CN106480474A - A kind of device of electrolytic acid copper chloride - Google Patents
A kind of device of electrolytic acid copper chloride Download PDFInfo
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- CN106480474A CN106480474A CN201510546470.2A CN201510546470A CN106480474A CN 106480474 A CN106480474 A CN 106480474A CN 201510546470 A CN201510546470 A CN 201510546470A CN 106480474 A CN106480474 A CN 106480474A
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- electrolyte
- pond
- electroplating pool
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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
The present invention relates to a kind of device of electrolytic acid copper chloride, including electrochemical pond (400) and electroplating pool (100)；In described electrification pond (400), described electrification pond (400) is divided into cathode chamber (410) and anode chamber (420) by ionic membrane, it is provided with positive plate (430) in cathode chamber (410), in anode chamber (420), be provided with negative plate (440)；Described electroplating pool (100) passes through pipeline communication with described anode chamber (420), electrolyte (200) in described electroplating pool (100) is pumped to described anode chamber (420), is pumped back to described electroplating pool (100) after reducing oxidation-reduction potential.Electrolyte is circulated in the anode chamber in electrochemical pond and electroplating pool, the state modulator making electrolyte controls all the time in OK range, being not required to just can be with electrolyzing copper with ionic membrane, and the copper being electrolysed out is attached to negative pole outer surface and smooth one-tenth is block, has higher recovery value.
Description
Technical field
The present invention relates to the electrolysis for production technology of copper, in particular, it is related to a kind of electrolytic acid copper chloride
Device.
Background technology
Acidic copper chloride is that Copper Ores are smelted, reclaimed conventional etching media during copper in old metal, leads to
Copper people in the copper-containing substances such as Copper Ores, old metal is dissolved in etching media by the mode crossing electrochemical reaction,
Obtain the very high acid chlorization copper liquor of copper ion concentration, also referred to as etching solution.In prior art from
Electrolytic recovery copper in acid copper chloride etching liquid, is all, with ionic membrane, etching solution is divided into two halves.On one side
For cathode chamber, it is used for putting into positive pole, another side is anode chamber, is used for putting into negative pole.Erosion in cathode chamber
Carve liquid because the Oxidation of positive pole, make the oxidation-reduction potential (abbreviation ORP) of etching solution in cathode chamber
More and more high, just separate out chlorine to last.Anode chamber etching solution because negative pole reduction, make
More and more low to etching solution ORP of anode chamber, last negative electricity solves metallic copper；But electrolysis gold out
Belong to copper very coarse, generally become copper powder state, also referred to as copper sludge, be deposited on the electroplating pool below negative pole
Bottom, needs further refine just can be reclaimed and use.
Content of the invention
The technical problem to be solved is, provides a kind of device of electrolytic acid copper chloride, solution
The metallic copper separating electroplating pool using ionic membrane, electrolysis obtains certainly is needed to be powdery, recovery in prior art
The problems such as be worth high.
The scheme that the present invention solves above-mentioned technical problem is to provide a kind of device of electrolytic acid copper chloride,
Including electrochemical pond and electroplating pool；In described electrification pond, described electrification pond is divided into cathode chamber by ionic membrane
And anode chamber, it is provided with positive plate in cathode chamber, in anode chamber, be provided with negative plate；Described electroplating pool with
Described anode chamber passes through pipeline communication, and the electrolyte in described electroplating pool is pumped to described anode chamber, reduces
It is pumped back to described electroplating pool after oxidation-reduction potential.
In the device of the electrolytic acid copper chloride that the present invention provides, in described electroplating pool, it is provided with staggered row
The positive plate of row and negative plate, copper separates out on negative plate surface.
The present invention provide electrolytic acid copper chloride device in, described electrification pond in electrolyte, electricity
In solution preocess, oxidation-reduction potential can rise, and is pumped to when the oxidation-reduction potential of electrolyte is higher than threshold value
Described anode chamber, is pumped back to described electroplating pool after the oxidation-reduction potential of described anode chamber reduction electrolyte.
Electricity in the device of the electrolytic acid copper chloride that the present invention provides, in described electrification pond and electroplating pool
Solution liquid recycle stream moves, and nationality is to control the oxidation-reduction potential in electrolyte.
In the device of the electrolytic acid copper chloride that the present invention provides, in described electrification pond, negative plate electric current
Density is less than 1A/dm2, it is aqueous sulfuric acid in cathode chamber.
Implement the present invention, have the advantages that：By the anode chamber in electrochemical pond for the electrolyte and electroplating pool
So that the state modulator of electrolyte controls all the time in OK range, being not required to can with ionic membrane for middle circulation
With electrolyzing copper, and the copper being electrolysed out is attached to negative pole outer surface and smooth one-tenth is block, has higher
Recovery value.
