CN106282567A - A kind of method reclaiming metal from useless acidic etching liquid - Google Patents
A kind of method reclaiming metal from useless acidic etching liquid Download PDFInfo
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- CN106282567A CN106282567A CN201510284808.1A CN201510284808A CN106282567A CN 106282567 A CN106282567 A CN 106282567A CN 201510284808 A CN201510284808 A CN 201510284808A CN 106282567 A CN106282567 A CN 106282567A
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Abstract
The invention belongs to cupric industrial waste comprehensive utilization of resources field, particularly relate to a kind of method reclaiming metal from useless acidic etching liquid.Comprise the steps of (1) mixed alkali neutralization precipitation；(2) sucking filtration drip washing dechlorination；(3) control to leach；(4) electro-deposition.The present invention is compared with existing acidic etching waste liquid resource treatment technique, alkaline consumption is low, Installed capital cost is low, wide adaptability, the selective electrodeposition technology that its end uses can adapt to higher copper-bath residual chlorine, output constant product quality, simple to operate.Full processing procedure, in addition to filtering strong brine and sending evaporation individual processing, produces without waste water；The application of selective electrodeposition equipment guarantees that the acid mist that electrolytic deposition process produces can be uniformly processed, harmless discharge；Overall process is without unnecessary waste residue output, it is possible to achieve PCB acidic etching waste liquid processes " zero ", has fully reclaimed Cu and Cl in acid waste liquid, can effectively protect environment.
Description
Technical field
The invention belongs to cupric industrial waste comprehensive utilization of resources field, particularly relate to a kind of method reclaiming metal from useless acidic etching liquid.
Background technology
It is more particularly related to one produces industrial raw materials metallic copper, and the method that the chloride ion in acidic etching waste liquid is prepared as industry NaCl from the acid moment waste liquid of printed electronic circuit board (hereinafter referred to as pcb board).
The consumption accounting of one national raw material copper directly represent its country manufacturing industry, development degree of information industry, and reclaimed copper yield accounting in its refined copper the most directly embodies the development degree of its country's reproductive vibration.There has been significant progress in China in waste metal copper, alloyed copper waste recovery comprehensive utilization of resources field over nearly 10 years；Have been set up several scale and be not less than 50,000 tons/year, define total reclaimed copper yield and reach 3,000,000 tons of reclaimed copper Large-scale enterprises.But the enterprise especially reclaiming copper from cupric refuse from discarded copper-containing compound is the most few, and not yet obtain the abundant attention of country's recycling of recyclable waste industry.
The industry total class of copper-containing compound waste resource is various, complex treatment process, reclaims, processes, that recirculation industrial chain relates to industry is the most relative complex, the most not yet forms the process technique that replicability is strong, with low cost.China is to be a manufacturing powerhouse present stage, and the industrial goods in the whole world more than 60% are by domestic product, and Science in Future in China can be a manufacturing industry power, and its core competitiveness will become apparent from IT and chemical industry.Flourish along with China's rough formula of IT industry, its Industrial Output industrial wastewater positive maximum threaten ecological environment the most fragile around.Wherein the acidic etching waste liquid as the PCB manufacturing enterprise output of IT industry foundation stone is exactly a kind of hazardous waste with the biggest recycling value.Realized the recycling of PCB etching waste liquor by industrialization means, save virgin materials consumption, protect environment, be a behave with strategic importance.
The domestic process usual product of PCB acidic etching waste liquid is the displacement cupric enriched substance such as copper powder, copper oxide mud, and switch selling；The former needs to consume a large amount of reduced iron powder, also can produce flood tide hydrogen；The copper oxide mud filtration difficulty of the latter's output, and sheet quantity of alkali consumption is huge.
In the PCB acidic etching waste liquid comprehensive utilization of resources technology the most announced, the modes such as the cracking of ionic membrane electrodeposition, high-temperature spray, explosive evaporation have certain technology perspective, but corresponding industrially scalable application is the most rare, extremely low for reason promotional values such as processing cost and relevant device are expensive.
The Publication No. 103803737 applied for a patent such as certain company
Copper chloride in discarded acidic etching liquid is replaced and is reduced to copper powder by the mode using aluminum reduction displacement of A, drip washing is fired into cupric oxide powder again, the more difficult control of its conforming product rate, the aluminium powder that its process relates to is expensive, the audient of output cupric oxide powder is the most less, does not possess large-scale industry promotional value.
