CN106245058A - A kind of method of the copper in electrolytic recovery brown oxide waste liquid - Google Patents
A kind of method of the copper in electrolytic recovery brown oxide waste liquid Download PDFInfo
- Publication number
- CN106245058A CN106245058A CN201610786695.XA CN201610786695A CN106245058A CN 106245058 A CN106245058 A CN 106245058A CN 201610786695 A CN201610786695 A CN 201610786695A CN 106245058 A CN106245058 A CN 106245058A
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- waste liquid
- copper
- oxide waste
- brown oxide
- brown
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/22—Inorganic acids
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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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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The method that the invention discloses copper in a kind of electrolytic recovery brown oxide waste liquid, brown oxide waste liquid is passed through stripping, oxidation and electrolysis step by this method, brown oxide waste liquid can obtain cathode copper with Direct Electrolysis after pretreatment, so that the copper resource of brown oxide waste liquid is utilized effectively.It is simple that the present invention processes technique, with low cost, and brown oxide waste liquid can be carried out resource and obtain dilute sulfuric acid and two kinds of products of copper, have good economic well-being of workers and staff and environmental benefit by environmental friendliness.
Description
Technical field
The present invention relates to industrial waste water treatment, especially relate to a kind of brown oxide waste liquid pretreatment electrolytic recovery copper
Method.
Background technology
Printed substrate (PCB) belongs to electronic equipment manufacturing industry, is to ensure that various electronic component forms the flat of electric interconnection
Platform.The polymeric substrate that PCB uses can be the epoxy resin that glass-fiber-fabric strengthens, or the polymer such as phenol, polyamide, it is possible to
To be other resins etc..One layer of thin copper is covered at polymeric substrate single or double, covering photoresist on copper face, exposed,
After development, etching, line pattern can be formed on copper face, so can produce the wiring board of single or double.
In PCB multilayer board manufacture process, a typical problem is to occur layering between copper and glue.Brown can prevent copper
It is corroded further, protects copper wire, improve acid resistance, it is ensured that the quality of PCB multilayer board and performance.Brown process is that copper exists
In acid medium, oxidized dose of copper surface is oxidized to Cu2O, the Red copper oxide film layer of formation have densification, complete, uniformly, thick
The features such as rugosity is consistent, for the physical arrangement that the formation offer of next step organic metal conversion film is good.Brown liquid was using
Cheng Zhong, also can occur dissolving to be reacted into brown liquid due to copper, and after copper ion enrichment, brown liquid too much will produce because of copper ion
Raw brown copper face turns white, the unequal quality problem of brown copper face color and luster, so after brown liquid uses to a certain extent, just can only
Discarded, form the sulfuric acid waste simultaneously containing corrosion inhibiter containing copper 2%.Brown oxide waste liquid contains higher metallic copper, contains simultaneously
Higher COD, and the sulphuric acid of about 20%, find a kind of effective brown oxide waste liquid processing scheme so necessary.
The process of brown oxide waste liquid is studied by the domestic personnel of having, and is concentrated mainly on following aspect: 1, depositing technology, should
Technique is acid-base neutralization method, is to add sheet alkali in brown oxide waste liquid to be neutralized waste water, and copper can be converted into precipitation.The program
Technique is simple, but it is big to have alkali consumption, and COD index is high, and discharged wastewater met the national standard difficulty is big, and copper resource degree is relatively low.
2, electrolysis process, utilizes the principle of hydrometallurgy that brown oxide waste liquid is entered electrolytic wire, allows copper realize at cathodic enrichment
Electrolysis, due to the existence of corrosion inhibiter, brown oxide waste liquid is little to Direct Electrolysis copper.CN201010610128.1 introduces one
Use addition polyvinyl alcohol and Cericammoniumsulfate to be electrolysed as assistant medicament, the cathode copper of redness can be obtained.But by
In introducing other metals and impurity, and it is unfavorable for the implementation of recycling economy, and electrolytic efficiency step-down, destroys value simultaneously
High corrosion inhibiter.
3, regeneration, CN201713399U introduces brown liquid through concentrating, becomes the concentration that content of copper ion is higher
Liquid, is then passed through crystallisation by cooling and separates out copper sulfate crystal, make solution content of copper ion reduce, effectively become finally by brown liquid
Divide analysis and regulation, obtain annex solution, be then added in brown production process, reach the purpose that brown liquid recycles.The program
Although reuse can be carried out to a certain extent, but the dissolubility of copper sulfate own is relatively big, and in concentration process, acidity of sulfuric acid can uprise,
Corrosion inhibiter can cause decomposition, can not is not back to produce by leather-silhouette show.
Summary of the invention
The problems referred to above existed for prior art, the applicant provides the copper in a kind of electrolytic recovery brown oxide waste liquid
Method.It is simple that the present invention processes technique, with low cost, environmental friendliness, brown oxide waste liquid can be carried out resource obtain dilute sulfuric acid and
Two kinds of products of copper, have good economic well-being of workers and staff and environmental benefit.
