CN1105341A - Process for producing cuprous chloride using waste etching liquid of copper chloride plate - Google Patents
Process for producing cuprous chloride using waste etching liquid of copper chloride plate Download PDFInfo
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- CN1105341A CN1105341A CN 94113822 CN94113822A CN1105341A CN 1105341 A CN1105341 A CN 1105341A CN 94113822 CN94113822 CN 94113822 CN 94113822 A CN94113822 A CN 94113822A CN 1105341 A CN1105341 A CN 1105341A
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- cuprous chloride
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Abstract
The process for producing cuprous chloride includes such technological steps as reaction of waste acidic copper chloride etching liquid on waste iron to displace out copper powder, then mixing with said etching liquid and chloride complexing agent, heating and holding temp. to generate cuprous chloride complex, addition of water for hydrolysis to generate deposition of white cuprous chloride, reducing suction filtering, washing with hydrochloric acid and then alcohol, drying and sealing package. It features high yield rate and no secondary pollution.
Description
The invention belongs to the environmental protective chemical industry field, particularly relate to a kind of method of utilizing producing cuprous chloride form deposed copper chloride fluid of etching board.
Spent acid cupric chloride etching liquid is the dense copper waste liquid that wiring board factory is produced, and to the processing of this kind waste liquid, four kinds of methods is arranged at present.First kind is to produce copper sponge with itself and scrap iron direct replacement; Second kind is that itself and cuprammonium erosion plate waste liquid are used simultaneously, produces copper sulfate; The third is to produce cupric chloride with its direct evaporation crystallization; The 4th kind is to produce cuprous chloride with itself and S-WAT reaction.
First method is direct, the simplest treatment process, but benefit is good inadequately, particularly owing to contain a large amount of hydrochloric acid in the waste liquid, consume a considerable amount of iron in vain, causes significant wastage.
Second method is two kinds of dense copper liquid combination treatment, and the treatment of wastes with processes of wastes against one another can be saved processing costs, but two kinds of waste liquid couplings must be arranged simultaneously.
The third method energy consumption in concentration process is big, and a large amount of hydrochloric acid volatilizations are arranged, and has both influenced environment, causes damage again.
The 4th kind of method has lack perfection at 2.First is because useless cupric chloride etching liquid contains a large amount of hydrochloric acid, so also during native copper, be accompanied by the side reaction of S-WAT and hydrochloric acid with S-WAT, cause S-WAT consumption excessive, and a large amount of poisonous sulfur dioxide gas generations are arranged; Second is that cuprous chloride crude product washing process uses Glacial acetic acid to make washing composition in the traditional method, and this washing composition costs an arm and a leg, and product yield is low.
Japanese Patent J56155020-A discloses a kind of production method of Red copper oxide, its content is that the waste liquid that discharges in the time of will handling copper coin with the copper chloride solution etch changes into the cuprous chloride aqueous solution, again with in this aqueous solution and the alkaline solution while injecting reactor, be to react under the condition of 8.5-12.5 at pH value, produce Red copper oxide.This patented method has related to the conversion of useless cupric chloride etching liquid to cuprous chloride, but the cuprous chloride that generates is just produced the intermediate steps of Red copper oxide, and is that form with the complex state cuprous chloride solution exists, and does not propose the finished product.
The objective of the invention is: provide a kind of new cupric chloride etching liquid that utilizes to produce the method for cuprous chloride, this method process stabilizing, yield height, the treatment of wastes with processes of wastes against one another, do not produce secondary pollution.