Brief description
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to reality
The accompanying drawing applying required use in example or description of the prior art be briefly described it should be apparent that, below
Accompanying drawing in description is only some embodiments of the present invention, for those of ordinary skill in the art,
On the premise of not paying creative work, can also obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is the structural representation of electrolytic acid copper chloride device preferred embodiment of the present invention.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out
Clearly and completely describe it is clear that described embodiment is only a part of embodiment of the present invention, and
It is not all, of embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art are not doing
The every other embodiment being obtained on the premise of going out creative work, broadly falls into the scope of protection of the invention.
In the technology of existing electrolytic recovery copper from acid copper chloride etching liquid, need using ionic membrane handle
Etching solution is divided into two halves, but the various ions in etching solution cannot be unobstructed by ionic membrane electronics,
In electrolytic process, bivalent cupric ion is reduced in negative pole, thus being electrolysed out metallic copper.The main wound of the present invention
New point is, separates electrolyte without using ionic membrane, and positive plate and negative plate are co-located in electroplating pool,
Electrolyte is circulated in the anode chamber in electrochemical pond and electroplating pool the oxidation-reduction potential ginseng so that electrolyte
Numerical control system controls all the time in OK range, coordinates the control of other aspect parameters, accurately controls electroplating pool
Erosiveness and throwing power, make metallic copper slowly from negative plate separate out and can smooth become bulk.
Fig. 1 shows the structure of electrolytic acid copper chloride device preferred embodiment of the present invention, as shown in figure 1,
The device of electrolytic acid copper chloride includes electroplating pool 100 and electrochemical pond 400.
In electroplating pool 100, need not ionic membrane be set, staggered positive plate 301,303,305 and negative
Pole piece 302,304 is immersed in electrolyte 200, copper ion with negative plate reduction in negative plate
Surface separates out, and the such as both sides of positive pole 303 are negative plate 302,304, and the both sides of negative plate 302 are just
Pole piece 301,303, the quantity of positive plate and negative plate can be reclaimed speed and be done with electroplating pool 100 size, copper
Suitably adjust, the quantity of positive plate and negative plate is more, it is faster that copper reclaims speed.Certainly, in electroplating pool
100 less when, a positive plate and negative plate can also realize the electroplating process of the present invention.By control
Parameter in electrolytic process processed, accurately controls erosiveness and the throwing power of electroplating pool 100, metallic copper
Slowly from negative plate surface separate out and can smooth become bulk
In the electrochemical pond 400 of the present embodiment, electrochemical pond 400 is divided into cathode chamber 410 He by ionic membrane
Anode chamber 420, is provided with positive plate 430, is provided with negative plate 440 in anode chamber 420 in cathode chamber 410,
It is same electrolyte 200 in anode chamber 420 and electroplating pool 100, be simply electrolysed with electroplating pool 100
The carrying out of process, oxidation-reduction potential can rise, when ORP is excessive, the erosiveness of electrolyte 200
Also bigger than throwing power, so precipitation copper cannot be electrolysed in electroplating pool 100.By electroplating pool 100 and negative pole
Pipeline communication is passed through in room 420, and the ORP of the electrolyte 200 in electroplating pool 100 is pumped to negative pole after raising
Room 420, after reducing oxidation-reduction potential by the reduction of anode chamber 420, is pumped back to electroplating pool
100.Circulated in the anode chamber 420 in electrochemical pond 400 and electroplating pool 100 by electrolyte 200 so that
All the time in OK range, the electrolysis that can continue in electroplating pool 100 separates out copper to the parameter of electrolyte 200.
Preferably, in electrochemical pond 400, negative plate 430 electric current density is less than 1A/dm2So that in anode chamber 420
Bivalent cupric ion Cu in electrolyte 2002+It is reduced to univalent copper ion Cu+, without being reduced to
Metallic copper separates out from negative plate, decreases bivalent cupric ion Cu in electrolyte 2002+Quantity, ORP is dropped
Low；It is aqueous sulfuric acid in cathode chamber 410 in electrochemical pond 400 as conducting medium, such as volume fraction
Aqueous sulfuric acid for 10%.
In the anode chamber 420 in electrochemical pond 400 and electroplating pool 100, the electrolyte 200 of circulation is acid chlorine
Change copper liquor, formed for mother liquor using acid copper chloride etching liquid, usual acidic copper chloride etching
Copper ion concentration in liquid, chlorine ion concentration, oxidation-reduction potential (abbreviation ORP) are all higher, no
Copper removal process can be completed directly as electrolyte 200.Now list the several of general acidic chlorination copper etchant solution
Item conventional parameter is as follows：
Copper content：100g/l～160g/l
Acidity：1.0N～3.0N
ORP：430mv～550mv
Chloride ion：200g/l～280g/l.