Technical scheme is as follows:
The method of the copper in a kind of electrolytic recovery brown oxide waste liquid, comprises the following steps:
(1) brown oxide waste liquid circulates in stripping tower, continues stripping and the oxidizing substance stripping in brown liquid is decomposed removing；
(2) brown oxide waste liquid of the non-oxidative species obtained in (1) is passed through oxidant, on having of affecting Direct Electrolysis
Machine thing is removed；
(3) the blue brown oxide waste liquid obtained in (2) is directly entered electrolytic tank electrolysis, i.e. can get cathode copper and dilute sulfur
Acid.
Oxidizing substance described in step (1) is hydrogen peroxide, Ammonium persulfate. or persulfuric acid.
Oxidant in step (2) is ozone or chlorine dioxide, and the method for being passed through is aeration.
Organic substance described in step (2) is 2-mercaptobenzothiazole i.e. MBT, methyl benzotriazole i.e. TTA, 2-(5-amyl group
Amine)-benzimidazole i.e. PAB, the benzotriazole i.e. i.e. 4-of BTA, 5-carboxyl benzotriazole i.e. 5-CBTA and 4-carboxyl benzotriazole
CBTA。
Electrolytic negative plate in step (3) is titanium plate；Positive plate is lead anode, electric current density 80～100A/m2, temperature is
Room temperature.
In above-mentioned steps (1), the complete stripping of oxidizing substance in stripping, brown oxide waste liquid decomposes, and no longer affects electricity
Solve；In above-mentioned steps (2), the oxidation operation of impact electrolysis can be processed completely by the oxidant of addition；Step (3) electrolysis can
To carry out thoroughly, cathode copper can be sold, and dilute sulfuric acid is pure.
Useful the having the technical effect that of the present invention
Present invention utilizes advanced person blow-off method to the oxide species removing in waste liquid, blow-off method be generally used for remove ammonia nitrogen
Class material, the removal for oxidative species (hydrogen peroxide, Ammonium persulfate. or persulfuric acid) rarely has report；This patent is found that
Affect the Organic substance of Direct Electrolysis copper, it is simply that the Organic substance carried in brown oxide waste liquid, 2-mercaptobenzothiazole i.e. MBT, methylbenzene
Triazole i.e. TTA, 2-(5-amylamine)-benzimidazole i.e. PAB, benzotriazole i.e. BTA, 5-carboxyl benzotriazole i.e. 5-CBTA and 4-
Carboxyl benzotriazole i.e. 4-CBTA, gets rid of this kind of material, and waste liquid just can be with Direct Electrolysis copper simple substance；This patent uses
Gas strong oxidizer ozone, chlorine dioxide remove the Organic substance affecting cathode copper.
Accompanying drawing explanation
Fig. 1 is the present invention process flow diagram to brown oxide waste liquid pretreatment electrolytic recovery copper.
Detailed description of the invention
Below in conjunction with the accompanying drawings 1 and embodiment, the present invention is specifically described.
Embodiment 1
Take the dark-brown brown oxide waste liquid 1000mL of certain PBC manufacturer production line, be circulated stripping with small-sized stripping tower,
Maintain 30 minutes；The waste liquid that stripping completes, with ozonation aerated 20 minutes, obtains blue copper-bath；Solution is put into electrolysis bath
In be electrolysed, minus plate is titanium plate；Positive plate is lead anode, electric current density 80A/m2, temperature is room temperature.Electrolysis obtains 18g
Red copper, electrolyte is colourless for dilute sulfuric acid.
Embodiment 2
Take the dark-brown brown oxide waste liquid 2000mL of certain PBC manufacturer production line, be circulated stripping with small-sized stripping tower,
Maintain 30 minutes；The waste liquid chlorine dioxide aeration that stripping completes 30 minutes, obtains blue copper-bath；Solution is put into electricity
Solving in groove and be electrolysed, minus plate is titanium plate；Positive plate is lead anode, electric current density 90A/m2, temperature is room temperature.Electrolysis obtains
38g redness copper, electrolyte is colourless for dilute sulfuric acid.
Embodiment 3
Take the dark-brown brown oxide waste liquid 3000mL of certain PBC manufacturer production line, be circulated stripping with small-sized stripping tower,
Maintain 30 minutes；The waste liquid that stripping completes, with ozonation aerated 20 minutes, obtains blue copper-bath；Solution is put into electrolysis bath
In be electrolysed, minus plate is titanium plate；Positive plate is lead anode, electric current density 100A/m2, temperature is room temperature.Electrolysis obtains 60g
Red copper, electrolyte is colourless for dilute sulfuric acid.
