CN103938222B - A kind of method reclaiming copper from acidic etching waste liquid - Google Patents
A kind of method reclaiming copper from acidic etching waste liquid Download PDFInfo
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- CN103938222B CN103938222B CN201410180467.9A CN201410180467A CN103938222B CN 103938222 B CN103938222 B CN 103938222B CN 201410180467 A CN201410180467 A CN 201410180467A CN 103938222 B CN103938222 B CN 103938222B
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- copper
- waste liquid
- acidic etching
- etching 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
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Abstract
<b> the invention discloses a kind of method reclaiming copper from acidic etching waste liquid, with the acidic etching waste liquid of </b><bGreatT.Gre aT.GTPCB</b><bGr eatT.GreaT.GT etching work procedure discharge for catholyte and anolyte, promotor is added successively in catholyte, grain-refining agent and leveling agent, under agitation condition, cathode current density is </b><bGreatT.Gre aT.GT100-1000A/m
2</b><bGreatT.Gre aT.GT carries out DC electrolysis, after electrolysis </b><bGreatT.Gre aT.GT10-30h</b>< b>, namely obtain metallic copper at cathode compartment, described promotor is the derivative of ammonia, and described grain-refining agent is with sulfonic organic sulfide, and described leveling agent is polyvinyl alcohol.The method directly obtains copper billet, and deposition high, the easy stripping of copper billet purity, without joint branch, can not barrier film be pierced through.</b>
Description
Technical field
The present invention relates to field of environment engineering technology, particularly relate to a kind of method reclaiming copper from acidic etching waste liquid.
Background technology
Acidic etching liquid is a kind of etching solution for etching work procedure in printed circuit board (particularly fine-line makes and the making of multi-ply wood internal layer) production process, mainly contains HCl/NaCl/CuCl
2system, HCl/NH
4cl/CuCl
2system, HCl/CuCl
2system.Along with the carrying out of etching work procedure, Cu in etching solution
2+concentration constantly reduces, Cu
+and total copper concentration constantly rises, etching speed declines, and now needs discharge etching waste liquor or regenerates.In etching waste liquor, copper is dense, and between 100g/L-160g/L, directly discharge meeting serious environment pollution, if can reclaim the copper of wherein high added value, will produce significant economic benefit and environmental benefit.Electrolytic process while cathode electrodeposition Footwall drift copper, at anode regeneration etching solution, can have broad application prospects.
The method of existing Direct Electrolysis recovery copper from acidic etching waste liquid is membrane electrolysis, owing to containing a large amount of Cl in acidic etching liquid
-(concentration is between 200g/L-330g/L), it has very strong unpolarizing, makes etching waste liquor facile copper in electrolytic process be powdery or produces serious joint branch phenomenon, saving dendritic copper and easily block or pierce through barrier film, cause electrolyzer to paralyse, impact is produced.And copper powder easily flakes off at the bottom of cathode can, also need the subsystem being equipped with copper powder taking-up specially, and copper powder very easily oxidation stain, affect purity, appearance is bad, and its value also can be had a greatly reduced quality.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of method reclaiming copper from acidic etching waste liquid, the method directly obtains copper billet, and deposition high, the easy stripping of copper billet purity, without joint branch, can not barrier film be pierced through.
For solving the problem, the technical solution adopted in the present invention is as follows:
A kind of method reclaiming copper from acidic etching waste liquid, with the acidic etching waste liquid of PCB etching work procedure discharge for catholyte and anolyte, in catholyte, add promotor, grain-refining agent and leveling agent successively, under agitation condition, cathode current density is 100-1000A/m
2carry out DC electrolysis, after electrolysis 10-30h, namely obtain metallic copper at cathode compartment; Described promotor is the derivative of ammonia, and described grain-refining agent is with sulfonic organic sulfide, and described leveling agent is polyvinyl alcohol.
Preferably, described promotor add-on is the 0.1-5.0% of catholyte volume, and described grain-refining agent and leveling agent add-on are respectively 5-100mg/L.
Preferably, described stirring velocity is 50r/min-500r/min.
Preferably, described DC electrolysis adopts gradient current density to carry out.
Preferably, described promotor be in hydrazine hydrate, azanol one or both.
Preferably, described grain-refining agent is for gathering any one or more in dithiopropane Huang Suan Na ﹑ dimethyl formamide base sodium sulfonate and 3-sulfydryl-1-propane sulfonic acid sodium.
In the present invention, by a small amount of promotor as hydrazine hydrate (H
2n-NH
2) or azanol (NH
2-OH) join as catholyte in the middle of acidic etching waste liquid, because it has strong reductibility, can by part Cu
2+be reduced to Cu
+, greatly reduce the etching speed of etching waste liquor, suppress returning of copper molten, improve current efficiency.On the other hand, can avoid forming joint branch because copper produces dislocation in cathode run.And the N element in promotor can with reaction product N
2and take away, other impurity components can not be introduced to etching solution.