The employing sulfate substitution chloride ion of Publication No. 101899665 A applied for a patent such as certain company and then obtain high concentration concentrated vitriol copper solution the most finely purification and prepare cupric sulphate crystal and cupric oxide powder, the sulfate substitution process reaction condition that it relates to requires high, high temperature, high HCl corrosive environment, although being obtained in that the most large marketable product, but its equipment is once invested and follow-up maintenance cost is the most high.
The ionic membrane exchange electrodeposition that uses of Publication No. 102912375 A of the patent applied for such as certain company obtains the technique that negative electrode separates out copper, its operation needs first high concentration to be discarded acidic etching liquid and is diluted to below 35g/L, and need ion exchange membrane and titanium coating anode, the GB product that audient is wider can be obtained, but equipment is once invested high, subsequent operation is the most complex due to the existence of ionic membrane.
To sum up, existing PCB acidic etching waste liquid processes technique or the harshest to etching waste liquor component requirements, it is impossible to the acidic etching waste liquid processing various complicated ingredients of wide spectrum；Integrated treatment cost is high, the low process of even can only losing money of processing procedure profit；Requiring high to equipment and materials, a construction investment is huge.
In a word, a kind of can wide spectrum, reduction process cost, low construction investment acid PCB etching waste liquor way of recycling still by the extensive concern of industry, it is desirable to have new technology fills up this vacancy.
Summary of the invention
The purpose of invention: for a kind of method providing effect preferably to reclaim metal from useless acidic etching liquid.
In order to reach as above purpose, the present invention adopts the following technical scheme that:
A kind of method reclaiming metal from useless acidic etching liquid, it is characterised in that it is characterized in that, comprise the steps of
(1) mixed alkali neutralization precipitation: after recovery gained is discarded acidic etching liquid filter cloth removing solid suspension, with NaOH and Na2CO3Mass ratio is the mixed base neutralization precipitation between 1:1 ~ 1:2, obtains acid high copper ashes；
(2) sucking filtration drip washing dechlorination: the free chloro ion of carrying secretly in acid high copper ashes is separated by the sucking filtration drip washing mode using vacuum filtration and drip washing to combine with copper；
(3) leaching is controlled: leach high copper ashes with the sulfur acid solution of rear end operation output, by the pH value adding the whole leaching process of constant airspeed of control sulfur acid solution between 2 ~ 4.5, the leaching of metal cation in control copper-rich slag, it is thus achieved that copper-bath；
(4) electro-deposition: use electrodeposition apparatus to deposit the copper ion in copper-bath to negative electrode, it is thus achieved that high-purity negative electrode precipitating metal.
The further technical scheme of the present invention is, it is characterised in that the filter cloth in step (1) is large aperture filter cloth, and it is that mesh number is at 100 ~ 200 acidproof filter clothes of purpose；Mixed alkali neutralization precipitation uses the acid-base neutralization coprecipitation mode added in mixed alkali serosity by discarded acidic etching liquid, controls in whole precipitation process neutralization reactor pH by 14 to 6.0 convergences, and guarantees that neutralization precipitation process occurs without pH and is less than the situation of 5.5；Accessible discarded acidic etching liquid is the copper chloride complicated solution without ammonium root, Cu2+Ion concentration between 0.5 ~ 150g/L, Cl-Ion concentration is between 5 ~ 300g/L.
The further technical scheme of the present invention is, in described step (2), drip washing dechlorination uses vacuum filtration and drip washing sucking filtration rather than pulping and washing filter pressing dechlorination.
The further technical scheme of the present invention is, described step (3) control the sulfur acid solution that leaching process uses be in process system rear end operation output containing acid waste liquid, rather than newly configured low acid solution.
The further technical scheme of the present invention is, step also comprises the steps of after (4):
Sucking filtration liquid evaporation and concentration preparation industry NaCl: the first-time filtrate obtained by sucking filtration adjusts pH to about 8.5, concentration and evaporation crystallization obtains industry NaCl.
The further technical scheme of the present invention is, if when the leachate chlorine ion concentration of step (3) output is higher than 2g/L, also comprised the steps of between step (3) and (4):
Fine dechlorination: use the mode of high temperature copper powder dechlorination or extraction dechlorination to become more meticulous the chloride ion in removing copper-bath.
The further technical scheme of the present invention is, described step (4) is selective electrodeposition, uses selective electrodeposition equipment to deposit the copper ion in copper-bath to negative electrode, it is thus achieved that high-purity negative electrode precipitating metal.
The further technical scheme of the present invention is, theoretical based on turbulent flow electrodeposition during described selective electrodeposition, swiftly flowing electrolyte solution can eliminate the unfavorable factor that electrolytic deposition process causes due to concentration polarization phenomenon；Negative electrode can be obtained under the most severe solution condition and separate out copper.