Technical scheme of the present invention comprises the steps:
At first displace copper powder with spent acid cupric chloride etching liquid and scrap iron reaction, copper powder is purified through the diluted acid deironing;
Made copper powder and spent acid cupric chloride etching liquid and muriate complexing agent are mixed, heating is insulation for some time also again, is become brownly by green up to solution, generates the cuprous chloride complexation thing this moment;
In described brown complex solution, add water, make described complex compound hydrolysis, generate white cuprous chloride precipitation;
Described cuprous chloride is precipitated through decompress filter, and, pack then through diluted mineral acid and washing with alcohol after drying;
The waste liquid of mother liquor after the hydrolysis of cuprous chloride complexation thing and diluted mineral acid washing cuprous chloride post precipitation merges, and displaces copper powder with iron, and copper powder is back to production; Last iron-bearing water is qualified discharge after alkali neutralization, filtration; The precipitating sludge security landfill, or produce the raw material of red iron oxide;
The waste liquid of washing with alcohol cuprous chloride post precipitation is reclaimed and reused in production through lime dehydration and distillation.
Further specify the processing condition of each step of the present invention below:
The preparation condition of copper powder:
The described useless cupric chloride etching liquid that is used to produce copper powder should towards rare be 24-30g/l to copper ion concentration.
The cuprous chloride synthetic reaction condition:
A. temperature of reaction is better in the time of 80-95 ℃, and is best in the time of 85-90 ℃.
Need when b. reacting to stir.
C. the reaction times generally at 15-35 minute better, is preferably 20-30 minute.
D. the complex compound add-on is that every liter of solution adds 0-100g.
The cuprous chloride hydrolysising condition:
The cuprous chloride complexation thing is adding under the water condition, generates the cuprous chloride precipitation through hydrolysis, and the multiple of thin up can be 4-6 times, is preferably 4-5 doubly.
Cuprous chloride washing of precipitate condition:
The used diluted mineral acid of washing cuprous chloride precipitation can be hydrochloric acid, and acidity is PH=1-2.5.
Cuprous chloride precipitation drying condition:
Bake out temperature is got 75-95 ℃ better, is preferably 80-90 ℃; Drying time is got 15-25 minute better, is preferably 15-20 minute.
The cuprous chloride production lucifuge of will trying one's best, ventilation will be got well, and the field personnel will wear masks and gloves.
Utilize the cupric chloride etching liquid to produce the method for cuprous chloride according to the present invention, process stabilizing, yield height, the treatment of wastes with processes of wastes against one another, do not produce secondary pollution.This method not only can be the difficulty of erosion plate waste liquid in circuit board plant solution place, promote the development of electronic circuit board industry, and can be country and save a large amount of copper resources, the more important thing is and to reduce the harm of copper environment structure, can be country and save the spent substantial contribution of these pollutents of harmless treatment, so social benefit also is very huge.After measured, the cuprous chloride product that the method according to this invention is produced, every index all is better than national standard, cuprous chloride content 〉=96.5% wherein, high mantoquita≤2.0%, acid non-soluble substance≤0.3%, iron≤0.005%, vitriol≤0.3%.
Embodiment 1:
It is 24g/l that spent acid cupric chloride etching liquid is diluted to copper ion concentration, and the scrap iron reaction that adds pickling displaces copper powder, and copper powder is purified through the dilute hydrochloric acid deironing;
Again made copper powder and spent acid cupric chloride etching liquid and sodium-chlor complexing agent (the sodium-chlor add-on is every liter of etching liquid 10g) are mixed, be heated to 80 ℃ and be incubated 35 minutes, in heating and the insulating process reactant is constantly stirred, become brownly by green up to solution, generate the cuprous chloride complexation thing this moment;
Thin up to 4 times in the described brown complex solution makes described complex compound hydrolysis, generates white cuprous chloride precipitation;
Above-mentioned cuprous chloride precipitation through decompress filter, and after the dilute hydrochloric acid of PH=1 and ethanol wash respectively, under 75 ℃ temperature dry 25 minutes, is packed then;
The waste liquid of mother liquor after the hydrolysis of cuprous chloride complexation thing and dilute hydrochloric acid washing cuprous chloride post precipitation merges, and displaces copper powder with iron, and copper powder is back to production; Last iron-bearing water is qualified discharge after alkali neutralization, filtration; Precipitating sludge is as the raw material of producing red iron oxide;
The waste liquid of washing with alcohol cuprous chloride post precipitation is reclaimed and reused in production through lime dehydration and distillation.
