CN1307107C - Method for producing cuprous chloride by using waste copper chloride etching plate liquid - Google Patents
Method for producing cuprous chloride by using waste copper chloride etching plate liquid Download PDFInfo
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- CN1307107C CN1307107C CNB2005100390770A CN200510039077A CN1307107C CN 1307107 C CN1307107 C CN 1307107C CN B2005100390770 A CNB2005100390770 A CN B2005100390770A CN 200510039077 A CN200510039077 A CN 200510039077A CN 1307107 C CN1307107 C CN 1307107C
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 66
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 title claims abstract description 50
- 238000005530 etching Methods 0.000 title claims abstract description 44
- 239000007788 liquid Substances 0.000 title claims abstract description 38
- 229910021591 Copper(I) chloride Inorganic materials 0.000 title claims abstract description 37
- 229940045803 cuprous chloride Drugs 0.000 title claims abstract description 37
- 239000002699 waste material Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000012452 mother liquor Substances 0.000 claims abstract description 22
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- 229960003280 cupric chloride Drugs 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 16
- 239000012530 fluid Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000010802 sludge Substances 0.000 claims description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- 229960004643 cupric oxide Drugs 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 2
- 238000000247 postprecipitation Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 4
- 239000005751 Copper oxide Substances 0.000 abstract 2
- 229910000431 copper oxide Inorganic materials 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000013872 defecation Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
A method for producing cuprous chloride by using waste copper chloride etching plate liquid comprises the following steps (1) adding copper oxide into the waste copper chloride etching plate liquid; (2) filtering the solution; (3) heating the clarified solution to 70-80 ℃, stirring the clarified solution under the condition of keeping the temperature, and introducing sulfur dioxide gas into the clarified solution; (4) cooling the solution and filtering the precipitated crystals from said mother liquor; (5) and washing the filtered crystal by using dilute hydrochloric acid and ethanol in sequence, and drying the crystal to obtain cuprous chloride. The method uses the waste copper chloride etching solution and copper oxide to generate cuprous chloride, and has the advantages of simple and stable process, high yield and no secondary pollution.
Description
Technical field
The present invention relates to a kind of treatment process of useless cupric chloride etching liquid, refer in particular to the method for utilizing producing cuprous chloride form deposed copper chloride fluid of etching board.
Background technology
Existing useless cupric chloride etching liquid has four kinds of treatment processs usually: a kind of is to displace copper powder with useless cupric chloride etching liquid and scrap iron; Second kind is that useless cupric chloride etching liquid and cuprammonium etching liquid are used simultaneously, produces copper sulfate; The third is to produce copper chloride dihydrate with useless cupric chloride etching liquid direct evaporation condensing crystal; The 4th kind is to produce cuprous chloride with copper powder reduction cupric chloride etching liquid.First kind is direct, the simplest treatment process, but of poor benefits, owing to contain a large amount of hydrochloric acid in the waste liquid, has wasted a considerable amount of iron, causes serious waste; Second kind is with two kinds of waste liquid combination treatment, but products obtained therefrom purity is low, and processing costs is higher; The third power consumption in concentration process is big, and the volatilization of a large amount of hydrochloric acid is arranged, not only contaminate environment but also cause damage, and also the market demand of gained copper chloride dihydrate is few; The 4th kind as described in the patent 94113822.4, to give up earlier cupric chloride etching liquid and scrap iron direct replaceed copper powder, add water then and fall acid and purification, the gained copper powder generates cuprous chloride with the reaction of cupric chloride etching liquid again, owing in the process that generates copper powder, need a large amount of water, add hydrolysis cuprous chloride complexation thing and also need the water of 4-6 times of volume, cause water resources consumption very big, and a large amount of iron content waste liquids that produce in this process have increased the weight of the burden of environmental protection treatment.
Japanese Patent J56155020-A discloses a kind of production method of Red copper oxide, its content is: when copper chloride solution is corroded the processing copper coin, the waste liquid of discharging changes into the cuprous chloride aqueous solution, again with this aqueous solution and alkaline solution while injecting reactor kind, be that reaction generates Red copper oxide under the condition of 8.5-12.5 in the pH value, this method comprises a plurality of steps, wherein related to of the conversion of useless cupric chloride etching liquid to cuprous chloride, but cuprous chloride exists with the complex state form, if expect the cuprous chloride product, also need a large amount of water, its complex steps has caused the wasting of resources again.
