CN104894607A - Method for purifying waste copper sulfate electrolyte - Google Patents
Method for purifying waste copper sulfate electrolyte Download PDFInfo
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- CN104894607A CN104894607A CN201510263335.7A CN201510263335A CN104894607A CN 104894607 A CN104894607 A CN 104894607A CN 201510263335 A CN201510263335 A CN 201510263335A CN 104894607 A CN104894607 A CN 104894607A
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Abstract
The invention discloses a method for purifying waste copper sulfate electrolyte; and the waste copper sulfate electrolyte is purified through three procedures of a waste electrolyte evaporation and condensation, cooling crystallization and redissolving procedure, a primary electrodeposition decoppering procedure and a secondary electrodeposition decoppering procedure of crystallization mother liquor. Through the method for purifying the waste copper sulfate electrolyte, the waste copper sulfate electrolyte is concentrated and crystallized to enrich impurities in secondary electrodeposition liquid; copper sulfate is redissolved to prepare primary electrodeposition liquid with replenishment liquid; all the output of the first-stage electrodeposition is standard cathode copper, which accounts for more than 65% of total decoppering quantity of waste electrolyte; and through evaporation and concentration, the solution volume of the secondary electrodeposition decoppering is decreased, the processing amount of a nickel sulfate procedure is reduced, and the operation cost is reduced.
Description
Technical field
The present invention relates to a kind of method of purifying electrolysis liquid, particularly a kind of method purifying waste copper sulfate electrolyte liquid.
Background technology
Removing the process of excess copper and other impurity in copper electrolyte, is the important component part of modern copper electrolyzing refining flow process.In copper electrolytic process, the copper in positive plate and arsenic impurities, antimony, bismuth constantly dissolve and accumulate in the electrolytic solution, after arsenic impurities, antimony, bismuth enter copper electrolyte, and As
3+and Sb
3+the O in electrolytic solution can be dissolved in gradually
2be oxidized to As
5+and Sb
5+, but As
3+oxidation rate comparatively Sb
3+oxidation rate faster, therefore under normal circumstances, the arsenic 90-95% in copper electrolyte is with As
5+form exist, antimony more than 90% is then with Sb
3+form exist.Bismuth in copper electrolyte without variation of valence, all with Bi
3+form exist.Due to the deposition potential of these impurity and the deposition potential of copper close, when arsenic impurities, antimony, bismuth run up to a certain degree in electrolytic solution, will separate out on negative electrode together with copper, affect the quality of cathode copper.For making each component content ratio in electrolytic solution keep within the limits prescribed, guaranteeing electrolytic copper quality product, regularly must quantitatively extract part electrolytic solution and carrying out purifying treatment, then returning electrolysis production system.The mode of the main employing copper stripping electrolysis of current cleaning copper electrolyte.
The principle of copper stripping electrolysis is under direct current effect, the excess copper in removing circular electrolyte and the process of other impurity.Anode material used is lead base silver (antimony) alloy, and negative electrode is copper.Main electrochemical reaction is:
CuSO
4+H
2O==Cu+H
2SO
4+1/2O
2
Lead based alloy anodes plate in sulfuric acid electrolytic solution during electrolysis, at the Pb that anode discharge generates
2+very easily be oxidized to Pb
4+, when the vitriol of the latter is hydrolyzed, generate PbO
2, this oxidate forms the fine and close protective membrane of one deck on the anode surface, makes lead based alloy anodes become insoluble anode.Cu in solution
2+concentration is along with Cu
2+continuous precipitation on negative electrode, and decline gradually.When dropping to finite concentration, the impurity such as the arsenic in solution, antimony, bismuth also can be separated out and remove from copper electrolyte on negative electrode.
Two sections of electrodeposition decopper(ing) methods are mainly taked in current traditional waste electrolyte purification, and first paragraph waste electrolyte (Cu: about 50g/L) enters parallel electrolytic groove and carries out electrolysis, and electrolytic solution Cu concentration is less than 18g/L and enters second segment operation; Second segment adopts series connection staged electrolyzer to carry out revulsion decopper(ing) removing impurities, and when Cu concentration is less than 5g/L, the whole liquid of decopper(ing) removing impurities electrodeposition returns copper electrolyzing refining system after the purification of nickel removal operation.In traditional copper stripping electrolysis method, often foreign matter content is higher more backward for first paragraph parallel electrolytic groove output negative plate, and in waste electrolyte, the copper of about 64% is converted into black copper plate, and can not reach cathode copper standard, added value is low; Second segment series connection staged electrolyzer then mainly produces black copper powder, and in waste electrolyte, the copper of about 26% is converted into black copper powder.Traditional copper stripping electrolysis method arsenic, antimony, bismuth decreasing ratio are about 55%, 73%, 79%, and output black copper plate (or black copper powder) copper arsenic ratio is about 6.6.
