CN104962742A - Method for recycling copper from acid waste etching solution - Google Patents
Method for recycling copper from acid waste etching solution Download PDFInfo
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- CN104962742A CN104962742A CN201510335589.5A CN201510335589A CN104962742A CN 104962742 A CN104962742 A CN 104962742A CN 201510335589 A CN201510335589 A CN 201510335589A CN 104962742 A CN104962742 A CN 104962742A
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- copper
- waste etching
- etching liquid
- organic phase
- acidic waste
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method for recycling copper from an acid waste etching solution. The method is characterized by comprising the following steps that firstly, an organic phase and the acid waste etching solution are subjected to 1-5 levels of extraction according to the volume ratio of 1-30:1, and copper is extracted; secondly, the load organic phase obtained in the first step and purified water are subjected to 1-5 levels of washing according to the volume ratio of 0.1-10:1; thirdly, the load organic phase washed in the second step and a copper sulphate solution including sulfur acid of 130-250 g/L and copper ions of 1-50 g/L are subjected to 1-3 levels of back extraction according to the volume ratio of 1-10:1, the organic phase obtained through back extraction is returned to the first step to be repeatedly used, and a water phase is a copper sulphate solution; fourthly, metal stainless steel 304 or stainless steel 316 or metal titanium is used as a cathode, the copper sulphate solution obtained in the third step is electroplated under the current density of 50-400 A/m<2>, electroplated copper is obtained, and the copper sulphate solution obtained after the copper is electroplated is returned to the third step to be repeatedly used. According to the method for recycling copper from the acid waste etching solution, the copper can be separated selectively from the acid waste etching solution, the technology is simple, and the separation effect is good.
Description
Technical field
The present invention relates to a kind of method reclaiming copper from acidic waste etching liquid.
Background technology
The technological process of production of printed circuit board (PCB) is long, and etching work procedure is the part that in PCB Production Flow Chart, proportion is maximum.In etching work procedure, when etching solution makes etching index too much due to the material dissolved, when comprising speed, lateral erosion coefficient, clean surface etc. lower than processing requirement, namely become spent etching solution.Etching solution comprises acidic etching liquid, alkaline etching liquid and micro etching solution.Acid etching is mainly used in the making of the internal layer circuit figure of multilayer circuit board, in general, often produces 1m
2wiring board need consume etching solution 2 ~ 2.5L, accordingly also output spent etching solution 2 ~ 2.5L, and its copper ion concentration is very high, reaches 120g/L or higher, and the main component of these spent etching solutions has: heavy metal copper, ammonium salt, phosphate radical and containing inorganicss such as iodine compounds; Sulfurous organic compound, nitrogen-containing heterocycle compound and containing the organism such as cyanogen radical compound; Polyoxyethylene type compounds, the contour molecular compound of polyvinyl alcohol compounds.PCB industry consumes smart copper more than 100,000 tons every year, in the copper-containing wastewater of output, total copper content is more than 50,000 tons, ammonium chloride is about l0 ten thousand tons, inorganic and organophosphorus about 4000 tons, sulfur-bearing nitrogen heterocyclic ring organism about 1000 tons, therefore can find out: the pollution index of spent etching solution is very high, be typical dangerous liquid refuse; Simultaneously spent etching solution or a kind of very worthy composite factor, having a high potential of its resource reclaim and regeneration.
Substitution method, electrolytic process, moderate water-cut stage etc. are mainly contained to acidic waste etching liquid treatment process both at home and abroad.It is not high that substitution method obtains copper sponge grade, the shortcomings such as tail washings copper content is high after recovery copper; Although the copper powder purity that electrolytic process is produced is high, performance is better than the copper powder that other method is produced, but the efficiency that electrolytic process produces copper powder is relatively low, current consumption is higher, and the concentration of heavy metal ion in waste liquid can not fall too low, strict improvement will be carried out before discharge, and electrolytic process easily produces chlorine; Moderate water-cut stage Treatment of Copper waste liquid, technique is simple, less investment, but after cupric sulphate crystal, mother liquor copper content is higher, need process further, can not utilize, cause serious environmental pollution to the inorganicss such as the ammonium salt in waste water and organic matter circling.Carried out the copper adopted in extracting process recovery etching solution at present both at home and abroad, its extraction agent is mainly the agent of Lix series extraction or M5640 extraction agent; When adopting LIX or M5640 extraction agent extraction copper, often extracting the copper of a molecule, just must discharge the H of two molecules
+; If the copper of extraction is more, the H of release
+also more, the acidity of solution is also larger; And LIX or M5640 extraction agent is very low to the percentage extraction of copper in acid condition.And LIX or M5640 extraction agent extraction copper belongs to oximes extraction agent, the H in saponification mode can being adopted unlike Phosphorus acidic extractant P204, P507 and in extraction agent
+, when making it extract, do not discharge H
+, keep the stable of material liquid pH; Therefore LIX or M5640 extraction agent cannot be applied, particularly in acid system in the extraction of high-copper feed liquid at present.