Summary of the invention
The object of the invention provides a kind of method with producing cuprous chloride form deposed copper chloride fluid of etching board, its technology simple and stable, yield height.
Technical scheme of the present invention is: a kind of method with producing cuprous chloride form deposed copper chloride fluid of etching board, it comprises the steps:
(1), in useless cupric chloride etching liquid, add cupric oxide, the pH value of regulator solution is to 1-1.5;
(2), filtering solution, remove insoluble substance, obtain settled solution;
(3), settled solution is heated to 70 ℃-80 ℃, under the condition that keeps temperature, stir settled solution, and in this settled solution, feed sulfur dioxide gas, when solution becomes light brown by green, stop logical sulfur dioxide gas, obtain mother liquor;
(4), cool off described mother liquor, sedimentary crystallization is filtered out from cooled mother liquor;
(5), with the crystallization that dilute hydrochloric acid, ethanol washing and filtering successively go out, after the dry described crystallization, obtain cuprous chloride.
The present invention compared with prior art, has following advantage: generate cuprous chloride with useless cupric chloride etching liquid and cupric oxide, its technology simple and stable, yield height, do not produce secondary pollution, not only can solve the difficulty of handling etching waste liquor, also can save copper resource and water resources, the more important thing is and to reduce the harm that copper causes physical environment.After measured in the cuprous chloride product of producing according to present method, the weight ratio of pure cuprous chloride 〉=98%, the weight ratio of high mantoquita≤1%, the weight ratio of acid non-soluble substance≤0.1%, the weight ratio of iron≤0.005%, the weight ratio of vitriol≤0.3%.
Embodiment
A kind of method with producing cuprous chloride form deposed copper chloride fluid of etching board, it comprises the steps:
(1), in useless cupric chloride etching liquid, add cupric oxide, the amount of the cupric oxide of adding should make it be enough to form insoluble substance in useless cupric chloride etching liquid, and the cupric oxide that adds is the oxidation copper sludge, and the pH value of regulator solution is to 1-1.5;
(2), filtering solution, remove insoluble substance, obtain settled solution;
(3), settled solution is heated to 70 ℃-80 ℃, under the condition that keeps temperature, stir settled solution, and in this settled solution, feed sulfur dioxide gas, when solution becomes light brown by green, stop logical sulfur dioxide gas, obtain mother liquor, the sulfur trioxide gas body and function sodium carbonate solution of generation absorbs sulfur trioxide gas, can obtain byproduct sulfite solution;
(4), cool off described mother liquor, sedimentary crystallization is filtered out from cooled mother liquor, drop into sodium hydroxide in the mother liquor after filtering, the reaction postprecipitation obtains copper, behind the useless cupric chloride etching liquid of the copper input that obtains, reenters step (1);
(5), the crystallization that goes out with dilute hydrochloric acid, ethanol washing and filtering successively, crystallize to 80 ℃-110 ℃ behind the heated scrub, and after 15-25 minute drying of insulation, obtain cuprous chloride, the waste liquid of gained is after lime dehydration and distillation behind the washing with alcohol crystallisate, regeneration ethanol.
In step (1) afterwards, measure cupric ion proportion in solution,, when copper ion concentration reaches the 115-130 grams per liter, enter step (2) again if copper ion concentration less than 115 grams per liters, then should add hydrochloric acid and repeating step (1) in solution.
Produce cuprous chloride with useless cupric chloride etching liquid and oxidation copper sludge, waste recycling, its process stabilizing, yield height, do not produce secondary pollution, not only can solve the difficulty of handling etching waste liquor, promote the development of electronic circuit board industry, also can save a large amount of copper resources, and reduce the harm of copper to environment structure, its economic benefit height can be saved the useless required fund that expends of cupric chloride etching liquid of handling.Below enumerate several embodiment and specify present method:
Embodiment 1
The useless cupric chloride etching liquid of will originating is regulated pH value to 1 with the copper that produces in oxidation copper sludge or the above-mentioned steps (4), measuring copper ion concentration is 115 grams per liters, remove by filter insoluble substance, adding hot filtrate to 70 ℃ constant temperature stirs, in filtrate, feed sulfur dioxide gas continuously, control sulfurous gas storage pressure is 0.02Mpa, after 35 minutes, solution becomes light brown by green, stop logical sulfur dioxide gas, make the solution cooling form crystallization and mother liquor, the sulfur trioxide gas that is produced absorbs through sodium carbonate solution, obtains byproduct sulfite solution.