Embodiment 2:
It is 30g/l that spent acid cupric chloride etching liquid is diluted to copper ion concentration, and the scrap iron reaction that adds pickling displaces copper powder, and copper powder is purified through dilute hydrochloric acid plinth iron;
Again made copper powder and spent acid cupric chloride etching liquid and Repone K complexing agent (the Repone K add-on is every liter of etching liquid 40g) are mixed, be heated to 95 ℃ and be incubated 15 minutes, in heating and the insulating process reactant is constantly stirred, become brownly by green up to solution, generate the cuprous chloride complexation thing this moment;
Thin up to 6 times in the above-mentioned brown complex solution makes described complex compound hydrolysis, generates white cuprous chloride precipitation;
Above-mentioned cuprous chloride precipitation through decompress filter, and after the dilute hydrochloric acid of PH=2.5 and ethanol wash respectively, under 95 ℃ temperature dry 15 minutes, is packed then;
The waste liquid of mother liquor after the hydrolysis of cuprous chloride complexation thing and dilute hydrochloric acid washing cuprous chloride post precipitation merges, and displaces copper powder with iron, and copper powder is back to production; Last iron-bearing water is qualified discharge after alkali neutralization, filtration; Precipitating sludge is done security landfill;
The waste liquid of washing with alcohol cuprous chloride post precipitation is reclaimed and reused in production through lime dehydration and distillation.
Embodiment 3:
It is 28g/l that spent acid cupric chloride etching liquid is diluted to copper ion concentration, and the scrap iron reaction that adds pickling displaces copper powder, and copper powder is purified through the dilute hydrochloric acid deironing;
Again made copper powder and spent acid cupric chloride etching liquid and sodium-chlor complexing agent (the sodium-chlor add-on is every liter of etching liquid 80g) are mixed, be heated to 85 ℃ and be incubated 30 minutes, in heating and the insulating process reactant is constantly stirred, become brownly by green up to solution, generate the cuprous chloride complexation thing this moment;
Thin up to 4 times in the described brown complex solution makes described complex compound hydrolysis, generates white cuprous chloride precipitation;
Above-mentioned cuprous chloride precipitation through decompress filter, and after the dilute hydrochloric acid of PH=1.8 and ethanol wash respectively, under 80 ℃ temperature dry 20 minutes, is packed then;
Other step is with embodiment 1.
Embodiment 4:
It is 26g/l that spent acid cupric chloride etching liquid is diluted to copper ion concentration, and the scrap iron reaction that adds pickling displaces copper powder, and copper powder is purified through dilute hydrochloric acid plinth iron;
Again made copper powder and spent acid cupric chloride etching liquid and sodium-chlor complexing agent (the sodium-chlor add-on is every liter of etching liquid 100g) are mixed, be heated to 90 ℃ and be incubated 20 minutes, in heating and the insulating process reactant is constantly stirred, become brownly by green up to solution, generate the cuprous chloride complexation thing this moment;
Thin up to 5 times in the described brown complex solution makes described complex compound hydrolysis, generates white cuprous chloride precipitation;
Above-mentioned cuprous chloride precipitation through decompress filter, and after the dilute hydrochloric acid of PH=2.0 and ethanol wash respectively, under 90 ℃ temperature dry 15 minutes, is packed then;
Other step is with embodiment 1.
Claims (8)
1, a kind of method of producing cuprous chloride form deposed copper chloride fluid of etching board of utilizing comprises the steps:
(1). at first displace copper powder with spent acid cupric chloride etching liquid and scrap iron reaction, copper powder is purified through diluted acid plinth iron;
(2). more made copper powder and spent acid cupric chloride etching liquid and muriate complexing agent are mixed, heating is insulation for some time also, is become brownly by green up to solution, generates the cuprous chloride complexation thing this moment;
(3). in described brown complex solution, add water, make described complex compound hydrolysis, generate white cuprous chloride precipitation;
(4). described cuprous chloride is precipitated through decompress filter, and, pack then through washings washing after drying.
