CN107557581A - A kind of method that copper is reclaimed from acidic waste etching liquid - Google Patents
A kind of method that copper is reclaimed from acidic waste etching liquid Download PDFInfo
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- CN107557581A CN107557581A CN201710597367.XA CN201710597367A CN107557581A CN 107557581 A CN107557581 A CN 107557581A CN 201710597367 A CN201710597367 A CN 201710597367A CN 107557581 A CN107557581 A CN 107557581A
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Abstract
A kind of method that copper is reclaimed from acidic waste etching liquid.It is characterized in that step is as follows：(1) 1 ~ 5 grade of extracting copper is passed through using the extractant and acidic waste etching liquid of N235 extractant TBP extractant kerosene；(2) load organic phases obtained by step (1) are washed with water；(3) load organic phases of step (2) and sulfur acid, the copper-bath of copper ion are stripped by 1 ~ 3 grade；(4) organic phase after step (3) is stripped is with pure water by 1 grade of washing；(5) metal stainless steel 304, Stainless steel 316 or Titanium are used as negative electrode, in 50 ~ 400A/m of current density2Copper-bath obtained by lower electrodeposition step (3), obtains acid copper.The present invention from acidic waste etching liquid reclaim copper method, can by copper from acidic waste etching liquid Selective Separation, technique is simple, good separating effect.
Description
Technical field
The present invention relates to a kind of method that copper is reclaimed from acidic waste etching liquid.
Background technology
The technological process of production length of printed circuit board (PCB), etching work procedure are proportion is maximum in PCB production procedures one
Point.Etching solution includes acidic etching liquid, alkaline etching liquid and micro etching solution.Acidic waste etching liquid copper ion concentration is very high, reaches
120g/L or higher, the main component of these spent etching solutions have：The inorganic matters such as heavy metal copper, ammonium salt.PCB industries consume essence every year
More than 100,000 tons of copper, total copper content is more than 50,000 tons in the copper-containing wastewater of output, ten thousand tons of ammonium chloride about l0.It can be seen that：
The pollution index of useless acidic etching liquid is very high, is typical dangerous liquid waste；Useless acidic etching liquid resource reclaim and again simultaneously
That makes profits has a high potential.
Mainly there are displacement method, electrolysis, neutralization precipitation method etc. to acidic waste etching liquid processing method both at home and abroad.Displacement method obtains
It is not high to sponge copper grade, reclaim copper after tail washings copper content it is high the shortcomings of；Electrolysis produces relatively inefficient, the power consumption of copper powder
Amount is higher, and the concentration of heavy metal ion in waste liquid can not be fallen too low, and strict improvement be carried out before discharge, and be electrolysed
Method easily produces chlorine；Neutralization precipitation method Treatment of Copper waste liquid, technique is simple, small investment, but cupric sulphate crystal Mother liquor contains
Amount of copper is higher, need to further handle, it is impossible to the inorganic matters such as the ammonium salt in waste water and organic matter circling are utilized, cause serious ring
Pollute in border.The copper reclaimed using extracting process in etching solution is carried out both at home and abroad at present, its extractant is mainly Lix series extractions
Agent or M5640 extractants；LIX or M5640 extractants belong to the special extractant of copper, high to selective copper extraction yield, to other
Metal extraction rate is low, is adapted to the selective extraction copper from more metallic solutions, reaches the purpose of separation copper.
CN201310321366.4, CN201510335589.5 are disclosed using LIX extractants and N235 extractant hybrid extraction copper
Better effects are achieved, but because LIX extractants are expensive, cause production cost to increase.Acidic waste etching liquid is containing only copper
Ion, other metal ions are seldom, less demanding to the selectivity of extractant, can select other cheap, extracting powers
Strong extractant.
The content of the invention
It is an object of the invention to provide a kind of method that copper is reclaimed from acidic waste etching liquid, the rate of recovery of copper is improved,
Reduce production cost.
Acidic waste etching liquid of the present invention, it is that etched the waste liquid of copper during printed circuit board etching work procedure,
The H of the waste liquid+Concentration is 0.01 ~ 2.6mol/L, 30 ~ 160g/L of copper ion and a large amount of chlorions.The present invention's loses from spent acidic
The method for carving recovery copper in liquid is as follows：
(1) extractant and spent acidic of the volume ratio for the kerosene of 5 ~ 15%N235-5 ~ 15%TBP of extractant extractants-70 ~ 90% are used
Etching solution by volume 1 ~ 30:1, by 1 ~ 5 grade of extracting copper；(2) load organic phases obtained by step (1) are washed with water 1 ~ 5
Level；(3) load organic phases and 130 ~ 250g/L of sulfur acid, 5 ~ 50g/L of copper ion copper-bath after step (2) is washed
By volume 1 ~ 10:1 by 1 ~ 3 grade of back extraction；Aqueous phase is copper-bath；(4) by step (3) be stripped after organic phase with
Pure water by volume 2 ~ 10:1 by 1 grade of washing；Extractant return to step (1) is reused after washing, aqueous phase return to step (2)
Instead of slurry；(5) metal stainless steel 304, Stainless steel 316 or Titanium are used as negative electrode, in 50 ~ 400A/ of current density
m2Copper-bath obtained by lower electrodeposition step (3), obtains acid copper, the copper-bath return to step after acid copper
(3) reuse.
