CN201686753U - Electrolysis device for extracting copper through electrolysis of alkaline waste etching solution - Google Patents

Electrolysis device for extracting copper through electrolysis of alkaline waste etching solution Download PDF

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Publication number
CN201686753U
CN201686753U CN2010201941457U CN201020194145U CN201686753U CN 201686753 U CN201686753 U CN 201686753U CN 2010201941457 U CN2010201941457 U CN 2010201941457U CN 201020194145 U CN201020194145 U CN 201020194145U CN 201686753 U CN201686753 U CN 201686753U
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electrolyzer
etching solution
electrolysis
copper
liquid
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CN2010201941457U
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Chinese (zh)
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王红雨
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The utility model discloses an electrolysis device for extracting copper through electrolysis of alkaline waste etching solution, and the electrolysis device comprises an electrolysis bath and at least one polar plate group arranged in the electrolysis bath, wherein each polar plate group consists of an anode and two cathodes. The electrolysis device can lead the electrolysis efficiency to achieve more than 90% and reduce the power consumption by about 30%.

Description

Be used for alkaline spent etching solution electrolysis and carry the electrolyzer of copper
Technical field
The utility model relates to a kind of electrolyzer, particularly the electrolyzer of electrowinning metallic copper from alkaline spent etching solution.
Background technology
Basis as electronic industry, information industry and household electric appliances, the printed circuit board enterprise of one of external heavy polluted industry shifts to China one after another over nearly 20 years, makes PCB (printed circuit board) industry of China keep 10~12% annual growth rate in recent years always.More than 3500 families of PCB enterprise of multiple scale are arranged at present, and annual production reaches 1.2 hundred million square metres, leaps to first of the whole world.Annual PCB enterprise mean consumption copper is more than 200,000 tons, and copper content has constituted serious harm more than 80,000 tons to the society especially water resources of PCB surrounding area in the waste liquid of output (spent etching solution).Etching is to consume the maximum operation of liquid medicine amount during PCB produces, and also is to produce waste liquid (being so-called Hazardous wastes---spent etching solution, by the waste separation name of State Environmental Protection Administration) and the maximum operation of waste water (being once washing waste water and secondary washing waste water).Generally speaking, it is 2~3 liters that the dual platen of one square metre of normal thickness of every production (18 μ m) consumes etching solution, and produces 2~3 liters of spent etching solutions, 50~75 liters of once washing waste water, 80~100 liters of secondary washing waste water.Present way be regularly or not timing ground from the very high spent etching solution of etching bath discharge section copper content, simultaneously to wherein adding new liquid medicine.Usually the best copper concentration in the etching solution is at 110~130 grams per liters, and when effluxing, then wishes copper concentration high more good more (usually at 150~160 grams per liters), to improve the etching solution utilising efficiency as far as possible, reduces the total usage quantity of solution.
On Financial cost, present way is unfavorable to PCB enterprise, and these enterprises need spend considerable cost constantly to buy new etching solution on the one hand, and the useful component beyond the copper removal all is dropped in the spent etching solution.For some small-sized PCB enterprises, they directly efflux spent etching solution especially, and copper wherein also abandons in the lump.On the other hand, the spent etching solution of discharging is worth not only can't offset the expense of buying new etching solution, the treatment cost of blowdown is also extremely expensive, spent etching solution is taked the area of special measure of control at some, spent etching solution is gratuitously taken away or bargain purchase by third party enterprise, when polluting transfer, also reduced the prospect interest of PCB enterprise.
At present, separating copper from spent etching solution usually, and, make spent solution regeneration by replenishing or adjusting other non-copper components, be recycled in the etch process.Processing spent etching solution commonly used is to reclaim wherein copper and the method for the etching solution of regenerating mainly contains extraction reextraction electrolytic process, membrane sepn electrolytic process and direct electrolysis method.
Extraction reextraction electrolytic process needs extraction agent, and extraction agent is limited work-ing life, and need be to the extraction agent subsequent disposal.Because residual extraction agent in the regeneration after etching liquid, etch-rate reduces, and cycle index is limited.This method complicated operation, operation are many, and occupation area of equipment is big, also has the secondary pollution problem.
Though it is simple to operate that the membrane sepn electrolytic process has, the advantage that floor space is little, this method will be used separatory membrane, and the cost that film is changed is very high, this method power consumption is also high simultaneously.And the ammonia escaped quantity is big in the electrolytic process, needs a large amount of ammonia that replenish during the regeneration etching solution.