Use the present invention of as above technical scheme, have the advantages that relative to prior art: the present invention is compared with existing acidic etching waste liquid resource treatment technique, alkaline consumption is low, Installed capital cost is low, wide adaptability, the selective electrodeposition technology that its end uses can adapt to higher copper-bath residual chlorine, output constant product quality, simple to operate.Full processing procedure, in addition to filtering strong brine and sending evaporation individual processing, produces without waste water；The application of selective electrodeposition equipment guarantees that the acid mist that electrolytic deposition process produces can be uniformly processed, harmless discharge；Overall process is without unnecessary waste residue output, it is possible to achieve PCB acidic etching waste liquid processes " zero ", has fully reclaimed Cu and Cl in acid waste liquid, can effectively protect environment.
Accompanying drawing explanation
In order to further illustrate the present invention, it is further illustrated below in conjunction with the accompanying drawings:
Fig. 1 is the process chart of invention.
Detailed description of the invention
Illustrating embodiments of the invention below in conjunction with the accompanying drawings, embodiment is not construed as limiting the invention:
Multiple purposes of the present invention are aiming at the PCB acidic etching waste liquid that complicated component is changeable, there is provided that a kind of adaptability is extensive, processing cost is cheap, a construction investment is low, simple to operate, the comprehensive utilization of resources technique of high-efficiency environment friendly, its major product is that negative electrode separates out GB copper, by-product industry NaCl, overall process meets three wastes process up to standard.
For realizing object above, the invention provides a kind of PCB acidic etching waste liquid comprehensive utilization of resources technique, this technique comprises:
Step 1, removes the insoluble bulky grain in PCB acidic etching waste liquid: by acidic etching waste liquid by acidproof bag filter, filtered by the solid suspension in Recycling of waste liquid.Acidproof bag filter filter bag filter cloth aperture is 100 ~ 200 mesh；
Step 2, mixed alkali deposited copper: according to the chloride ion total amount of pending etching solution, calculate Na ion total demand according to mol than for 1:1, by calculating gained configuration quality ratio for 3:2 ~ 2:1 sodium carbonate and sodium hydroxide mixed base；The wash water of the mixed base new water or the subsequent technique output that take about 1/5 total amount stirs into serosity in the reactor；With low discharge acidproof corrosion free pump, etching solution is added in reactor, keeps reactor stirs continuous running therebetween；When in question response device, serosity pH drops between 8 ~ 9, according in reactor serosity admittedly hang thing how much not have mixed base to float on slurry surface as foundation, as much as possible residue mixed base is added in reactor；Etching solution is added reactor and drops between 5.5 ~ 6.5 to the pH value of mixed serum in reactor by continuation pump；
Step 3, filtration washing: by the above-mentioned pH serosity vacuumizing filtration between 5.5 ~ 6.5 that is neutralized to, and add the new water wash of gross mass 0.75 times by about etching solution；Filtrate and leacheate separate collection, filtrate is NaCl near saturated solution, and leacheate can directly substitute the new water joining alkali demand in follow-up technique；
Step 4, orients molten copper: has been consumed etching solution and carries the clear water of metering 1.4 times and soak with being about by the copper-rich slag being filtrated to get, has been slowly added to concentrated sulphuric acid or high sour water, soaks and dissolve copper-rich slag, controls that the pH of course of dissolution leachate is constant is more than 2；
Step 5, degree of depth dechlorination: the residual chlorine in leachate is removed by the mode using rising leachate temperature to add 200 granularity copper powders or extraction with the form of Cu-lyt. sediment or raffinate；Cu-lyt. sediment can return directly to acid etching and sink copper process and use as basic auxiliary, and raffinate can use as joining the new water of alkali；
Step 6, regulation acidity selective electrodeposition: by the copper-bath after degree of depth dechlorination containing acid regulation to 150 ~ 180g/L, using and can adapt to complicated cation and the copper ion in copper-bath is deposited on cathode surface and forms negative electrode and separate out copper products by the very competent selective electrodeposition technology of anti-chlorine ion, the purity of copper products meets GB 0# copper standard；
Step 7, filtrate steams salt: after the strong brine obtained by filtration washing adjusts pH to about 8.5, concentration and evaporation, and every m strong brine can separate out industry NaCl150 ~ 200kg, and sodium chloride crystalline particle uniform coloration is pure white.
The above-mentioned method reclaiming copper from acidic etching waste liquid, wherein the whole N-process of step 2 is not allow for the pH situation appearance less than 5, and the copper-rich slag otherwise obtained is difficult to filter.