N235 belongs to amine extractant, chelate can be formed with acid and chlorion, in chloride system and acid system
It is higher to the extraction yield of copper.TBP extractants belong to a kind of conventional extractant, and extracting power is strong, cheap, only LIX extractions
Take 1/5th of agent price.Synergic solvent extraction refers to that two or more extractant extracts to certain component jointly, and it extracts
Ability is taken to be more than the extracting power sum that each extractant is used alone.TBP（Tributyl phosphate）With the extraction of N235 mixed systems
Ability is significantly stronger than single TBP or N235.The present invention by N235 extractants, TBP extractant mixing synergic solvent extraction copper, by copper from
Extracted in useless acidic etching liquid, so as to improve the extraction yield of copper in acid extract system；Then with anti-from having washed
The acid solution wash load extractant of extractant after extraction, washes the other cations and chlorion of entrainment off, is finally stripped copper
Take off, electro-deposition is metallic copper.
The method that copper is reclaimed from acidic waste etching liquid of the present invention, copper can be extracted, extract from acidic waste etching liquid
Efficiency high, cost are low.
Embodiment
Embodiment 1
Certain acidic waste etching liquid, wherein H+Concentration is 0.012mol/L, copper ion 120g/L and a large amount of chlorions；Using volume ratio
It is 10 by volume for the extractant and acidic waste etching liquid of the kerosene of 5%N235 extractant -5%TBP extractants -90%:1 three-level extracts
Take, it is 1.5/L that extraction post analysis, which measure Cu in waste water concentration, is computed extraction of copper up to 98.75%；Then by load organic phases
Washed with from the aqueous phase for having washed back extraction organic phase by three-level；After washing, by load organic phases and sulfur acid 131g/L, copper
Ion 6g/L copper-bath is 10 by volume:1 is stripped compared to two level, and aqueous phase is copper-bath；After back extraction, have
Machine phase and pure water by volume 10:1 by 1 grade of washing；Organic phase, which returns, to be reused, and aqueous phase returns to wash load organic phase；
Copper-bath is in current density 75A/m2Under, obtain cathode copper, cathode copper purity in Stainless steel 316 negative electrode electro-deposition
99.95%, sulfur acid 130g/L, copper ion 5g/L copper-baths after acid copper return to back extraction organic phase.
Embodiment 2
Certain acidic waste etching liquid, wherein H+Concentration is 1.0mol/L, copper ion 140g/L and a large amount of chlorions；Use volume ratio for
The extractant of the kerosene of 15%N235 extractant -15%TBP extractants -70% is 30 by volume with acidic waste etching liquid:1 one-level extracts
Take, it is 1g/L that extraction post analysis, which measure Cu in waste water concentration, is computed extraction of copper up to 99.3%；Then load organic phases are used
Washed from the aqueous phase for having washed back extraction organic phase by one-level；After washing, by load organic phases and sulfur acid 240g/L, copper from
Sub- 9g/L copper-bath is 5 by volume:1 is stripped compared to two level, and aqueous phase is copper-bath；It is organic after back extraction
Mutually with pure water by volume 2:1 by 1 grade of washing；Organic phase, which returns, to be reused, and aqueous phase returns to wash load organic phase；Sulfuric acid
Copper solution is in current density 320A/m2Under, stainless steel 304 negative electrode electro-deposition obtains cathode copper, cathode copper purity 99.96%, and electricity sinks
Sulfur acid 200g/L, copper ion 26g/L copper-baths after product copper return to back extraction organic phase.
Embodiment 3
Certain acidic waste etching liquid, wherein H+Concentration is 2.6mol/L, copper ion 100g/L and a large amount of chlorions；Use volume ratio for
The extractant of the kerosene of 15%N235 extractant -5%TBP extractants -75% is 20 by volume with acidic waste etching liquid:1 one-level extracts
Take, it is 0.5g/L that extraction post analysis, which measure Cu in waste water concentration, is computed extraction of copper up to 99.5%；Then by load organic phases
Washed with from the aqueous phase for having washed back extraction organic phase by Pyatyi；After washing, by load organic phases and sulfur acid 220g/L, copper
Ion 20g/L copper-bath is 5 by volume:1 is stripped compared to two level, and aqueous phase is copper-bath；After back extraction, have
Machine phase and pure water by volume 5:1 by 1 grade of washing；Organic phase, which returns, to be reused, and aqueous phase returns to wash load organic phase；Sulphur
Sour copper solution is in current density 300A/m2Under, metallic titanium plate negative electrode electro-deposition obtains cathode copper, cathode copper purity 99.96%, electricity
Deposit the sulfur acid 180g/L after copper, copper ion 29g/L copper-baths return to back extraction organic phase.