Summary of the invention
The object of the present invention is to provide a kind of method reclaiming copper from acidic waste etching liquid, improve the purity and quality that reclaim copper, increase economic efficiency, to reduce quantity of wastewater effluent.
Acidic waste etching liquid of the present invention, it is the waste liquid that etched copper in printed circuit board etching work procedure process, the H of this waste liquid
+concentration is 0.01 ~ 3mol/L, cupric ion 5 ~ 160g/L and chlorion.The method reclaiming copper from acidic waste etching liquid of the present invention is as follows:
(1) by organic phase and acidic waste etching liquid by volume 1 ~ 30: 1, through 1 ~ 5 grade of extracting copper; (2) load organic phases of step (1) gained and pure water through 1 ~ 5 grade are washed by volume at 0.1 ~ 10: 1; (3) by step (2) wash after load organic phases and sulfur acid 130 ~ 250g/L, cupric ion 5 ~ 50g/L copper-bath through 1 ~ 3 grade strip at 1 ~ 10: 1 by volume, the organic phase after reextraction returns step (1) and reuses; Aqueous phase is copper-bath; (4) metal stainless steel 304, Stainless steel 316 or metal titanium is adopted to be negative electrode, at current density 50 ~ 400A/m
2lower electrodeposition step (3) gained copper-bath, obtain acid copper, the copper-bath after acid copper returns step (3) and reuses.
Described organic phase is the Lix of volume ratio 5 ~ 20%
?the mixed extractant of series extraction agent and amine extractant and 80 ~ 95% kerosene or 200
#solvent oil.
Described Lix
?series extraction agent is Lix84-I, Lix973 or Lix984.
Described amine extractant is N235 or N263.
Described Lix
?the volume ratio of series extraction agent and amine extractant is 0.05 ~ 8: 1.
Due to Lix
?extraction agent extraction copper belongs to oximes extraction agent, the H in saponification mode can being adopted unlike Phosphorus acidic extractant P204, P507 and in extraction agent
+, when making it extract, do not discharge H
+, keep the stable of material liquid pH; The present invention utilizes Lix
?the highly selective of series extraction agent extracting copper and amine extractant can extract the feature of acid, by amine extractant and Lix
?extraction agent mixes, and makes amine extractant absorb Lix
?the hydrogen ion discharged during extraction agent extraction copper, thus ensure that extraction system pH value is stablized, ensure that the percentage extraction of copper.Copper is extracted from spent etching solution; Then wash load extraction agent, wash other positively charged ion and chlorion of carrying secretly off, finally stripped by copper, galvanic deposit is metallic copper.
The method reclaiming copper from acidic waste etching liquid of the present invention, can by copper selective separation from acidic waste etching liquid, and technique is simple, and good separating effect, electrolysis metallic copper purity is out high, and content oxygen amount is low.
Embodiment
Embodiment 1
Certain acidic waste etching liquid, wherein H
+concentration is 0.012mol/L, cupric ion 120g/L and chlorion; The organic phase of 1%Lix84-I, 14%N235 and 85% kerosene and acidic waste etching liquid are 10: 1 three grades by volume extract, it is 3g/L that extraction post analysis records Cu in waste water concentration, and extraction of copper reaches 97.5% as calculated; Then load organic phases and pure water are 10: 1 three grades by volume to wash, after washing, be that compared with in the of 10: 1, secondary is stripped by volume by load organic phases and the copper-bath of sulfur acid 131g/L, cupric ion 6g/L, after reextraction, organic phase returns to be reused, aqueous phase is copper-bath, current density 55A/m
2under, obtain electrolytic copper at Stainless steel 316 cathode electrodeposition, electrolytic copper purity 99.95%, the sulfur acid 130g/L after acid copper, cupric ion 5g/L copper-bath return reextraction organic phase.
