CN106245058B - A kind of method of copper in electrolytic recovery brown oxide waste liquid - Google Patents
A kind of method of copper in electrolytic recovery brown oxide waste liquid Download PDFInfo
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- CN106245058B CN106245058B CN201610786695.XA CN201610786695A CN106245058B CN 106245058 B CN106245058 B CN 106245058B CN 201610786695 A CN201610786695 A CN 201610786695A CN 106245058 B CN106245058 B CN 106245058B
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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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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of methods of the copper in 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.Treatment process of the present invention is simple, of low cost, environmental-friendly, can brown oxide waste liquid be carried out recycling and obtain two kinds of products of dilute sulfuric acid and copper, there is good economic well-being of workers and staff and environmental benefit.
Description
Technical field
The present invention relates to industrial waste water treatments, and electrolytic recovery copper is pre-processed more particularly, to a kind of brown oxide waste liquid
Method.
Background technology
Printed wiring board (PCB) belongs to electronic equipment manufacturing industry, is to ensure that various electronic components form the flat of electric interconnection
Platform.The polymeric substrate that PCB is used can be the polymer such as epoxy resin or phenol, the polyamide of glass-fiber-fabric enhancing, also may be used
To be other resins etc..One layer of thin copper is covered in polymeric substrate single or double, covers photoresist on copper face, exposed,
After development, etching, line pattern can be formed on copper face, can so produce the wiring board of single or double.
In PCB multilayer board manufacturing process, the problem of typical case, is layered between copper and glue.Brown can prevent copper
It is further corroded, protects copper wire, improve acid resistance, ensure that the quality and performance of PCB multilayer board.Brown process is that copper exists
In acid medium, copper surface is by oxidizing into Cu2O, the cuprous oxide film layer of formation is with fine and close, complete, uniform, thick
The features such as rugosity is consistent, the formation for next step organic metal conversion film provide good physical arrangement.Brown liquid was using
Cheng Zhong is reacted into brown liquid since dissolving can also occur for copper, and after copper ion enrichment, brown liquid will produce due to copper ion is excessive
The quality problems such as raw brown copper face whitens, brown copper face uneven color, so after brown liquid uses to a certain extent, just can only
It is discarded, it is formed containing the sulfuric acid waste containing corrosion inhibiter simultaneously of copper 2%.Brown oxide waste liquid contains higher metallic copper, contains simultaneously
The sulfuric acid of higher COD and 20% or so, so necessary find a kind of effective brown oxide waste liquid processing scheme.
The country has personnel to study the processing of brown oxide waste liquid, is concentrated mainly on following aspect：1st, depositing technology, should
Technique is acid-base neutralization method, is to add in piece alkali into brown oxide waste liquid to neutralize waste water, copper can be converted into precipitation.The program
Simple for process but big with alkali consumption, COD indexs are high, and discharged wastewater met the national standard difficulty is big, and copper resource degree is relatively low.
Brown oxide waste liquid is entered electrolytic wire by the 2nd, electrolysis process using hydrometallurgical principle, and copper is allowed to be realized in cathodic enrichment
Electrolysis, due to the presence of corrosion inhibiter, brown oxide waste liquid can hardly Direct Electrolysis copper.It is introduced in CN201010610128.1 a kind of
It is electrolysed using polyvinyl alcohol and Cericammoniumsulfate is added in as assistant medicament, red cathode copper can be obtained.But by
In introducing other metals and impurity, it is unfavorable for the implementation of circular economy, and electrolytic efficiency is lower, while destroys value
High corrosion inhibiter.
3rd, regeneration, CN201713399U are introduced brown liquid by concentrating, and become the higher concentration of content of copper ion
Liquid, then by crystallisation by cooling be precipitated copper sulfate crystal, make solution content of copper ion reduction, finally by brown liquid effectively into
Divide analysis and regulation, obtain annex solution, be then added in brown production process, achieve the purpose that brown liquid recycles.The program
Although reuse can be carried out to a certain extent, copper sulphate solubility itself is larger, and acidity of sulfuric acid can increase in concentration process,
Corrosion inhibiter can cause to decompose, and can not be back to production by leather-silhouette show completely.