Comparatively speaking, the direct electrolysis method energy consumption is low, working cost is low, easy and simple to handle, occupation area of equipment is little, environment is not polluted, and regenerated etching solution etching quality is stable.
It is still higher that yet directly the electrolytic efficiency and the energy consumption of copper put forward in electrolysis, thereby be necessary to improve electrolyzer with further raising electrolytic efficiency with cut down the consumption of energy.
The utility model content
At above problem, the purpose of this utility model provides a kind of electrolytic efficiency that can make and reaches more than 90%, and power consumption reduces about 30% the electrolyzer that copper is carried in alkaline spent etching solution electrolysis that is used for.
For this reason, provide a kind of electrolyzer that alkaline spent etching solution is carried copper that is used for.Described electrolyzer comprises electrolyzer; At least one group of pole plate group with being arranged on described electrolyzer inside is characterized in that, each described pole plate group is made up of a slice anode and a slice negative electrode.
According to preferred embodiment, described electrolyzer further comprises: the liquid-inlet pipe that is arranged in described bottom of electrolytic tank; Be arranged in the drain pipe at described electrolyzer top; With the circulation groove that contiguous described electrolyzer is provided with, wherein said liquid-inlet pipe and described drain pipe have the opening that is arranged in the circulation groove respectively.
The aperture that has many upward openings on the tube wall of preferred described liquid-inlet pipe.More preferably described liquid-inlet pipe is for example arranged with the S type so that described aperture is evenly distributed on the mode of the bottom of electrolyzer arranges.
In addition, described circulation groove has the volume that can hold or more electrolytic solution essentially identical with described electrolyzer.
According to the embodiment of optimum, the distance between described negative plate and described positive plate is 40cm, and described negative plate and described positive plate have the size of 1200mm * 1000mm respectively.
Electrolyzer of the present utility model has by a slice anode and two pole plate groups that negative electrode is formed, compare with traditional pole plate group of forming by a slice anode and a slice negative electrode, the cathode area of cupric ion contact is multiplied, thereby improved electrolytic efficiency greatly, but power consumption is multiplied.In addition, by the circulation groove of extra setting, and the liquid-inlet pipe with many apertures that is arranged in bottom of electrolytic tank strengthened the circulation of electrolytic solution, electrolytic solution can constantly be mixed fully, thereby further improved electrolytic efficiency, and significantly reduced power consumption.
Description of drawings
The following drawings has shown preferred implementation of the present utility model, and wherein identical Reference numeral refers to identical parts.
Fig. 1 is the schematic flow sheet that extracts metallic copper with direct electrolysis method from alkaline spent etching solution;
Fig. 2 is the structural representation of the utility model electrolyzer.
Accompanying drawing among the application is synoptic diagram, one skilled in the art will understand that to clearly illustrating or outstanding some part, and size shown in the figure is not a physical size by the dwindling or amplifies of same ratio, and the shape of some parts is not the shape of reality yet.
Embodiment
In order further to improve electrolytic efficiency, to reduce power consumption, the utility model provides a kind of and has been used for from the electrolyzer of alkaline spent etching solution separating copper.
According to a kind of embodiment of the present utility model, think example below, the process of carrying copper from alkaline spent etching solution electrolysis is described with reference to figure 1.
In step 101, the alkaline spent etching solution that PBC enterprise discharges is introduced electrolyzer, wherein PCB enterprise discharges the spent etching solution that copper ion concentration exceeds processing requirement, and at this moment the concentration of cupric ion is called mother liquor usually more than 150g/L in the spent etching solution.In step 102, adjust the ionic concn of spent etching solution, usually by dilution, the concentration of adjusting cupric ion etc. is to be suitable for electrolysis.For example copper ion concentration can be adjusted to 20~120g/L.In step 103, carry out electrolysis then.Electrolysis obtains metallic copper and surplus liquid after finishing.Metallic copper reclaims from cathodic disbonding.The surplus liquid of part is restored in the electrolyzer, mixes as thinner and mother liquor in the ionic concn set-up procedure, obtains being suitable for electrolytic electrolytic solution.Other surplus liquid are allocated in step 104, to replenish non-copper component, as chlorine, return etching work procedure then in step 105, are utilized again as new etching liquid medicine.
In electrolytic process, cupric ion is reduced, and separating out at negative electrode becomes metallic copper, certain negatively charged ion in the while solution, and for example hydroxide ion or chlorion are reduced according to voltage is different.
In the electrolytic process, the spent etching solution stirring that constantly circulates is stably carried out to guarantee the oxidation-reduction reaction in the electrolysis.Cupric ion is lower than for example 20g/L in the surplus liquid of final electrolysis, but is not limited thereto, and can adjust as required.