Add in catholyte minute quantity (5-100mg/L) with sulfonic organic sulfide, as poly-dithiopropane sodium sulfonate (SPS) ﹑ dimethyl formamide base sodium sulfonate (TPS) ﹑ 3-sulfydryl-1-propane sulfonic acid sodium (MPS) etc., for surfactant, with the Cl in acidic etching waste liquid
-in electrolytic process, play coordinative role, reach the object of crystal grain thinning.
Owing to containing a large amount of Cl in acidic etching liquid
-, its strong unpolarizing, makes the deposited copper in electrolytic process easily produce joint branch.Add the polyvinyl alcohol of minute quantity (5-100mg/L) in catholyte, wetting, leveling effect can be played, improve cathodic polarization, suppress the growth of joint branch.
Cl in acidic etching waste liquid
-, sulfonic organic sulfide, polyvinyl alcohol play synergy in electrolytic process, makes that the copper billet of deposition is fine and close, without joint branch, and the additive of trace can not affect the performance of acidic etching liquid.
Described cathode current density is 100-1000A/m
2, current density is little, avoids separating out hydrogen due to negative electrode and causes peeling off of copper billet.Simultaneously in anolyte compartment, by anodic reaction by cuprous ion (Cu
+) be oxidized to cupric ion (Cu
2+), reach the object of regeneration etching solution.
Directly can take out negative electrode after electrolysis terminates, because the layers of copper of deposition is dense, there is certain thickness simultaneously, can be come by cathodic disbonding after simple flushing.Copper billet easy cleaning, and resistance of oxidation is better than copper powder, therefore purity >=99.5%.
Compared to existing technology, beneficial effect of the present invention is:
1, adopt method of the present invention can deposit comparatively fine and close copper billet by Direct Electrolysis, nothing joint branch, can not pierce through barrier film and easily stripping is shaping;
2, method of the present invention is adopted, bed Electrowinning of Copper current efficiency >=90%, average deposition copper speed >=1.07g/ (Ah), copper billet purity >=99.5%;
3, adopt method of the present invention, can also anode regenerated acidic etching solution be passed through, the object of cyclically utilizing can be reached through simple adjustment.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Acidic etching waste liquid is taken from the acid etching production line of Electronics Factory of Guangdong Province, and solution is blackish green.By analysis, its total copper content is 152.2g/L, HCl content is 73.5g/L, Cl
-content is 305.6g/L.In this, as being anolyte and catholyte, first adding 50% hydrazine hydrate of 1.0% before electrolysis to catholyte, making it fully react, and then add the poly-dithiopropane sodium sulfonate (SPS) of 20mg/L and the polyvinyl alcohol of 20mg/L.By DC electrolysis, under agitation condition (100r/min), be respectively 1000A/m by cathode current density
2, 600A/m
2, 300A/m
2condition under successively electrolysis 8h can obtain comparatively fine and close copper billet.
The copper billet of cathodic deposition is without joint branch, and can not pierce through barrier film and easily peel off shaping, bed Electrowinning of Copper current efficiency is 91.6%, and average deposition copper speed is 1.086g/ (Ah).Copper billet purity is 99.8% after testing.Acidic etching liquid after adjustment regeneration, through this factory eight laminate etching work procedure test, etching factor is 3.8, reaches this factory's acid etching production requirement standard.
Embodiment 2
Acidic etching waste liquid is taken from the acid etching production line of Electronics Factory of Guangdong Province, and solution is blackish green.By analysis, its total copper content is 127.5g/L, HCl content is 64.6g/L, Cl
-content is 273.5g/L.In this, as being anolyte and catholyte, 50% azanol of 0.8% is first added to catholyte before electrolysis, make it fully react, and then add 15mg/L dimethyl formamide base sodium sulfonate (TPS) and poly-dithiopropane sodium sulfonate (SPS) composition, the polyvinyl alcohol of 15mg/L.By DC electrolysis, under agitation condition (200r/min), be respectively 800A/m by cathode current density
2, 500A/m
2, 300A/m
2condition under successively electrolysis 7h can obtain comparatively fine and close copper billet.
The copper billet of cathodic deposition is without joint branch, and can not pierce through barrier film and easily peel off shaping, bed Electrowinning of Copper current efficiency is 93.2%, and average deposition copper speed is 1.105g/ (Ah).Copper billet purity is 99.6% after testing.Acidic etching liquid after adjustment after regeneration, through this factory ten laminate etching work procedure test, etching factor is 3.6, reaches this factory's acid etching production requirement standard.