Invention content
In view of the above-mentioned problems existing in the prior art, the applicant provides the copper in a kind of electrolytic recovery brown oxide waste liquid
Method.Treatment process of the present invention is simple, of low cost, environmental-friendly, can by brown oxide waste liquid carry out recycling obtain dilute sulfuric acid and
Two kinds of products of copper, there is good economic well-being of workers and staff and environmental benefit.
Technical scheme is as follows：
A kind of method of copper in electrolytic recovery brown oxide waste liquid, includes the following steps：
(1) brown oxide waste liquid recycles in stripping tower, continues stripping and the oxidizing substance stripping in brown liquid is decomposed removing；
(2) oxidant is passed through in the brown oxide waste liquid of non-oxidative species obtained in (1), is had to influencing Direct Electrolysis
Machine object is removed；
(3) brown oxide waste liquid of blue obtained in (2) is directly entered electrolytic tank electrolysis, you can obtain cathode copper and dilute sulphur
Acid.
Oxidizing substance described in step (1) is hydrogen peroxide, ammonium persulfate or persulfuric acid.
Oxidant in step (2) is ozone or chlorine dioxide, is passed through method as aeration.
Organic matter described in step (2) is 2-mercaptobenzothiazole, that is, MBT, methyl benzotriazole, that is, TTA, 2- (5- amyls
Amine)-benzimidazole, that is, PAB, benzotriazole, that is, BTA, 5- carboxyl benzotriazole, that is, 5-CBTA and 4- carboxyl benzotriazoles, that is, 4-
CBTA。
Electrolytic negative plate in step (3) is titanium plate；Anode plate is lead anode, 80~100A/m of current density2, temperature is
Room temperature.
In above-mentioned steps (1), by stripping, the complete stripping of oxidizing substance in brown oxide waste liquid decomposes, and no longer influences electricity
Solution；In above-mentioned steps (2), the oxidant of addition can be handled the oxidation operation for influencing electrolysis completely；Step (3) electrolysis can
Thorough to carry out, cathode copper can be sold, and dilute sulfuric acid is pure.
The present invention is beneficial to be had technical effect that：
Present invention utilizes advanced blow-off methods to remove the oxide species in waste liquid, and blow-off method is generally used for removal ammonia nitrogen
Class substance is rarely reported the removal of oxidative species (hydrogen peroxide, ammonium persulfate or persulfuric acid)；It is found that in this patent
Influence Direct Electrolysis copper organic matter, be exactly in brown oxide waste liquid carry organic matter, 2-mercaptobenzothiazole, that is, MBT, methylbenzene
Triazole, that is, TTA, 2- (5- amylamines)-benzimidazole, that is, PAB, benzotriazole, that is, BTA, 5- carboxyl benzotriazole, that is, 5-CBTA and 4-
Carboxyl benzotriazole, that is, 4-CBTA gets rid of this kind of substance, waste liquid can Direct Electrolysis go out copper simple substance；This patent uses
Gas strong oxidizer ozone, chlorine dioxide influence the organic matter of cathode copper to remove.
Description of the drawings
Fig. 1 is the process flow diagram that the present invention pre-processes brown oxide waste liquid electrolytic recovery copper.
Specific embodiment
Below in conjunction with the accompanying drawings 1 and embodiment, the present invention is specifically described.
Embodiment 1
The dark-brown brown oxide waste liquid 1000mL of certain PBC manufacturers production line is taken, circulation blow-removing is carried out with small-sized stripping tower,
It maintains 30 minutes；The waste liquid that stripping is completed obtained blue copper-bath with ozonation aerated 20 minutes；Solution is put into electrolytic cell
In be electrolysed, cathode plate is titanium plate；Anode plate is lead anode, current density 80A/m2, temperature is room temperature.Electrolysis obtains 18g
Red copper, colourless electrolyte is dilute sulfuric acid.