Further describe electrolyzer of the present utility model below in conjunction with accompanying drawing 2 with concrete preferred implementation.
With reference to figure 2, electrolyzer 1 of the present utility model has a rectangle electrolyzer 100, is provided with some groups of negative and positive substrate in batch 110 in electrolyzer.Every set of substrate batch is made up of two negative plates 111 and a slice positive plate 112.
Cathode-anode plate in the conventional electrolysis groove is to be provided with in pairs.And in the utility model, each substrate in batch 110 is made up of two negative plates 111 and a slice positive plate 112.The area of negative plate is multiplied, thus increased with electrolytic solution in the contact area of cupric ion, help improving electrolytic efficiency, and power consumption is constant substantially.In a preferred implementation, the spacing between negative plate 111 and the positive plate 112 is set at 40cm, and the pole plate size all is set at 1200mm * 1000mm.Can obtain more optimal electrolytic efficiency like this.Consider economy and wearing quality, positive plate adopts the low resistance high-density graphite usually, and negative plate adopts stainless steel plate, but is not limited thereto, and those skilled in the art can appropriately select according to concrete needs.
Electrolyzer will have one group of pole plate group at least, and its number can be set according to treatment capacity.As being shown as 5 groups among Fig. 2, but be not limited thereto.For example according to above-mentioned preferred design, month 10 tons of waste liquids of processing can be provided with the substrate in batch about 10 groups.
As previously mentioned, in electrolytic process, to be lower than the ionic concn of solution inside near the ionic concn that participates in reaction in the pole plate place solution.Therefore, stir electrolytic solution and make wherein reactive ion must help to accelerate the electrolysis process near constantly adding to pole plate, improve electrolytic efficiency.But the pole plate of electrolyzer internal arrangement has hindered the uniform mixing of electrolytic solution.In some electrolyzers, pole plate is staggered, make electrolytic solution between pole plate with S type flow (as disclosed electrolyzer among the CN2551659Y).Yet so still can not make the abundant mixing of electrolytic solution.
In the preferred implementation of the present utility model, traditional return line is replaced with similar even bigger to the electrolyzer 100 substantially circulation groove 200 of a volume that holds electrolytic solution, and at bottom of electrolytic tank liquid-inlet pipe 120 is set, the top is provided with drain pipe 130.Liquid-inlet pipe 120 and drain pipe 130 are provided with opening (121 and 131) respectively in this circulation groove 200, thereby constitute electrolytic solution in circulation groove 200 and 100 loops that circulate of electrolyzer.
Liquid-inlet pipe 120 is provided with an opening 121 in circulation groove, by the pump (not shown) liquid in the circulation groove 200 is transported in the liquid-inlet pipe 120.Liquid-inlet pipe 120 is evenly distributed on electrolyzer 200 bottoms (for example with the S type), and has the aperture 122 of many upward openings on the tube wall, and the direction of electrolytic solution arrow in the figure is upwards flowed.
Drain pipe 130 is arranged on the top of electrolyzer 100, and has a opening 131 to circulation groove 200, flow out under the promotion of stream at liquid-inlet pipe 120, electrolytic solution flows to the top from the bottom of electrolyzer 100, and flows in the circulation groove 200 along the direction of arrow by drain pipe 130.Enter in the electrolyzer 100 by liquid-inlet pipe 120 again after electrolytic solution is mixed in circulation groove 200 fully and participate in electrolysis.
For making the electrolytic solution thorough mixing, also whipping appts can be set further in the circulation groove 200.
Because electrolytic solution has obtained sufficient mixing, can keep having and the inner essentially identical reactive ion concentration of electrolytic solution near the pole plate, thereby electrolytic efficiency is improved greatly.
Circulation groove 200 not only plays the well-mixed effect of electrolytic solution that makes, and can also the refrigerating unit (not shown) for example be set in circulation groove, plays electrolytic solution is carried out the refrigerative effect, thereby omitted the occupied volume of extra cooling apparatus.
According to preferred examples, electrolyzer of the present utility model has 10 groups of pole plate groups, and the cathode-anode plate spacing is 40cm, and pole plate is of a size of 1200mm * 1000mm, and the controlled liq flow velocity is about 10L/ branch, and selecting current density is 5~10A/dm 2, when electrolysis voltage was 6V, the power consumption of 1 ton of copper of electrolysis only was about 3500 degree, and like product needs about 5000 degree of power consumption; Electrolytic efficiency reaches more than 90%, and electrolytic speed is fast simultaneously, and the quality of metallic copper is also fine.
Below describe the utility model by specific embodiment in detail.Yet those of ordinary skill in the art should be understood that the above preferred embodiment of the present utility model that only is, is not to be used to limit protection domain of the present utility model.All any modifications of within spirit of the present utility model and principle, being done, be equal to replacement, improvement etc., all should be included within the protection domain of the present utility model.