The above-mentioned method reclaiming copper from acidic etching waste liquid, wherein step 5, as used solution in copper powder dechlorination process not to be stirred vigorously, prevent the Cu-lyt. sediment formed to be oxidized to copper chloride and reenter solution；As used extraction removing chloride ion to need total chloridion concentration in the raffinate noting recycling in extraction process must not be higher than 40g/L.
| Cost | The suitability | Operation | Disposable investment | Environmental protection situation | |
| The present invention | tCu≤8000RMB | Extensively；Product is GB copper | Simply | Ton copper annual capacity investment not higher than 8000 yuan | Excellent, without waste water, waste sludge discharge, waste gas can focus on |
| Aluminum reduction | tCu≥10000RMB | Extensively；Product is displacement copper powder | Simply | Ton copper annual capacity invests about 10500 yuan | Good, it is high that waste water need to evaporate cost, has aluminum chloride slag, and waste gas is difficult to collection and processes |
| Atomization volatilization | tCu≥11000RMB | Narrow；Product is cupric sulfate crystals | Highly difficult | Ton copper annual capacity invests about 12000 yuan | Waste gas can focus on recovery, and equipment corrosion is difficult to solve, and maintenance cost is high |
Laboratory Examples 1:
1)
Take 2,5L beaker, peristaltic pump 1,100w 1, agitator of test；
2)
Taking PCB acidic etching waste liquid 3 ~ 4L to be placed in a 5L beaker, assay knows Cu in acid waste liquid2+Ion concentration is 116g/L, Cl-Ion concentration is 274g/L；The anticipated Na+ ion processing 3L etching solution needs is 23.15mol；Configuration quality is than sodium carbonate and the sheet alkali mixed base 1107g for 2:1；
3)
Remaining 5L beaker is placed under 100w stirring, makes agitator as close possible to beaker bottom (being not more than 1.5cm at the bottom of stirring perigee distance beaker)；To adding new water (can be tap water) in beaker to water surface covering stirring paddle；Start agitator, about 300g mixed base is equipped with in the stirring beaker of water, breaks into serosity；
4)
Start peristaltic pump, the acid waste liquid being placed in first beaker slowly joins in the 5L beaker of mixed alkali serosity, often add about 300ml etching solution and i.e. detect the pH value of serosity in beaker with accurate pH test paper, when pH drops to about 8.5 in serosity, remaining mixed base is all added in beaker；
5)
According to solution foaming degree in beaker, regulate the interpolation speed of acid waste liquid until serosity pH drops between 5.5 ~ 6.5 again in beaker；Stopping stirring, recording now acidic etching liquid actual interpolation total amount is 2.9L；
6)
The serosity of acquisition is carried out successively sucking filtration and drip washing；Obtaining sucking filtration filtrate 3.07L, pouring scouring water is 2.2L, it is thus achieved that drip washing filtrate amounts to 2.28L；
7)
Being placed in plastics open trough by sucking filtration filter cake, add 5.8L clear water submergence, Xiang Shuizhong adds concentrated sulphuric acid 20ml until pH value of solution constant can be less than 3.0 time sides and no longer add every 5min；
8)
Take in leaching supernatant 5L is placed in beaker and be warming up to 85 DEG C, add 200 mesh granularity copper powder stirring reaction 1h, the most constant solution temperature；Course of reaction can be seen that occur white suspension in solution, is Cu-lyt. granule；
9)
Abundant and copper powder reaction solution are cooled to rapidly 40 DEG C, filter and obtain Cu-lyt. sediment and the copper-bath of fully dechlorination；
10) copper-bath regulating acidity and start selective electrodeposition to 150g/L, electrolytic deposition process electric current density is 500 ~ 1000A/, voltage 2.2 ~ 2.4V between cathode-anode plate；Continue electrodeposition 1h, it is thus achieved that negative electrode separates out copper 85g.
11) sucking filtration gained strong brine is colourless transparent liquid, and its Cl is known in sample presentation analysis-Ion concentration is 186.74g/L, for nearly saturated NaCl solution.
The continuous production example in workshop 2:
1)
Build successively in workshop: per hour 1t steam boiler 1, can evaporate that water 1t triple effect evaporator 1 overlaps, 20m sinks copper groove 1 per hour, 1, vacuum band-type filter machine filter, per hour extracting Cu 100kg copper 1, line of extraction, produce per year and separate out copper 300t selective electrodeposition equipment 1 and overlap.
