper scap material is slightly walked screening and classification through artificial, remove rubber, plastics, the organic impuritys such as paint class, bulk (being greater than 250mm), irregular copper billet material will cut, 5 ~ 10mm single-size material is ground into by Belt Conveying to metal pulverizer, the charging opening being delivered to microvesicle molten copper device by hopper is stand-by, then being joined by raw material copper scap material is equipped with in the molten copper device of sulfuric acid microvesicle, leaching temperature controls at 82 DEG C, stripping obtains copper ion concentration 65g/l, sulfuric acid concentration is the copper-bath of 70g/l, for subsequent use, molten copper speed reaches as high as 500Kg/m
3.d(mainly pulverulent material), lumpy material also can reach 300Kg/m
3.d,
(2) copper-bath step 1) obtained filters through secondary filter equipment, and filtration velocity is 5 m
3/ h, removing suspended substance, organic matter and particulate contamination, filter residue returns in step 1) and mixes with raw material, and filtrate carries out next step operation;
(3) by step 2) in the filtrate that obtains proceed in reservoir, the pH value of filtrate is 2, and temperature is 40 DEG C, squeezes in electrodeposition circulation groove by recycle pump by filtrate, and the flow of recycle pump is 160m
3/ h, described electrodeposition circulation groove is connected with swirl electrolysis device, in swirl electrolysis device, carry out cyclone electrolytic cell decopper(ing), separate out copper pipe, when copper pipe grows to 25kg, reclaim collecting device collection by electrowinning intelligence to enter low-concentration sulfuric acid wash water and scald in 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 after decopper(ing) (this electrolytic solution copper ion concentration is 12g/l, and sulfuric acid concentration is 170g/l) for subsequent use;
(4) copper pipe obtained in step 3) enters Product processing unit, is processed into standard electrodeposition cathode plate, and the electrolytic solution after decopper(ing) is back to the molten copper leaching vat device in step (1);
(5) copper ion concentration in copper-bath is reduced to 12g/l by 60g/l by step 3), current density 500A/m
2, the flow velocity of electrolytic solution is 15000 l/hr.
Claims (3)
1. cyclone electrolytic cell technical finesse copper scap material electrodeposition reclaims process for copper, it is characterized in that comprising the steps:
1) sort: by raw material copper scap material through the screening of artificial thick step and classification, remove rubber, plastics, paint class organic impurity;
2) broken: step 1) is ground into 5-10mm single-size material through the copper scap metal pulverizer of sorting, so that the leaching yield feeding intake, accelerate reaction efficiency, improve copper;
3) the molten copper of aeration air supporting: by step 2) copper scap that obtains a material material adds molten copper reactor, air is blasted molten copper reactor by the microporous membrane pipe of molten copper reactor and micro porous hollow plate aeration, fully emulsified with the sulfuric acid of 100 g/L, 120 g/L or 180g/L, obtain copper scap leach liquor, described leaching temperature 82 DEG C or 85 DEG C, molten copper speed is 300Kg/m
3d, 350Kg/m
3d, 400Kg/m
3d, 450Kg/m
3d, 500Kg/m
3d, described microporous membrane pipe and micro porous hollow panel aperture are 7 μm;
4) secondary filter: copper scap leach liquor step 3) obtained carries out secondary filter process, described filtration velocity is 4.5 m
3/ h, 5 m
3/ h or 5.5 m
3/ h, the pH value of filtrate is 1,2,3,4 or 5, and temperature is 20 DEG C, 40 DEG C or 60 DEG C;
5) cyclone electrolytic cell produces cathode copper: the leach liquor after precision is under the effect of recycle pump, electrodeposition circulation groove is squeezed into the flow velocity be exceedingly fast, enter again in the swirl electrolysis device that is connected with electrodeposition circulation groove and carry out cyclone electrolytic cell decopper(ing), the negative electrode copper pipe generated is collected by collector, the electrodeposition lean solution obtained after cyclone electrolytic cell decopper(ing) returns the molten copper device of aeration air supporting and leaches copper scap material as reaction acid, described current density 220-800A/m
2, electrolyte flow rate is 12000-18000L/h, and the flow of described recycle pump is 120-200m
3/ h, in described electrodeposition lean solution, copper ion concentration is 5-15g/L, and sulfuric acid concentration is 160-180g/L;
6) negative electrode copper pipe step 5) obtained is put into and is scalded board slot with scalding that liquid carries out washing, drying treatment containing dilute sulphuric acid, obtain clean negative electrode copper pipe, this negative electrode copper pipe is entered Product processing unit, be processed into standard copper coin, described to scald liquid be pH 2.5 or 3.5 dilution heat of sulfuric acid, the time of scalding is 25 minutes or 30 minutes, and the temperature of scalding board slot is 120 DEG C, 150 DEG C or 180 DEG C.
2. cyclone electrolytic cell technical finesse copper scap material electrodeposition according to claim 1 reclaims process for copper, and it is characterized in that the copper ion concentration 20-70g/L in the copper scap leach liquor described in step 3), sulfuric acid concentration is the copper-bath of 60-100g/L.
3. the various copper scap of cyclone electrolytic cell technical finesse according to claim 1 reclaims process for copper, it is characterized in that the current density 300-800A/m described in step 5)
2, electrolyte flow rate is 13000-17000L/h.
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| CN103320813B (en) * | 2013-06-09 | 2015-07-15 | 东江环保股份有限公司 | Eddy flow electrowinning tank and application thereof |
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| 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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| CN106319564B (en) * | 2016-09-13 | 2019-07-05 | 广沣金源（北京）科技有限公司 | A kind of method of the method and electrolytic metal ion of metallic copper, Treatment of Copper ion waste water |
| 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 |
| CN111850603B (en) * | 2020-07-08 | 2021-11-23 | 珠海格力绿色再生资源有限公司 | Recovery device and recovery method for oil-containing copper sludge |
| CN112342395A (en) * | 2020-11-03 | 2021-02-09 | 吕圣快 | Process and equipment for recycling processing waste of copper-based wear-resistant material |
| CN113005291A (en) * | 2021-04-30 | 2021-06-22 | 邱小华 | Scrap copper refining process |
| 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 |
| CN114892221A (en) * | 2022-05-09 | 2022-08-12 | 惠州市华盈科技有限公司 | Cyclone electrolysis method for manufacturing cathode copper sheet |
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