Summary of the invention
The object of the invention is to overcome traditional waste electrolyte purification decopper(ing) efficiency not high, the method for the purification waste copper sulfate electrolyte liquid that a kind of method is simple, decopper(ing) removing impurities efficiency is high, running cost is low is provided.
A kind of method purifying waste copper sulfate electrolyte liquid of the present invention, adopts following step to be achieved:
Step 1, waste electrolyte evaporation concentration, crystallisation by cooling and heavy molten operation: in the temporary storage tank of waste copper sulfate electrolyte liquid waste copper sulfate electrolyte liquid through 3# header tank to evaporating kettle, by the evaporation concentration under the condition of vacuum of the waste copper sulfate electrolyte liquid in evaporating kettle, to decrystallize still crystallisation by cooling through concentrated waste copper sulfate electrolyte liquid, gained slurry carries out solid-liquor separation through filter, wherein the thick copper sulfate of gained delivers to 1# header tank after weight fluid bowl is heavily molten, and gained cupric sulphate crystal mother liquor is through being pumped to 2# header tank; In an electrodeposition fluid infusion groove, the replenisher of sulfuric acid concentration >=180g/L directly removes 1# header tank;
Step 2, an electrodeposition decopper(ing) operation: above-mentioned through heavy fluid bowl heavy molten after deliver to thick copper sulfate in 1# header tank and after 1# header tank mixes, enter an electrodeposition decopper(ing) system from the replenisher in an electrodeposition fluid infusion groove and carry out an electrodeposition decopper(ing), gained electro deposited copper enters copper and collects storehouse, decopper(ing) liquid is through a Lower tank part through pumping into heavy fluid bowl, and another part returns rectification systems;
Step 3, crystalline mother solution secondary electrodeposition decopper(ing) operation: gained stores up the cupric sulphate crystal mother liquor in 2# header tank (5) temporarily in step one, enter secondary electrodeposition decopper(ing) system (6) and carry out secondary electrodeposition decopper(ing), the black copper plate of gained removes smelting system, and the whole liquid of secondary decopper(ing) of gained enters nickel removal operation (8) through Lower tank (7) and reclaims nickel;
Adopt the method for above-mentioned purification waste copper sulfate electrolyte liquid, the operating pressure of evaporating kettle described in step 1 is-70KPa, and working temperature is 80 ~ 90 DEG C; The density of the waste copper sulfate electrolyte liquid after gained concentrates is: 1.204 ~ 1.208kg/m
3; Filter in step 1 is belt vacuum filter; Filter in step 1 is belt vacuum filter, and wherein the operating pressure of belt vacuum filter is vacuum tightness 0.053MPa.
As a further improvement on the present invention, the replenisher in an electrodeposition fluid infusion groove be one in the copper-bath or dilution heat of sulfuric acid that storage tank composition temporary with waste copper sulfate electrolyte liquid is identical or its combine.The copper-bath that preferably storage tank composition temporary with waste copper sulfate electrolyte liquid is identical.
As the preferred technical solution of the present invention, an electrodeposition decopper(ing) system in the step 2 of technique scheme is adopted to comprise well heater, header tank and a cuprum-doffing electrolytic tank, wherein: through heavy fluid bowl heavy molten after deliver to thick copper sulfate in 1# header tank and after 1# header tank mixes, enter heater heats from the replenisher in an electrodeposition fluid infusion groove after enter header tank, from inflow cuprum-doffing electrolytic tank, carry out an electrodeposition decopper(ing).
As a further improvement on the present invention, the secondary electrodeposition system in the step 3 of technique scheme is adopted to comprise well heater, main and auxiliary liquid feeder and secondary cuprum-doffing electrolytic tank, successively main and auxiliary liquid feeder is entered successively after wherein entering heater heats from the cupric sulphate crystal mother liquor in 2# header tank, secondary cuprum-doffing electrolytic tank, wherein secondary cuprum-doffing electrolytic tank carries out revulsion decopper(ing) removing impurities according to main and auxiliary liquid feeder to liquid measure.