2, the method for utilizing the cupric chloride etching liquid to produce cuprous chloride as claimed in claim 1, it is characterized in that: the sedimentary washings of described washing cuprous chloride is dilute hydrochloric acid and ethanol, washing process is for using this two kinds of detergent washings successively respectively.
3, the method for utilizing the cupric chloride etching liquid to produce cuprous chloride as claimed in claim 2, it is characterized in that: the waste liquid of mother liquor after the hydrolysis of cuprous chloride complexation thing and dilute hydrochloric acid washing cuprous chloride post precipitation is merged, displace copper powder with iron, copper powder is back to production; Last iron-bearing water is qualified discharge after alkali neutralization, filtration; With formed precipitating sludge security landfill, or produce the raw material of red iron oxide.
4, the method for utilizing the cupric chloride etching liquid to produce cuprous chloride as claimed in claim 2 is characterized in that: the waste liquid of described washing with alcohol cuprous chloride post precipitation is back to production after lime dehydration and distillation regeneration.
5, the method for utilizing the cupric chloride etching liquid to produce cuprous chloride as claimed in claim 1 or 2 is characterized in that: the described useless cupric chloride etching liquid that is used to produce copper powder should towards rare be 24-30g/l to copper ion concentration.
6, the method for utilizing the cupric chloride etching liquid to produce cuprous chloride as claimed in claim 1 or 2, it is characterized in that: the reaction conditions of described generation cuprous chloride complexation thing is: temperature of reaction is 80-95 ℃; Need during reaction to stir; Reaction times is 15-35 minute.
7, the method for utilizing the cupric chloride etching liquid to produce cuprous chloride as claimed in claim 1 or 2 is characterized in that: the multiple of the thin up of described cuprous chloride complexation thing hydrolysis is 4-6 times.
8, the method for utilizing the cupric chloride etching liquid to produce cuprous chloride as claimed in claim 2, it is characterized in that: described cuprous chloride bake out temperature is 75-95 ℃; Drying time is 15-25 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113822A CN1035109C (en) | 1994-11-04 | 1994-11-04 | Process for producing cuprous chloride using waste etching liquid of copper chloride plate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113822A CN1035109C (en) | 1994-11-04 | 1994-11-04 | Process for producing cuprous chloride using waste etching liquid of copper chloride plate |
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| CN1105341A true CN1105341A (en) | 1995-07-19 |
| CN1035109C CN1035109C (en) | 1997-06-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN94113822A Expired - Fee Related CN1035109C (en) | 1994-11-04 | 1994-11-04 | Process for producing cuprous chloride using waste etching liquid of copper chloride plate |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307107C (en) * | 2005-04-21 | 2007-03-28 | 吴江市阮氏化工有限公司 | Method for producing cuprous chloride by using waste copper chloride etching plate liquid |
| CN100369833C (en) * | 2006-04-24 | 2008-02-20 | 深圳市危险废物处理站 | Method for removing arsenic from waste solution of etching PCB in order to produce feed additive of copper |
| CN1840738B (en) * | 2005-03-31 | 2010-05-12 | 鹤见曹达株式会社 | Refining method for copper chloride etching waste liquid and refined copper chloride solution |
| CN1995015B (en) * | 2006-01-06 | 2010-11-10 | 深圳市危险废物处理站 | Method for preparing feed grade methionine copper chelate using waste etching liquor |