Embodiment 4
Certain acidic waste etching liquid, wherein H+Concentration is 0.01mol/L, copper ion 30g/L and a large amount of chlorions；Use volume ratio for
The extractant of the kerosene of 10%N235 extractant -15%TBP extractants -75% is 1 by volume with acidic waste etching liquid:1 one-level extracts
Take, it is 3.0mg/L that extraction post analysis, which measure Cu in waste water concentration, is computed extraction of copper up to 99%；Then load organic phases are used
Washed from the aqueous phase for having washed back extraction organic phase by 3 grades；After washing, by load organic phases and sulfur acid 220g/L, copper from
Sub- 42g/L copper-bath is 1 by volume:1 is stripped compared to one-level, and aqueous phase is copper-bath；It is organic after back extraction
Mutually with pure water by volume 5:1 by 1 grade of washing；Organic phase, which returns, to be reused, and aqueous phase returns to wash load organic phase；Sulfuric acid
Copper solution is in current density 390A/m2Under, Stainless steel 316 negative electrode electro-deposition obtains cathode copper, cathode copper purity 99.97%, and electricity sinks
Sulfur acid 220g/L, copper ion 10g/L copper-baths after product copper return to back extraction organic phase.
Claims (1)
1. a kind of method that copper is reclaimed from acidic waste etching liquid, the acidic waste etching liquid is printed circuit board etching work procedure mistake
The waste liquid of copper, the H of the waste liquid are etched in journey+Concentration is 0.01 ~ 2.6mol/L, 30 ~ 160g/L of copper ion and a large amount of chlorions,
It is characterized in that comprise the steps of：(1) volume ratio is used as the coal of 5 ~ 15%N235-5 ~ 15%TBP of extractant extractants-70 ~ 90%
Extractant and the acidic waste etching liquid of oil by volume 1 ~ 30:1, by 1 ~ 5 grade of extracting copper；(2) by step (1) obtained by load
Organic phase is washed with water 1 ~ 5 grade；(3) load organic phases and 130 ~ 250g/L of sulfur acid, copper ion 5 after step (2) is washed ~
50g/L copper-bath by volume 1 ~ 10:1 by 1 ~ 3 grade of back extraction；Aqueous phase is copper-bath；(4) by step (3)
Organic phase after back extraction and pure water by volume 2 ~ 10:1 by 1 grade of washing；Extractant return to step (1) repeats to make after washing
With aqueous phase return to step (2) replaces slurry；(5) metal stainless steel 304, Stainless steel 316 or Titanium are used as negative electrode,
In 50 ~ 400A/m of current density2Copper-bath obtained by lower electrodeposition step (3), obtains acid copper, the sulphur after acid copper
Sour copper solution return to step (3) is reused.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110453245A (en) * | 2018-05-07 | 2019-11-15 | 卫司特科技股份有限公司 | Copper waste etching solution copper ion handles recovery method |
| 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 |
| CN114703377A (en) * | 2022-04-15 | 2022-07-05 | 重庆康普化学工业股份有限公司 | Method for extracting copper from acidic etching waste liquid |
| CN116891949A (en) * | 2023-06-06 | 2023-10-17 | 西部矿业股份有限公司 | Process for recycling three-phase slag produced in wet copper extraction process |
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|---|---|---|---|---|
| CN104962742A (en) * | 2015-06-17 | 2015-10-07 | 陈飙 | Method for recycling copper from acid waste etching solution |
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2017
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104962742A (en) * | 2015-06-17 | 2015-10-07 | 陈飙 | Method for recycling copper from acid waste etching solution |
Non-Patent Citations (2)
| Title |
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| 中国有色金属工业协会: "《有金属系列丛书 中国钴业》", 31 August 2012 * |
| 谢琦莹: "N235萃取HCl体系中TBP消除第三相的作用机理", 《无机化学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110453245A (en) * | 2018-05-07 | 2019-11-15 | 卫司特科技股份有限公司 | Copper waste etching solution copper ion handles recovery method |
| CN110453245B (en) * | 2018-05-07 | 2021-12-28 | 卫司特科技股份有限公司 | Method for treating and recovering copper ions in copper etching waste liquid |
| 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 |
| CN114703377A (en) * | 2022-04-15 | 2022-07-05 | 重庆康普化学工业股份有限公司 | Method for extracting copper from acidic etching waste liquid |
| CN116891949A (en) * | 2023-06-06 | 2023-10-17 | 西部矿业股份有限公司 | Process for recycling three-phase slag produced in wet copper extraction process |
| CN116891949B (en) * | 2023-06-06 | 2024-05-03 | 西部矿业股份有限公司 | Process for recycling three-phase slag produced in wet copper extraction process |
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Application publication date: 20180109 |