Filter, separate cuprous chloride crystallization and mother liquor, the cuprous chloride crystallization under 80 ℃ of temperature dry 25 minutes, packs after the dilute hydrochloric acid of pH=1 and ethanol wash respectively then.Waste liquid after mother liquor and the crystallization of dilute hydrochloric acid washing cuprous chloride merges, and with the sodium hydroxide neutralization, the copper sludge of generation can drop in the useless cupric chloride etching liquid and be back to production.Waste liquid behind the washing with alcohol cuprous chloride crystal is collected the ethanol of regeneration to be back to production after lime dehydration and distillation.
Embodiment 2
The useless cupric chloride etching liquid of will originating is regulated pH value to 1.5 with the oxidation copper sludge, and measuring copper ion concentration is 120 grams per liters, and filtering and impurity removing obtains settled solution.The settled solution that obtains is heated to 73 ℃ of constant temperature to be stirred, in settled solution, feed sulfur dioxide gas continuously, control sulfurous gas storage pressure is 0.03Mpa, after 30 minutes, solution becomes yellow by green, stops logical sulfur dioxide gas, and stirred solution and cooling back form cuprous chloride crystallization and mother liquor, the sulfur trioxide gas body and function sodium carbonate solution that produces in this process absorbs, and obtains byproduct sulfite solution.
Filter, separate cuprous chloride crystallization and mother liquor, the cuprous chloride crystallization is after the dilute hydrochloric acid of pH=1 and ethanol wash respectively, drying is 20 minutes under 90 ℃ of temperature, pack then, mother liquor then with the crystallization of dilute hydrochloric acid washing cuprous chloride after waste liquid merge, with the sodium hydroxide neutralization, sedimentary copper sludge can be back to production.Waste liquid after the crystallization of washing with alcohol cuprous chloride is after lime dehydration and distillation, and the ethanol of regeneration can be back to production.
Embodiment 3
The useless cupric chloride etching liquid of will originating is regulated pH value to 1 with the copper sludge that produces in oxidation copper sludge and the above-mentioned steps (4), and measuring copper ion concentration is 125 grams per liters, removes by filter insoluble substance, obtains clear filtrate.Constant temperature stirs after the hot defecation filtrate to 75 ℃, in clear filtrate, feed sulfur dioxide gas continuously, control sulfurous gas storage pressure is 0.04Mpa, after 35 minutes, solution becomes light brown by green, stops logical sulfur dioxide gas, cooling solution, obtain mother liquor and the cuprous chloride crystallization that is deposited in the mother liquor, the sulfur trioxide gas body and function sodium carbonate solution that produces in this process absorbs, and obtains byproduct sulfite solution.
Filter, after the cuprous chloride crystallization that obtains was washed respectively with the dilute hydrochloric acid of pH=2 and ethanol, dry cuprous chloride crystallization was 15 minutes under 100 ℃ temperature condition, and the cuprous chloride with gained packs then.
Other step is identical with embodiment 1.
Embodiment 4
The useless cupric chloride etching liquid of will originating is regulated pH value to 1.5 with the copper sludge that produces in oxidation copper sludge and the above-mentioned steps (4), and measuring copper ion concentration is 130 grams per liters, removes by filter insoluble substance.Constant temperature stirred after the filtrate that obtains was heated to 80 ℃, in this filtrate, feed sulfur dioxide gas continuously, control sulfurous gas storage pressure is 0.05Mpa, after 30 minutes, solution becomes light brown by green, stops logical sulfur dioxide gas, cool off amber solution, obtain mother liquor and the cuprous chloride crystallization that is deposited in the mother liquor, the sulfur trioxide gas body and function sodium carbonate solution that produces in this process absorbs, and obtains byproduct sulfite solution.
Filter to isolate the cuprous chloride crystallization, wash the cuprous chloride crystallization respectively with dilute hydrochloric acid and the ethanol of pH=2.5, dry cuprous chloride crystallization 15 minutes under 105 ℃ of temperature condition then packs the cuprous chloride that obtains.
Other step is identical with embodiment 1.