In embodiment 1～3, oxidizing substance is hydrogen peroxide, Ammonium persulfate. or persulfuric acid.Organic substance is 2-sulfydryl benzo
Thiazole i.e. MBT, methyl benzotriazole i.e. TTA, 2-(5-amylamine)-benzimidazole i.e. PAB, benzotriazole i.e. BTA, 5-carboxyl benzo
Triazole i.e. 5-CBTA and the 4-i.e. 4-CBTA of carboxyl benzotriazole.Electrolytic recovery rate >=99.9% of copper, its purity >=99.99%,
The dilute sulfuric acid mass fraction reclaimed reaches 20%.
Claims (5)
1. the method for the copper in an electrolytic recovery brown oxide waste liquid, it is characterised in that comprise the following steps:
(1) brown oxide waste liquid circulates in stripping tower, continues stripping and the oxidizing substance stripping in brown liquid is decomposed removing；
(2) brown oxide waste liquid of the non-oxidative species obtained in (1) is passed through oxidant, on the Organic substance affecting Direct Electrolysis
It is removed；
(3) the blue brown oxide waste liquid obtained in (2) is directly entered electrolytic tank electrolysis, i.e. can get cathode copper and dilute sulfuric acid.
Method the most according to claim 1, it is characterised in that: the oxidizing substance described in step (1) is hydrogen peroxide, mistake
Ammonium sulfate or persulfuric acid.
Method the most according to claim 1, it is characterised in that: the oxidant in step (2) is ozone or chlorine dioxide
Body, the method for being passed through is aeration.
Method the most according to claim 1, it is characterised in that: the Organic substance described in step (2) is 2-sulfydryl benzo thiophene
Azoles i.e. MBT, methyl benzotriazole i.e. TTA, 2-(5-amylamine)-benzimidazole i.e. PAB, benzotriazole i.e. BTA, 5-carboxyl benzo three
Azoles i.e. 5-CBTA and the 4-i.e. 4-CBTA of carboxyl benzotriazole.
Method the most according to claim 1, it is characterised in that: the electrolytic negative plate in step (3) is titanium plate；Positive plate is
Lead anode, electric current density 80～100A/m2, temperature is room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610786695.XA CN106245058B (en) | 2016-08-30 | 2016-08-30 | A kind of method of copper in electrolytic recovery brown oxide waste liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610786695.XA CN106245058B (en) | 2016-08-30 | 2016-08-30 | A kind of method of copper in electrolytic recovery brown oxide waste liquid |
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| Publication Number | Publication Date |
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| CN106245058A true CN106245058A (en) | 2016-12-21 |
| CN106245058B CN106245058B (en) | 2018-06-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610786695.XA Active CN106245058B (en) | 2016-08-30 | 2016-08-30 | A kind of method of copper in electrolytic recovery brown oxide waste liquid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114293205A (en) * | 2021-12-17 | 2022-04-08 | 新疆新能源(集团)准东环境发展有限公司 | Device and method for recovering and treating PVC acetylene purification waste sulfuric acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531296A (en) * | 2012-02-14 | 2012-07-04 | 深圳市银台环保工程技术有限公司 | Comprehensive electroplating wastewater treatment method |
| CN103510107A (en) * | 2013-09-24 | 2014-01-15 | 湖南凯天重金属污染治理工程有限公司 | Method for recovering copper from brownification waste liquid |
| CN104372376A (en) * | 2014-06-20 | 2015-02-25 | 商实企业有限公司 | Method for recovering copper from brown oxidation waste liquid |
| CN105502760A (en) * | 2015-12-23 | 2016-04-20 | 苏州卓融新能源科技有限公司 | Browning wastewater treatment process |
| CN105714280A (en) * | 2016-04-06 | 2016-06-29 | 武汉创新特科技有限公司 | Browning treatment liquid for printed circuit board |
-
2016
- 2016-08-30 CN CN201610786695.XA patent/CN106245058B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531296A (en) * | 2012-02-14 | 2012-07-04 | 深圳市银台环保工程技术有限公司 | Comprehensive electroplating wastewater treatment method |
| CN103510107A (en) * | 2013-09-24 | 2014-01-15 | 湖南凯天重金属污染治理工程有限公司 | Method for recovering copper from brownification waste liquid |
| CN104372376A (en) * | 2014-06-20 | 2015-02-25 | 商实企业有限公司 | Method for recovering copper from brown oxidation waste liquid |
| CN105502760A (en) * | 2015-12-23 | 2016-04-20 | 苏州卓融新能源科技有限公司 | Browning wastewater treatment process |
| CN105714280A (en) * | 2016-04-06 | 2016-06-29 | 武汉创新特科技有限公司 | Browning treatment liquid for printed circuit board |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114293205A (en) * | 2021-12-17 | 2022-04-08 | 新疆新能源(集团)准东环境发展有限公司 | Device and method for recovering and treating PVC acetylene purification waste sulfuric acid |
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| CN106245058B (en) | 2018-06-19 |
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