As a further improvement on the present invention, the secondary electrodeposition decopper(ing) system in the step 3 of technique scheme is adopted to comprise well heater, main and auxiliary liquid feeder and secondary cuprum-doffing electrolytic tank, successively main and auxiliary liquid feeder is entered successively after wherein entering heater heats from the cupric sulphate crystal mother liquor in 2# header tank, secondary cuprum-doffing electrolytic tank, described secondary cuprum-doffing electrolytic tank carries out revulsion decopper(ing) removing impurities according to main and auxiliary liquid feeder to liquid measure.
The nickel removal operation in the step 3 of technique scheme is adopted to comprise freezing and crystallizing groove and pressure filter, wherein: the whole liquid of secondary decopper(ing) entering nickel removal operation carries out freezing and crystallizing through being pumped to freezing and crystallizing groove, the slurry of gained is pumped to pressure filter press filtration, the mother liquor of gained returns electrolytic system, the crude product single nickel salt packaging and warehousing of gained after heating.
In sum, adopt the purifying method of Waste Sulfuric Acid copper of the present invention, waste copper sulfate electrolyte liquid passes through condensing crystal, by impurity enriched in secondary electric effusion, copper sulfate is moltenly mixed with an electric effusion with the replenisher of sulfuric acid concentration >=180g/L through overweight, one section of whole output criteria cathode copper of electrodeposition can be reached, account for more than 65% of waste electrolyte decopper(ing) total amount, and pass through evaporation concentration, the liquor capacity of secondary electrodeposition decopper(ing) is reduced, decrease the treatment capacity of single nickel salt operation, reduce running cost.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention;
In figure, the temporary storage tank of 1 waste copper sulfate electrolyte liquid; 2 3# header tanks; 3 evaporating kettles; 4 filters; 5 2# header tanks; 6 two electrodeposition decopper(ing) systems; 7 2# Lower tanks; 8 nickel removal operations; 9 heavy fluid bowls; 10 electrodeposition decopper(ing) systems; 11 1# Lower tanks; 12 rectification systems; 13 crystallization kettles; 14 1# header tanks; 15 bronze medals collect storehouse; 16 electrodeposition fluid infusion grooves.
Embodiment
Below in conjunction with embodiment, the present invention will be further described:
The waste copper sulfate electrolyte liquid amount that this example evaporation concentration adopts is 154m
3, wherein in solution, the mass body volume concentrations of main component is respectively: Cu:49g/L, H
2sO
4: 180 g/L, As:8 g/L, Sb:0.5 g/L, Bi:0.5 g/L, Ni:15 g/L.
Embodiment one:
154 m3 waste copper sulfate electrolyte liquids are pumped in the temporary storage tank 1 of waste copper sulfate electrolyte liquid, and to be controlled in the waste copper sulfate electrolyte liquid in temporary for a part of waste copper sulfate electrolyte liquid storage tank 1 in 2h through 3# header tank 2 from flowing into enamel evaporating kettle 3, the vacuum in evaporating kettle 3 is made to maintain-70KPa by hydraulic ejector, the temperature controlled in evaporating kettle 3 is 87 DEG C and carries out vacuum evaporation 16h, wherein evaporated water 70m
3, the density of the waste copper sulfate electrolyte liquid after concentrated is: 1.206kg/m
3.4 10m are discharged to after concentrated end
3stainless steel crystallization kettle 13, blowing time 2h, through crystallisation by cooling 10h, slurry carries out solid-liquor separation through belt vacuum filter 4 under vacuum tightness 0.053MPa, obtains thick copper sulfate 21387kg(Cu:23.5%), cupric sulphate crystal mother liquor 84 m
3(Cu:30g/L, H
2sO
4: 330 g/L, As:14.67g/L, Sb:0.92 g/L, Bi:0.92 g/L, Ni:27.5 g/L.) enter 2# header tank 5.One time electrodeposition fluid infusion groove 16 supplies 102.6m in 1# header tank 14
3, H
2sO
4concentration is the dilute sulphuric acid of 220 g/L, the thick copper sulfate of 21387kg with electrodeposition circulation fluid heavy molten after add in an electrodeposition decopper(ing) system 10, one time electric effusion enters heavy fluid bowl 9 after being pumped to heater heats, from inflow cuprum-doffing electrolytic tank, carry out an electrodeposition decopper(ing), output meets the electro deposited copper warehouse-in of GB/T 467-1997 standard, liquid (Cu:0.5 g/L, H after a decopper(ing)
2sO
4: 250 g/L) part circulates, and part open circuit returns electrolytic system.Enter secondary electrodeposition decopper(ing) system 6 from the cupric sulphate crystal mother liquor in 2# header tank 5 and carry out decopper(ing) removal of impurities: the cupric sulphate crystal mother liquor in 2# header tank 5 through be pumped to heater heats laggard enter main and auxiliary liquid feeder, by flowing automatically into secondary cuprum-doffing electrolytic tank to liquid measure, carry out revulsion decopper(ing) removing impurities, 84 m overflowed