In the electroplating pool 100 of the present invention, control electrolyte 200 parameter is：
Copper ion concentration：15g/l～55g/l
Oxidation-reduction potential：250mv～380mv
Cathodal current density：3.0A/dm2～6.0A/dm2
Acidity 0.5N～3.0N
Chlorine ion concentration is 100g/l～280g/l
Positive pole electric current density 2.0A/dm2～12.0A/dm2.
For the work process of the clearer explanation present invention, now with regard to changing in electroplating pool 100 and controlling ginseng
The process of number is explained as follows one by one：
(1) copper ion concentration：During beginning, copper chloride acid etching liquid dilute with water can be made copper content
Drop to above-mentioned parameter scope.Copper ion can be become copper billet by cathodic reduction afterwards, is affixed on negative plate,
Copper ion concentration constantly declines, and requires supplementation with into acidic etching liquid to maintain copper ion concentration in above-mentioned parameter
Scope.
(2) oxidation-reduction potential：ORP is bivalent cupric ion Cu in electrolyte 2002+With univalent copper ion
Cu+Ratio, i.e. bivalent cupric ion Cu in electrolyte 2002+More, ORP is just higher.Make in the present invention
In above-mentioned electroplating pool 100, when ORP is too high, the erosiveness of electrolyte 200 compares throwing power
Also big, negative pole just cannot separate out copper, so reducing ORP with electrochemical pond 400.
(3) cathodal current density：In electrolytic process, cathodal current density maintains in the range of above-mentioned parameter.
(4) acidity：In electrolytic process, copper ion is changed into copper, releases the hydrochloric acid of complexation, thus sour
Degree can rise gradually, to saturation during 3.0N.But the change of acidity affects on the efficiency of electrolytic copper and the quality of copper
Less.
(5) chlorine ion concentration：Chloride ion affects less on the quality of electrolytic efficiency and copper, as long as keeping chlorine
It is just permissible that ion is not more than 280g/l.Being continuously replenished in the case that etching solution enters electroplating pool 100, chlorine from
Son can rise to identical with chlorine ion concentration in etching solution gradually.
(6) positive pole electric current density：Positive pole electric current density affects less on the quality of electrolytic efficiency and copper, only
Electric current density is wanted to be not more than 12A/dm2With regard to permissible.
(7) stir：In electrolytic process, electrolyte 200 does not stir, and the adding procedure of etching solution is with steady
Slowly it is advisable, does not play the effect of stirring, such negative plate outer surface has coated univalent copper ion layer, one
Valency copper ion layer outer cladding bivalent cupric ion layer.Univalent copper ion layer and bivalent cupric ion layer meet folder
Layer state is so that the metallic copper quality separating out on negative plate is more homogeneous, molding is more complete, surface more light
Sliding.
In the present invention, electrolyte 200 is followed in the anode chamber 420 in electrochemical pond 400 and electroplating pool 100
Ring is so that the oxidation-reduction potential of electrolyte 200 controls all the time in OK range, in order to clearer
The control process of the oxidation-reduction potential of electrolyte 200 is described, following of multiple electrolyte 200 can be adopted
Ring mode, substantially can be divided into discontinuous circulation and continuous circulation, and for example, discontinuous circulation is typically
By the ORP setting highest threshold value of electrolyte 200 in electroplating pool 100, with electrolyte 200 electrolytic process
Carrying out, ORP can rise, when the oxidation-reduction potential of electrolyte 200 is higher than highest threshold value, plating
Pond 100 quits work, and electrolyte 200 is pumped into anode chamber 420, and anode chamber 420 reduces electrolyte 200
ORP to OK range when, that is, be pumped back to electroplating pool 100, open electroplating pool 100 and continue copper and reclaimed
Journey.Continuous circulation then can not stop electroplating pool 100, but by electrochemical pond 400 and electroplating pool 100
Electrolyte 200 circulates, and the electrolyte 200 in electroplating pool 100 is pumped into electrification with certain speed
Pond 400, simultaneously the electrolyte 200 in electrochemical pond 400 electroplating pool 100 is pumped into certain speed, only need
Electrolyte 200 oxidation-reduction potential in electroplating pool 100 to be maintained is in the range of suitable parameters.