Claims (6)

1. one kind is used for the electrolyzer that copper is carried in alkaline spent etching solution electrolysis, and described electrolyzer comprises: electrolyzer; With at least one group of pole plate group that is arranged on described electrolyzer inside,
It is characterized in that each described pole plate group is made up of a slice positive plate and two negative plates.
2. according to claim 1ly be used for the electrolyzer that copper is carried in alkaline spent etching solution electrolysis, further comprise:
Be arranged in the liquid-inlet pipe of described bottom of electrolytic tank;
Be arranged in the drain pipe at described electrolyzer top; With
The circulation groove that contiguous described electrolyzer is provided with,
Wherein said liquid-inlet pipe and described drain pipe have the opening that is arranged in the circulation groove respectively.
3. according to claim 2ly be used for the electrolyzer that copper is carried in alkaline spent etching solution electrolysis, have the aperture of many upward openings on the tube wall of wherein said liquid-inlet pipe.
4. according to claim 3ly be used for the electrolyzer that copper is carried in alkaline spent etching solution electrolysis, wherein said liquid-inlet pipe is so that described aperture is evenly distributed on the mode of the bottom of electrolyzer arranges.
According in the claim 2~4 any one describedly be used for the electrolyzer that copper is carried in alkaline spent etching solution electrolysis, wherein said circulation groove has the volume that can hold or more electrolytic solution essentially identical with described electrolyzer.
6. according to claim 1 and 2ly be used for the electrolyzer that copper is carried in alkaline spent etching solution electrolysis, the distance between wherein said negative plate and described positive plate is 40cm, and described negative plate and described positive plate have the size of 1200mm * 1000mm respectively.
CN2010201941457U 2010-05-13 2010-05-13 Electrolysis device for extracting copper through electrolysis of alkaline waste etching solution Expired - Fee Related CN201686753U (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102206823A (en) * 2011-05-16 2011-10-05 东莞市绿瀚环保设备科技有限公司 Process for directly electrolyzing waste etching solution to extract copper
CN104775132A (en) * 2015-03-27 2015-07-15 张家港联合铜业有限公司 Trapezoidal flow electrodeposition apparatus

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102206823A (en) * 2011-05-16 2011-10-05 东莞市绿瀚环保设备科技有限公司 Process for directly electrolyzing waste etching solution to extract copper
CN104775132A (en) * 2015-03-27 2015-07-15 张家港联合铜业有限公司 Trapezoidal flow electrodeposition apparatus

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C17 Cessation of patent right
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Granted publication date: 20101229

Termination date: 20130513