3(wherein the content of main component is the whole liquid of secondary decopper(ing): Cu:0.5g/L, H
2sO
4: 375 g/L, As:5.13g/L, Sb:0.14 g/L, Bi:0.14g/L, Ni:27.5 g/L) from flowing into the whole liquid bath of secondary decopper(ing), 53 m
3the whole liquid of secondary decopper(ing) send nickel removal operation 8 to reclaim nickel, and all the other return electrolytic system.(wherein the content of main component is Cu:60% to the black copper plate of secondary decopper(ing) output, As:15.5 %, Sb:1.26%, Bi:1.26%) packing Returning smelting system, when going out groove, supernatant liquor and black copper mud stream are to black copper mud storage tank, and be pumped to pressure filter press filtration, filtrate returns secondary cuprum-doffing electrolytic tank, filter cake (i.e. black copper powder, composition is with black copper plate) Returning smelting system.Freezing and crystallizing groove delivered to by the whole liquid pump of secondary decopper(ing) entered except nickel operation, and carry out freezing and crystallizing, crystallization terminates post crystallization slurry pumping to pressure filter press filtration, and (wherein the content of main component is Cu:0.56%, H for filtrate and single nickel salt crystalline mother solution
2sO
4: 375 g/L, As:5.75 g/L, Sb:0.16 g/L, Bi:0.16g/L, Ni:12.4%) after heating, return electrolytic system, filter cake (i.e. crude nickle sulphate, Ni:18%) packaging and warehousing.
As calculated wherein, the decreasing ratio of arsenic, antimony, bismuth is respectively 65%, 85% and 85%.Producing standard cathode copper amount is 66.6% of decopper(ing) total amount.
Embodiment two:
In the present embodiment, flow process and embodiment one is identical, and difference is the amount that electrodeposition fluid infusion groove 16 supplies 1# header tank 14 is 125 m
3its composition is the same with the moiety of the waste copper sulfate electrolyte liquid in the temporary storage tank of waste copper sulfate electrolyte liquid 1, and (namely wherein the content of the main component of waste copper sulfate electrolyte liquid is: Cu:49g/L, H
2sO
4: 180 g/L, As:8 g/L, Sb:0.5 g/L, Bi:0.5 g/L, Ni:15 g/L), the thick copper sulfate of 21387kg with electrodeposition circulation fluid heavy molten after add in an electrodeposition decopper(ing) system 10, one time electric effusion enters header tank after being pumped to heater heats, from flowing into a cuprum-doffing electrolytic tank, carry out an electrodeposition decopper(ing), output meets GB/T 467-1997 standard electro deposited copper warehouse-in, liquid (Cu:35 g/L, H after a decopper(ing)
2sO
4: 263 g/L, As:8g/L, Sb:0.5 g/L, Bi:0.5 g/L, Ni:15 g/L) part circulates, and part open circuit returns electrolytic system.
As calculated wherein, the decreasing ratio of arsenic, antimony, bismuth is respectively 65%, 85% and 85%.Producing standard cathode copper amount is 73.5% of decopper(ing) total amount.
Claims (9)
1. purify a method for waste copper sulfate electrolyte liquid, it is characterized in that adopting following steps:
Step 1, waste electrolyte evaporation concentration, crystallisation by cooling and heavy molten operation: in the temporary storage tank of waste copper sulfate electrolyte liquid (1) waste copper sulfate electrolyte liquid through 3# header tank (2) to evaporating kettle (3), by the evaporation concentration under the condition of vacuum of the waste copper sulfate electrolyte liquid in evaporating kettle (3), to decrystallize still (13) crystallisation by cooling through concentrated waste copper sulfate electrolyte liquid, gained slurry carries out solid-liquor separation through filter (4), wherein the thick copper sulfate of gained delivers to 1# header tank (14) after weight fluid bowl (9) is heavily molten, gained cupric sulphate crystal mother liquor is through being pumped to 2# header tank (5),
In an electrodeposition fluid infusion groove (16), the replenisher of sulfuric acid concentration >=180g/L directly removes 1# header tank (14);
Step 2, an electrodeposition decopper(ing) operation: above-mentioned through heavy fluid bowl (9) heavy molten after deliver to thick copper sulfate in 1# header tank (14) and after 1# header tank (14) mixes, enter an electrodeposition decopper(ing) system (10) from the replenisher in an electrodeposition fluid infusion groove (16) and carry out an electrodeposition decopper(ing), gained electro deposited copper enters copper and collects storehouse (15), decopper(ing) liquid is through Lower tank (11) part through pumping into heavy fluid bowl (9), and another part returns rectification systems (12);
Step 3, crystalline mother solution secondary electrodeposition decopper(ing) operation: gained stores up the cupric sulphate crystal mother liquor in 2# header tank (5) temporarily in step one, enter secondary electrodeposition decopper(ing) system (6) and carry out secondary electrodeposition decopper(ing), the black copper plate of gained removes smelting system, and the whole liquid of secondary decopper(ing) of gained enters nickel removal operation (8) through Lower tank (7) and reclaims nickel.