Claims (8)
1, a kind of method with producing cuprous chloride form deposed copper chloride fluid of etching board, it is characterized in that: it comprises the steps:
(1), in useless cupric chloride etching liquid, add cupric oxide, the pH value of regulator solution is to 1-1.5;
(2), filtering solution, remove insoluble substance, obtain settled solution;
(3), settled solution is heated to 70 ℃-80 ℃, under the condition that keeps temperature, stir settled solution, and in this settled solution, feed sulfur dioxide gas, when solution becomes light brown by green, stop logical sulfur dioxide gas, obtain mother liquor;
(4), cool off described mother liquor, sedimentary crystallization is filtered out from cooled mother liquor;
(5), with the crystallization that dilute hydrochloric acid, ethanol washing and filtering successively go out, after the dry described crystallization, obtain cuprous chloride.
2, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1, it is characterized in that: in step (1), the amount of the cupric oxide of adding should make it be enough to form insoluble substance in useless cupric chloride etching liquid.
3, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1, it is characterized in that: afterwards in step (1), measure cupric ion proportion in solution, if copper ion concentration is less than 115 grams per liters, then should in solution, add hydrochloric acid and repeating step (1), when copper ion concentration reaches the 115-130 grams per liter, enter step (2) again.
4, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1, it is characterized in that: in step (1), the cupric oxide of adding is the oxidation copper sludge.
5, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1, it is characterized in that: produce sulfur trioxide gas after in settled solution, feeding sulfur dioxide gas in the step (3), absorb sulfur trioxide gas with sodium carbonate solution, obtain byproduct sulfite solution.
6, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1, it is characterized in that: drop into sodium hydroxide in the mother liquor after in step (4), filtering, the reaction postprecipitation obtains copper, behind the useless cupric chloride etching liquid of the copper input that obtains, reenters step (1).
7, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1 is characterized in that: in step (5), behind the washing with alcohol crystallisate waste liquid of gained after lime dehydration and distillation, regeneration ethanol.
8, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1 is characterized in that: in step (5), crystallize to 80 ℃-110 ℃ behind the heated scrub, and after 15-25 minute drying of insulation, obtain cuprous chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100390770A CN1307107C (en) | 2005-04-21 | 2005-04-21 | Method for producing cuprous chloride by using waste copper chloride etching plate liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100390770A CN1307107C (en) | 2005-04-21 | 2005-04-21 | Method for producing cuprous chloride by using waste copper chloride etching plate liquid |
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| CN1696062A CN1696062A (en) | 2005-11-16 |
| CN1307107C true CN1307107C (en) | 2007-03-28 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415650C (en) * | 2006-08-07 | 2008-09-03 | 阮玉根 | Method for producing cuprous chloride by using copper oxychloride |
| CN104591256B (en) * | 2015-01-12 | 2017-04-05 | 广东光华科技股份有限公司 | A kind of method that cuprous oxide is prepared under copper chloride system |
| CN105016373A (en) * | 2015-08-03 | 2015-11-04 | 沈国强 | Method for producing copper chloride through waste etching liquid containing copper |
| CN105060567A (en) * | 2015-08-23 | 2015-11-18 | 长春黄金研究院 | Treating method for acid waste water containing chlorine |
| CN107740088B (en) * | 2017-09-24 | 2020-05-19 | 盐城师范学院 | Interface rapid and controllable preparation method of cuprous chloride microcrystalline material |
| CN107662939B (en) * | 2017-09-24 | 2019-08-06 | 盐城师范学院 | A kind of quick controllable method for preparing in interface of the stannous chloride nano-sheet crystals material of iron ion induction |
| CN109626411B (en) * | 2017-10-09 | 2021-06-25 | 上海集承环保技术有限公司 | Production process of anhydrous cuprous chloride |
| CN108706803A (en) * | 2018-05-08 | 2018-10-26 | 太仓市勤红防腐设备有限公司 | A kind of electronic circuit board industry wastewater treatment recovery method |
| CN111392944A (en) * | 2020-03-24 | 2020-07-10 | 宁波神化特种化学品集成有限公司 | Treatment method of cuprous cyanide production wastewater |
| CN112062148A (en) * | 2020-09-09 | 2020-12-11 | 东华大学 | Method for preparing cuprous chloride by using copper-containing sludge in electroplating circuit board wastewater |
| CN115367784A (en) * | 2022-08-20 | 2022-11-22 | 杭州富阳鸿源再生资源利用有限公司 | Method for producing cuprous chloride product by using acidic etching waste liquid |
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| CN1696062A (en) | 2005-11-16 |
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