Claims (5)
1. a kind of device of electrolytic acid copper chloride is it is characterised in that include electrochemical pond (400) and electricity
Plating pond (100)；In described electrification pond (400), described electrification pond (400) is divided into by ionic membrane
Cathode chamber (410) and anode chamber (420), are provided with positive plate (430) in cathode chamber (410), bear
It is provided with negative plate (440) in pole room (420)；Described electroplating pool (100) and described anode chamber (420)
By pipeline communication, the electrolyte (200) in described electroplating pool (100) is pumped to described anode chamber (420),
It is pumped back to described electroplating pool (100) after reducing oxidation-reduction potential.
2. the device of electrolytic acid copper chloride according to claim 1 is it is characterised in that described electricity
Be provided with plating pond (100) staggered positive plate (301,303,305) and negative plate (302,
304), copper separates out on negative plate (302,304) surface.
3. the device of electrolytic acid copper chloride according to claim 1 is it is characterised in that described electricity
Change the electrolyte (200) in pond (400), in electrolytic process, oxidation-reduction potential can rise, and works as electrolyte
(200) oxidation-reduction potential is pumped to described anode chamber (420), described anode chamber when being higher than threshold value
(420) it is pumped back to described electroplating pool (100) after the oxidation-reduction potential reducing electrolyte (200).
4. the device of electrolytic acid copper chloride according to claim 1 is it is characterised in that described electricity
The electrolyte (200) changed in pond (400) and electroplating pool (100) circulates, and nationality is to control electrolyte
In oxidation-reduction potential.
5. the device of electrolytic acid copper chloride according to claim 1 is it is characterised in that described electricity
Change in pond (400), negative plate electric current density is less than 1A/dm2, it is that sulphuric acid is water-soluble in cathode chamber (410)
Liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510546470.2A CN106480474A (en) | 2015-08-31 | 2015-08-31 | A kind of device of electrolytic acid copper chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510546470.2A CN106480474A (en) | 2015-08-31 | 2015-08-31 | A kind of device of electrolytic acid copper chloride |
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| Publication Number | Publication Date |
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| CN106480474A true CN106480474A (en) | 2017-03-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510546470.2A Pending CN106480474A (en) | 2015-08-31 | 2015-08-31 | A kind of device of electrolytic acid copper chloride |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113774430A (en) * | 2021-09-15 | 2021-12-10 | 广东德同环保科技有限公司 | Equipment and method for electrolyzing acidic etching solution without chlorine gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1215099A (en) * | 1997-10-21 | 1999-04-28 | 奥克斯累研究股份有限公司 | Apparatus and process for regenrating CuClz etchant solution |
| CN201501929U (en) * | 2009-08-18 | 2010-06-09 | 李海涛 | Recycling device for on-line extraction of copper and etching solution of chloride system circuit board etching solution |
| CN103422154A (en) * | 2012-05-24 | 2013-12-04 | 叶福祥 | Cuprous chloride (Cu+, cuCL) ion diaphragm electrodeposition regeneration of circuit board acidic waste etching solution |
| CN204959050U (en) * | 2015-08-31 | 2016-01-13 | 东莞市锦卫水处理设备有限公司 | Device of acid copper chloride of electrolysis |
-
2015
- 2015-08-31 CN CN201510546470.2A patent/CN106480474A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1215099A (en) * | 1997-10-21 | 1999-04-28 | 奥克斯累研究股份有限公司 | Apparatus and process for regenrating CuClz etchant solution |
| CN201501929U (en) * | 2009-08-18 | 2010-06-09 | 李海涛 | Recycling device for on-line extraction of copper and etching solution of chloride system circuit board etching solution |
| CN103422154A (en) * | 2012-05-24 | 2013-12-04 | 叶福祥 | Cuprous chloride (Cu+, cuCL) ion diaphragm electrodeposition regeneration of circuit board acidic waste etching solution |
| CN204959050U (en) * | 2015-08-31 | 2016-01-13 | 东莞市锦卫水处理设备有限公司 | Device of acid copper chloride of electrolysis |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113774430A (en) * | 2021-09-15 | 2021-12-10 | 广东德同环保科技有限公司 | Equipment and method for electrolyzing acidic etching solution without chlorine gas |
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Effective date of registration: 20180906 Address after: 528203 4, 401, dun Shang Road, Jiujiang Town, Nanhai District, Foshan, Guangdong, 401 (residence declaration) Applicant after: Guangdong Tatong Environmental Protection Technology Co., Ltd. Address before: 523936 Guangdong province Dongguan city Humen Town Sha Jiao management area Lantau Peak Phoenix two road Applicant before: DONGGUAN JINWEI WATER TREATMENT EQUIPMENT CO., LTD. |
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Application publication date: 20170308 |