Embodiment 3
Acidic etching waste liquid is taken from the acid etching production line of Electronics Factory of Guangdong Province, and solution is blackish green.By analysis, its total copper content is 108.2g/L, HCl content is 57.2g/L, Cl
-content is 266.8g/L.In this, as being anolyte and catholyte, first adding 50% hydrazine hydrate of 0.5% before electrolysis to catholyte, making it fully react, and then add 3-sulfydryl-1-propane sulfonic acid sodium (MPS) of 15mg/L and the polyvinyl alcohol of 10mg/L.By DC electrolysis, under agitation condition (150r/min), be respectively 700A/m by cathode current density
2, 500A/m
2, 200A/m
2condition under successively electrolysis 7h can obtain comparatively fine and close copper billet.
The copper billet of cathodic deposition is without joint branch, and can not pierce through barrier film and easily peel off shaping, bed Electrowinning of Copper current efficiency is 92.8%, and average deposition copper speed is 1.096g/ (Ah).After testing, copper billet purity is 99.7%.Acidic etching liquid after adjustment regeneration, through this factory eight laminate etching work procedure test, etching factor is 3.7, reaches this factory's acid etching production requirement standard.
The equipment used in the present invention is conventional equipment.
To one skilled in the art, according to technical scheme described above and design, other various corresponding change and deformation can be made, and all these change and deformation all should belong within the protection domain of the claims in the present invention.
Claims (6)
1. one kind is reclaimed the method for copper from acidic etching waste liquid, it is characterized in that, with the acidic etching waste liquid of PCB etching work procedure discharge for catholyte and anolyte, in catholyte, add promotor, grain-refining agent and leveling agent successively, under agitation condition, cathode current density is 100-1000A/m
2carry out DC electrolysis, after electrolysis 10-30h, namely obtain metallic copper at cathode compartment; Described promotor is the derivative of ammonia, and described grain-refining agent is with sulfonic organic sulfide, and described leveling agent is polyvinyl alcohol.
2. from acidic etching waste liquid, reclaim the method for copper as claimed in claim 1, it is characterized in that, described promotor add-on is the 0.1-5.0% of catholyte volume, and described grain-refining agent and leveling agent add-on are respectively 5-100mg/L.
3. from acidic etching waste liquid, reclaim the method for copper as claimed in claim 1 or 2, it is characterized in that, described stirring velocity is 50r/min-500r/min.
4. from acidic etching waste liquid, reclaim the method for copper as claimed in claim 3, it is characterized in that, described DC electrolysis adopts gradient current density to carry out.
5. from acidic etching waste liquid, reclaim the method for copper as claimed in claim 3, it is characterized in that, described promotor be in hydrazine hydrate, azanol one or both.
6. from acidic etching waste liquid, reclaim the method for copper as claimed in claim 3, it is characterized in that, described grain-refining agent is for gathering any one or more in dithiopropane Huang Suan Na ﹑ dimethyl formamide base sodium sulfonate and 3-sulfydryl-1-propane sulfonic acid sodium.
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| CN201410180467.9A CN103938222B (en) | 2014-04-30 | 2014-04-30 | A kind of method reclaiming copper from acidic etching waste liquid |
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| CN103938222B true CN103938222B (en) | 2016-04-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2715836C1 (en) * | 2019-07-23 | 2020-03-03 | Тураев Дмитрий Юрьевич | Reagent-electrolysis method for regeneration of hydrochloric copper-chloride solutions of copper etching |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451770B (en) * | 2014-12-20 | 2017-01-11 | 井冈山大学 | Combined resource utilization method and device of brownification waste liquid and microetching waste liquid |
| CN110872715A (en) * | 2019-12-03 | 2020-03-10 | 深圳市瑞盛环保科技有限公司 | Acid etching waste liquid electrolysis additive |
| CN111020633A (en) * | 2019-12-23 | 2020-04-17 | 广东臻鼎环境科技有限公司 | Treatment method of acidic etching waste liquid |
| CN112626568A (en) * | 2020-11-23 | 2021-04-09 | 江苏净源新材料有限公司 | Method for preparing copper powder by recovering copper from etching solution and electrolyzing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532136A (en) * | 2009-04-21 | 2009-09-16 | 广州有色金属研究院 | Electrolytic regeneration method of acidic etching waste solution |
| CN102206835A (en) * | 2011-05-19 | 2011-10-05 | 广州鸿葳科技股份有限公司 | Acid etchant online electrolytic recycling device and etchant regenerating method |
-
2014
- 2014-04-30 CN CN201410180467.9A patent/CN103938222B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532136A (en) * | 2009-04-21 | 2009-09-16 | 广州有色金属研究院 | Electrolytic regeneration method of acidic etching waste solution |
| CN102206835A (en) * | 2011-05-19 | 2011-10-05 | 广州鸿葳科技股份有限公司 | Acid etchant online electrolytic recycling device and etchant regenerating method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2715836C1 (en) * | 2019-07-23 | 2020-03-03 | Тураев Дмитрий Юрьевич | Reagent-electrolysis method for regeneration of hydrochloric copper-chloride solutions of copper etching |
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