2. a kind of method purifying waste copper sulfate electrolyte liquid according to claim 1, it is characterized in that the operating pressure of evaporating kettle described in step 1 (3) is for-70KPa, working temperature is 80 ~ 90 DEG C.
3. a kind of method purifying waste copper sulfate electrolyte liquid according to claim 1, it is characterized in that gained described in step 1 concentrate after the density of waste copper sulfate electrolyte liquid be 1.204 ~ 1.208kg/m
3.
4. a kind of method purifying waste copper sulfate electrolyte liquid according to claim 1, is characterized in that the filter (4) in described step 1 is belt vacuum filter.
5. a kind of method purifying waste copper sulfate electrolyte liquid according to claim 4, is characterized in that the operating pressure of described belt vacuum filter is 0.053MPa.
6. a kind of method purifying waste copper sulfate electrolyte liquid according to claim 1, the replenisher that it is characterized in that in an electrodeposition fluid infusion groove (16) be one in the copper-bath or dilution heat of sulfuric acid that storage tank composition temporary with waste copper sulfate electrolyte liquid is identical or its combine.
7. a kind of method purifying waste copper sulfate electrolyte liquid according to claim 1, it is characterized in that an electrodeposition decopper(ing) system (10) in described step 2 comprises well heater, header tank and a cuprum-doffing electrolytic tank, wherein: through heavy fluid bowl (9) heavy molten after deliver to thick copper sulfate in 1# header tank (14) and after 1# header tank (14) mixes, enter heater heats from the replenisher in an electrodeposition fluid infusion groove (16) after enter header tank, from inflow cuprum-doffing electrolytic tank, carry out an electrodeposition decopper(ing).
8. a kind of method purifying waste copper sulfate electrolyte liquid according to claim 1, it is characterized in that secondary electrodeposition decopper(ing) system (6) in described step 3 comprises well heater, main and auxiliary liquid feeder and secondary cuprum-doffing electrolytic tank, successively main and auxiliary liquid feeder is entered successively after wherein entering heater heats from the cupric sulphate crystal mother liquor in 2# header tank (5), secondary cuprum-doffing electrolytic tank, described secondary cuprum-doffing electrolytic tank carries out revulsion decopper(ing) removing impurities according to main and auxiliary liquid feeder to liquid measure.
9. a kind of method purifying waste copper sulfate electrolyte liquid according to claim 1, it is characterized in that the nickel removal operation (8) in described step 3 comprises freezing and crystallizing groove and pressure filter, wherein: the whole liquid of secondary decopper(ing) entering nickel removal operation carries out freezing and crystallizing through being pumped to freezing and crystallizing groove, the slurry of gained is pumped to pressure filter press filtration, the mother liquor of gained returns electrolytic system, the crude product single nickel salt packaging and warehousing of gained after heating.