Embodiment 2
Certain acidic waste etching liquid, wherein H
+concentration is 1.0mol/L, cupric ion 140g/L and chlorion; By 10%Lix973,10%N263 extraction agent and 80%200
#the organic phase of solvent oil and acidic waste etching liquid are that 30: 1 one-levels extract by volume, and it is 2.8g/L that extraction post analysis records Cu in waste water concentration,
Extraction of copper reaches 98% as calculated; Then be that 5: 1 secondarys wash by volume by load organic phases and pure water, after washing, be that compared with in the of 5: 1, secondary is stripped by volume by load organic phases and the copper-bath of sulfur acid 240g/L, cupric ion 9g/L, after reextraction, organic phase returns to be reused, aqueous phase is copper-bath, at current density 220A/m
2under, stainless steel 304 cathode electrodeposition obtains electrolytic copper, electrolytic copper purity 99.98%, and the sulfur acid 200g/L after acid copper, cupric ion 26g/L copper-bath return reextraction organic phase.
Embodiment 3
Certain acidic waste etching liquid, wherein H
+concentration is 2.9mol/L, cupric ion 100g/L and chlorion; Be that 20: 1 one-levels extract by volume by the organic phase of 4.3%Lix984,0.7%N235 extraction agent and 95% kerosene and acidic waste etching liquid, it is 1g/L that extraction post analysis records Cu in waste water concentration, and extraction of copper reaches 99% as calculated; Then be that 0.2: 1 one-level is washed by volume by load organic phases and pure water, after washing, be that compared with in the of 5: 1, secondary is stripped by volume by load organic phases and the copper-bath of sulfur acid 220g/L, cupric ion 20g/L, after reextraction, organic phase returns to be reused, aqueous phase is copper-bath, at current density 300A/m
2under, metallic titanium plate cathode electrodeposition obtains electrolytic copper, electrolytic copper purity 99.96%, and the sulfur acid 180g/L after acid copper, cupric ion 29g/L copper-bath return reextraction organic phase.
Embodiment 4
Certain acidic waste etching liquid, wherein H
+concentration is 0.01mol/L, cupric ion 6g/L and chlorion; Be that 1: 1 one-level extracts by volume by the organic phase of 4%Lix84-I, 1%N235 extraction agent and 95% kerosene and acidic waste etching liquid, it is 0.60mg/L that extraction post analysis records Cu in waste water concentration, and extraction of copper reaches 99% as calculated; Then be that 1: 1 one-level is washed by volume by load organic phases and pure water, after washing, be that compared with in the of 1: 1, one-level is stripped by volume by load organic phases and the copper-bath of sulfur acid 220g/L, cupric ion 42g/L, after reextraction, organic phase returns to be reused, aqueous phase is copper-bath, at current density 390A/m
2under, Stainless steel 316 cathode electrodeposition obtains electrolytic copper, electrolytic copper purity 99.97%, and the sulfur acid 220g/L after acid copper, cupric ion 10g/L copper-bath return reextraction organic phase.
Claims (5)
1. from acidic waste etching liquid, reclaim a method for copper, described acidic waste etching liquid is the waste liquid that etched copper in printed circuit board etching work procedure process, the H of this waste liquid
+concentration is 0.01 ~ 3mol/L, cupric ion 5 ~ 160g/L and chlorion, it is characterized in that being made up of following steps: (1) by organic phase and acidic waste etching liquid by volume 1 ~ 30: 1, through 1 ~ 5 grade of extracting copper; (2) load organic phases of step (1) gained and pure water through 1 ~ 5 grade are washed by volume at 0.1 ~ 10: 1; (3) by step (2) wash after load organic phases and sulfur acid 130 ~ 250g/L, cupric ion 5 ~ 50g/L copper-bath through 1 ~ 3 grade strip at 1 ~ 10: 1 by volume, the organic phase after reextraction returns step (1) and reuses; Aqueous phase is copper-bath; (4) metal stainless steel 304, Stainless steel 316 or metal titanium is adopted to be negative electrode, at current density 50 ~ 400A/m
2lower electrodeposition step (3) gained copper-bath, obtain acid copper, the copper-bath after acid copper returns step (3) and reuses.
2. the method reclaiming copper from acidic waste etching liquid according to claim 1, is characterized in that described organic phase is the Lix of volume ratio 5 ~ 20%
?the mixed extractant of series extraction agent and amine extractant and 80 ~ 95% kerosene or 200
#solvent oil.
3. the method reclaiming copper from acidic waste etching liquid according to claim 2, is characterized in that described Lix
?series extraction agent is Lix84-I, Lix973 or Lix984.
4. the method reclaiming copper from acidic waste etching liquid according to claim 2, is characterized in that described amine extractant is N235 or N263.