| CN101928098A (en) * | 2010-04-22 | 2010-12-29 | 江苏技术师范学院 | Method for preparing cuprous oxide powder by copper-containing electroplating sludge pressure hydrogen reduction |
| CN102190327A (en) * | 2010-03-08 | 2011-09-21 | 沈祖达 | Cuprous oxide preparation method |
| CN104098122A (en) * | 2013-04-03 | 2014-10-15 | 中国科学院生态环境研究中心 | Technology for non-acidification synthesis of cuprous chloride from waste circuit board |
| CN104591256A (en) * | 2015-01-12 | 2015-05-06 | 广东光华科技股份有限公司 | Method for preparing cuprous oxide in copper chloride system |
| CN105060567A (en) * | 2015-08-23 | 2015-11-18 | 长春黄金研究院 | Treating method for acid waste water containing chlorine |
| CN107662939A (en) * | 2017-09-24 | 2018-02-06 | 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 |
| 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 |
| CN114058869A (en) * | 2021-10-22 | 2022-02-18 | 广东佳纳能源科技有限公司 | Method for recovering copper from copper-manganese solution |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1409589A1 (en) * | 1986-02-03 | 1988-07-15 | Предприятие П/Я А-3481 | Method of producing copper (i) chloride |
| SU1370077A1 (en) * | 1986-07-29 | 1988-01-30 | МГУ им.М.В.Ломоносова | Method of obtaining copper (i) chloride |
| CN1030139C (en) * | 1993-07-19 | 1995-10-25 | 董才华 | Rapid method for producing cuprous chloride by using waste acid and waste copper material |
| CN1041405C (en) * | 1994-05-17 | 1998-12-30 | 西安建筑科技大学 | Process for producing cuprous chloride by combined method |
-
1994
- 1994-11-04 CN CN94113822A patent/CN1035109C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840738B (en) * | 2005-03-31 | 2010-05-12 | 鹤见曹达株式会社 | Refining method for copper chloride etching waste liquid and refined copper chloride solution |
| CN1307107C (en) * | 2005-04-21 | 2007-03-28 | 吴江市阮氏化工有限公司 | Method for producing cuprous chloride by using waste copper chloride etching plate liquid |
| CN1995015B (en) * | 2006-01-06 | 2010-11-10 | 深圳市危险废物处理站 | Method for preparing feed grade methionine copper chelate using waste etching liquor |
| CN100369833C (en) * | 2006-04-24 | 2008-02-20 | 深圳市危险废物处理站 | Method for removing arsenic from waste solution of etching PCB in order to produce feed additive of copper |
| CN102190327A (en) * | 2010-03-08 | 2011-09-21 | 沈祖达 | Cuprous oxide preparation method |
| CN101928098A (en) * | 2010-04-22 | 2010-12-29 | 江苏技术师范学院 | Method for preparing cuprous oxide powder by copper-containing electroplating sludge pressure hydrogen reduction |
| CN101928098B (en) * | 2010-04-22 | 2012-07-25 | 江苏技术师范学院 | Method for preparing cuprous oxide powder by copper-containing electroplating sludge pressure hydrogen reduction |
| CN104098122B (en) * | 2013-04-03 | 2015-07-15 | 中国科学院生态环境研究中心 | Technology for non-acidification synthesis of cuprous chloride from waste circuit board |
| CN104098122A (en) * | 2013-04-03 | 2014-10-15 | 中国科学院生态环境研究中心 | Technology for non-acidification synthesis of cuprous chloride from waste circuit board |
| CN104591256A (en) * | 2015-01-12 | 2015-05-06 | 广东光华科技股份有限公司 | Method for preparing cuprous oxide in copper chloride system |
| CN105060567A (en) * | 2015-08-23 | 2015-11-18 | 长春黄金研究院 | Treating method for acid waste water containing chlorine |
| CN107662939A (en) * | 2017-09-24 | 2018-02-06 | 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 |
| 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 |
| 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 |
| CN114058869A (en) * | 2021-10-22 | 2022-02-18 | 广东佳纳能源科技有限公司 | Method for recovering copper from copper-manganese solution |
| CN114058869B (en) * | 2021-10-22 | 2022-11-01 | 广东佳纳能源科技有限公司 | Method for recovering copper from copper-manganese solution |
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| CN1035109C (en) | 1997-06-11 |
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