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Cited By (13)
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| CN105463490A (en) * | 2015-12-23 | 2016-04-06 | 无锡市瑞思科环保科技有限公司 | Method for reclaiming copper and recycling sulfuric acid through copper pipe pickling wastewater |
| CN105921075A (en) * | 2016-06-17 | 2016-09-07 | 张家港联合铜业有限公司 | Automatic fluid supplementing structure for reaction kettle |
| CN105970249A (en) * | 2016-07-11 | 2016-09-28 | 铜陵有色金属集团股份有限公司金冠铜业分公司 | Electrodeposition purification system of copper electrolysis waste liquid and purification method thereof |
| CN106435654A (en) * | 2016-08-31 | 2017-02-22 | 河南豫光金铅股份有限公司 | Elimination method for cathode plate copper liquid level line white crystals in copper electrolytic refining |
| CN106521184A (en) * | 2016-11-04 | 2017-03-22 | 金少平 | Process for extracting copper sulfate through waste copper scraps |
| CN108408759A (en) * | 2018-04-02 | 2018-08-17 | 深圳市星河环境技术有限公司 | A kind of copper sulphate mother liquor purification recrystallization system and method |
| CN108546963A (en) * | 2018-05-31 | 2018-09-18 | 西北矿冶研究院 | Method for improving purification efficiency of copper electrolyte |
| CN109536992A (en) * | 2019-02-01 | 2019-03-29 | 阳谷祥光铜业有限公司 | A kind of method of two de- two products purifying copper electrolytes |
| CN109628956A (en) * | 2019-03-01 | 2019-04-16 | 阳谷祥光铜业有限公司 | A kind of preparation method and device of tough cathode |
| CN109957815A (en) * | 2017-12-22 | 2019-07-02 | 中国瑞林工程技术有限公司 | The purification method of copper electrolyte |
| CN110724977A (en) * | 2019-11-05 | 2020-01-24 | 杭州美时美刻物联网科技有限公司 | Electrolytic copper waste liquid regeneration and reuse treatment system |
| CN110938842A (en) * | 2019-12-06 | 2020-03-31 | 中国瑞林工程技术股份有限公司 | Copper electrolyte purification method |
| CN112725844A (en) * | 2020-12-21 | 2021-04-30 | 万载志成实业有限公司 | Electrolyte purification method for electrolytic copper production process |
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| CN105463490A (en) * | 2015-12-23 | 2016-04-06 | 无锡市瑞思科环保科技有限公司 | Method for reclaiming copper and recycling sulfuric acid through copper pipe pickling wastewater |
| CN105921075A (en) * | 2016-06-17 | 2016-09-07 | 张家港联合铜业有限公司 | Automatic fluid supplementing structure for reaction kettle |
| CN105970249A (en) * | 2016-07-11 | 2016-09-28 | 铜陵有色金属集团股份有限公司金冠铜业分公司 | Electrodeposition purification system of copper electrolysis waste liquid and purification method thereof |
| CN105970249B (en) * | 2016-07-11 | 2018-01-09 | 铜陵有色金属集团股份有限公司金冠铜业分公司 | The electrodeposition cleaning system and its purification method of waste solution of copper electrolysis |
| CN106435654A (en) * | 2016-08-31 | 2017-02-22 | 河南豫光金铅股份有限公司 | Elimination method for cathode plate copper liquid level line white crystals in copper electrolytic refining |
| CN106521184A (en) * | 2016-11-04 | 2017-03-22 | 金少平 | Process for extracting copper sulfate through waste copper scraps |
| CN109957815A (en) * | 2017-12-22 | 2019-07-02 | 中国瑞林工程技术有限公司 | The purification method of copper electrolyte |
| CN108408759A (en) * | 2018-04-02 | 2018-08-17 | 深圳市星河环境技术有限公司 | A kind of copper sulphate mother liquor purification recrystallization system and method |
| CN108408759B (en) * | 2018-04-02 | 2024-03-12 | 深圳星河环境股份有限公司 | Copper sulfate mother liquor purifying and recrystallizing system and method |
| CN108546963A (en) * | 2018-05-31 | 2018-09-18 | 西北矿冶研究院 | Method for improving purification efficiency of copper electrolyte |
| CN109536992A (en) * | 2019-02-01 | 2019-03-29 | 阳谷祥光铜业有限公司 | A kind of method of two de- two products purifying copper electrolytes |
| CN109628956A (en) * | 2019-03-01 | 2019-04-16 | 阳谷祥光铜业有限公司 | A kind of preparation method and device of tough cathode |
| CN110724977A (en) * | 2019-11-05 | 2020-01-24 | 杭州美时美刻物联网科技有限公司 | Electrolytic copper waste liquid regeneration and reuse treatment system |
| CN110938842A (en) * | 2019-12-06 | 2020-03-31 | 中国瑞林工程技术股份有限公司 | Copper electrolyte purification method |
| CN112725844A (en) * | 2020-12-21 | 2021-04-30 | 万载志成实业有限公司 | Electrolyte purification method for electrolytic copper production process |
| CN112725844B (en) * | 2020-12-21 | 2023-04-07 | 万载志成实业有限公司 | Electrolyte purification method for electrolytic copper production process |
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