5. the method reclaiming copper from acidic waste etching liquid according to claim 1 and 2, is characterized in that described Lix
?the volume ratio of series extraction agent and amine extractant is 0.05 ~ 8: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510335589.5A CN104962742A (en) | 2015-06-17 | 2015-06-17 | Method for recycling copper from acid waste etching solution |
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|---|---|---|---|
| CN201510335589.5A CN104962742A (en) | 2015-06-17 | 2015-06-17 | Method for recycling copper from acid waste etching solution |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106348334A (en) * | 2016-11-18 | 2017-01-25 | 东莞市新意工业废物处理有限公司 | Feed-level copper sulfate and production technology thereof |
| CN106400050A (en) * | 2016-09-21 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Method for preparing high-quality electro-deposited copper from waste copper liquid |
| CN107313069A (en) * | 2017-05-22 | 2017-11-03 | 广东省稀有金属研究所 | A kind of method by acid, the mashed up recovery copper of alkali spent etching solution |
| CN107385470A (en) * | 2016-05-17 | 2017-11-24 | 陕西安信显像管循环处理应用有限公司 | Cupric spent etching solution recovery method |
| CN107557581A (en) * | 2017-07-20 | 2018-01-09 | 陈飙 | A kind of method that copper is reclaimed from acidic waste etching liquid |
| CN112522514A (en) * | 2020-11-17 | 2021-03-19 | 陕西三秦环保科技股份有限公司 | Copper-containing etching solution recycling treatment system and method |
| CN112626567A (en) * | 2020-11-23 | 2021-04-09 | 江苏净源新材料有限公司 | Method for preparing nano copper powder by recovering copper by using etching solution |
| CN112941562A (en) * | 2021-01-13 | 2021-06-11 | 湖南埃格环保科技有限公司 | Combined treatment method for copper-containing sludge and copper-containing etching waste liquid |
| CN114892020A (en) * | 2022-05-29 | 2022-08-12 | 成武县元信昇环保科技有限公司 | Process for preparing electrodeposited copper from copper-containing waste liquid |
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| CN101008052A (en) * | 2006-11-15 | 2007-08-01 | 长沙绿铱环保科技有限公司 | Method for recovering copper from PCB copper etching liquor separated by solvent extraction technology |
| CN103233128A (en) * | 2013-05-13 | 2013-08-07 | 陈飙 | Method for recovering copper from acid waste etching solution |
| CN103397341A (en) * | 2013-07-29 | 2013-11-20 | 陈飙 | Method for recycling copper from basic waste etching liquid |
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2015
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Patent Citations (3)
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| CN101008052A (en) * | 2006-11-15 | 2007-08-01 | 长沙绿铱环保科技有限公司 | Method for recovering copper from PCB copper etching liquor separated by solvent extraction technology |
| CN103233128A (en) * | 2013-05-13 | 2013-08-07 | 陈飙 | Method for recovering copper from acid waste etching solution |
| CN103397341A (en) * | 2013-07-29 | 2013-11-20 | 陈飙 | Method for recycling copper from basic waste etching liquid |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107385470A (en) * | 2016-05-17 | 2017-11-24 | 陕西安信显像管循环处理应用有限公司 | Cupric spent etching solution recovery method |
| CN106400050A (en) * | 2016-09-21 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Method for preparing high-quality electro-deposited copper from waste copper liquid |
| CN106348334A (en) * | 2016-11-18 | 2017-01-25 | 东莞市新意工业废物处理有限公司 | Feed-level copper sulfate and production technology thereof |
| CN106348334B (en) * | 2016-11-18 | 2018-04-13 | 东莞市新意工业废物处理有限公司 | A kind of feed-grade bluestone and its production technology |
| CN107313069A (en) * | 2017-05-22 | 2017-11-03 | 广东省稀有金属研究所 | A kind of method by acid, the mashed up recovery copper of alkali spent etching solution |
| CN107557581A (en) * | 2017-07-20 | 2018-01-09 | 陈飙 | A kind of method that copper is reclaimed from acidic waste etching liquid |
| CN112522514A (en) * | 2020-11-17 | 2021-03-19 | 陕西三秦环保科技股份有限公司 | Copper-containing etching solution recycling treatment system and method |
| CN112626567A (en) * | 2020-11-23 | 2021-04-09 | 江苏净源新材料有限公司 | Method for preparing nano copper powder by recovering copper by using etching solution |
| CN112626567B (en) * | 2020-11-23 | 2022-03-29 | 江苏净源新材料有限公司 | Method for preparing nano copper powder by recovering copper by using etching solution |
| CN112941562A (en) * | 2021-01-13 | 2021-06-11 | 湖南埃格环保科技有限公司 | Combined treatment method for copper-containing sludge and copper-containing etching waste liquid |
| CN114892020A (en) * | 2022-05-29 | 2022-08-12 | 成武县元信昇环保科技有限公司 | Process for preparing electrodeposited copper from copper-containing waste liquid |
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Application publication date: 20151007 |