Embodiment 2
The dark-brown brown oxide waste liquid 2000mL of certain PBC manufacturers production line is taken, circulation blow-removing is carried out with small-sized stripping tower,
It maintains 30 minutes；The waste liquid that stripping is completed is aerated 30 minutes with chlorine dioxide, obtains blue copper-bath；Solution is put into electricity
It is electrolysed in solution slot, cathode plate is titanium plate；Anode plate is lead anode, current density 90A/m2, temperature is room temperature.Electrolysis obtains
38g red copper, colourless electrolyte is dilute sulfuric acid.
Embodiment 3
The dark-brown brown oxide waste liquid 3000mL of certain PBC manufacturers production line is taken, circulation blow-removing is carried out with small-sized stripping tower,
It maintains 30 minutes；The waste liquid that stripping is completed obtained blue copper-bath with ozonation aerated 20 minutes；Solution is put into electrolytic cell
In be electrolysed, cathode plate is titanium plate；Anode plate is lead anode, current density 100A/m2, temperature is room temperature.Electrolysis obtains 60g
Red copper, colourless electrolyte is dilute sulfuric acid.
In Examples 1 to 3, oxidizing substance is hydrogen peroxide, ammonium persulfate or persulfuric acid.Organic matter is 2- sulfydryl benzos
Thiazole, that is, MBT, methyl benzotriazole, that is, TTA, 2- (5- amylamines)-benzimidazole, that is, PAB, benzotriazole, that is, BTA, 5- carboxyl benzo
Triazole, that is, 5-CBTA and 4- carboxyl benzotriazoles, that is, 4-CBTA.Electrolytic recovery rate >=99.9% of copper, purity >=99.99%,
The dilute sulfuric acid mass fraction of recycling reaches 20%.
Claims (3)
1. the method for the copper in a kind of electrolytic recovery brown oxide waste liquid, it is characterised in that include the following steps：
(1) brown oxide waste liquid recycles in stripping tower, continues stripping and the oxidizing substance stripping in brown liquid is decomposed removing；
(2) oxidant is passed through in the brown oxide waste liquid of non-oxidative species obtained in (1), to influencing the organic matter of Direct Electrolysis
It is removed；
(3) brown oxide waste liquid of blue obtained in (2) is directly entered electrolytic tank electrolysis, you can obtain cathode copper and dilute sulfuric acid；
Oxidant in step (2) is ozone or chlorine dioxide, is passed through method as aeration；
Electrolytic negative plate in step (3) is titanium plate；Anode plate is lead anode, 80~100A/m of current density2, temperature is room temperature.
2. according to the method described in claim 1, it is characterized in that：Oxidizing substance described in step (1) is hydrogen peroxide, mistake
Ammonium sulfate or persulfuric acid.
3. according to the method described in claim 1, it is characterized in that：Organic matter described in step (2) is 2- sulfydryl benzo thiophenes
Azoles, that is, MBT, methyl benzotriazole, that is, TTA, 2- (5- amylamines)-benzimidazole, that is, PAB, benzotriazole, that is, BTA, 5- carboxyl benzo three
Azoles, that is, 5-CBTA and 4- carboxyl benzotriazoles, that is, 4-CBTA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| 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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| 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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| CN106245058A CN106245058A (en) | 2016-12-21 |
| CN106245058B true CN106245058B (en) | 2018-06-19 |
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| 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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| CN102531296B (en) * | 2012-02-14 | 2014-03-12 | 深圳市银台环保工程技术有限公司 | Comprehensive electroplating wastewater treatment method |
| CN103510107B (en) * | 2013-09-24 | 2015-12-23 | 湖南凯天重金属污染治理工程有限公司 | A kind of method reclaiming copper from brown oxide 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 |
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