2)
The preset fresh water (FW) that be enough to flood stirring paddle in heavy copper groove, and it is added to sheet alkali to supersaturation；Start etching solution to add；Constantly mix alkali by 2:1 mass ratio in heavy copper groove, add mixed alkali, and persistently add acidic etching waste liquid；In heavy copper groove, liquid level stops adding mixed alkali when reaching the 60% of total liquid level degree of depth, and persistently interpolation etching solution is reduced to 6.5 to serosity pH in heavy copper groove；
3)
By gained serosity band filter sucking filtration drip washing, it is thus achieved that copper-rich slag with backend process raffinate leach；
4)
Raffinate leaches gained supernatant and for extracting and enriching copper ion and removes the chloride ion in leachate；The electric rich solution that extraction back extraction obtains directly send selectivity electro-deposition system electro deposited copper；
5)
The production electric current density of selective electrodeposition system electro deposited copper is 800 ~ 1000A/.
It should be noted that multiple schemes that this patent provides comprise the basic scheme of itself, separate, the most mutually restrict, but it can also be mutually combined in the case of not conflicting, reach multiple effect and jointly realize.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.Those skilled in the art is it should be recognized that the present invention is not restricted to the described embodiments; the principle that the present invention is simply described described in above-described embodiment and description; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements both fall within claimed scope.
Claims (8)
1. the method reclaiming metal from useless acidic etching liquid, it is characterised in that it is characterized in that, comprise the steps of
(1) mixed alkali neutralization precipitation: after recovery gained is discarded acidic etching liquid filter cloth removing solid suspension, with NaOH and Na2CO3Mass ratio is the mixed base neutralization precipitation between 1:1 ~ 1:2, obtains acid high copper ashes；
(2) sucking filtration drip washing dechlorination: the free chloro ion of carrying secretly in acid high copper ashes is separated by the sucking filtration drip washing mode using vacuum filtration and drip washing to combine with copper；
(3) leaching is controlled: leach high copper ashes with the sulfur acid solution of rear end operation output, by the pH value adding the whole leaching process of constant airspeed of control sulfur acid solution between 2 ~ 4.5, the leaching of metal cation in control copper-rich slag, it is thus achieved that copper-bath；
(4) electro-deposition: use electrodeposition apparatus to deposit the copper ion in copper-bath to negative electrode, it is thus achieved that high-purity negative electrode precipitating metal.
A kind of method reclaiming metal from useless acidic etching liquid, it is characterised in that the filter cloth in step (1) is large aperture filter cloth, it is that mesh number is at 100 ~ 200 acidproof filter clothes of purpose；Mixed alkali neutralization precipitation uses the acid-base neutralization coprecipitation mode added in mixed alkali serosity by discarded acidic etching liquid, controls in whole precipitation process neutralization reactor pH by 14 to 6.0 convergences, and guarantees that neutralization precipitation process occurs without pH and is less than the situation of 5.5；Accessible discarded acidic etching liquid is the copper chloride complicated solution without ammonium root, Cu2+Ion concentration between 0.5 ~ 150g/L, Cl-Ion concentration is between 5 ~ 300g/L.
A kind of method reclaiming metal from useless acidic etching liquid, it is characterised in that it is characterized in that, in described step (2), drip washing dechlorination uses vacuum filtration and drip washing sucking filtration rather than pulping and washing filter pressing dechlorination.
A kind of method reclaiming metal from useless acidic etching liquid, it is characterized in that, it is characterized in that, described step (3) control the sulfur acid solution that leaching process uses be in process system rear end operation output containing acid waste liquid, rather than newly configured low acid solution.
A kind of method reclaiming metal from useless acidic etching liquid, it is characterised in that it is characterized in that, step also comprises the steps of after (4):
Sucking filtration liquid evaporation and concentration preparation industry NaCl: the first-time filtrate obtained by sucking filtration adjusts pH to about 8.5, concentration and evaporation crystallization obtains industry NaCl.
A kind of method reclaiming metal from useless acidic etching liquid, it is characterized in that, it is characterized in that, if when the leachate chlorine ion concentration of step (3) output is higher than 2g/L, also comprised the steps of between step (3) and (4):
Fine dechlorination: use the mode of high temperature copper powder dechlorination or extraction dechlorination to become more meticulous the chloride ion in removing copper-bath.
A kind of method reclaiming metal from useless acidic etching liquid, it is characterized in that, it is characterised in that described step (4) is selective electrodeposition, selective electrodeposition equipment is used to deposit the copper ion in copper-bath to negative electrode, it is thus achieved that high-purity negative electrode precipitating metal.
A kind of method reclaiming metal from useless acidic etching liquid, it is characterized in that, it is characterized in that, theoretical based on turbulent flow electrodeposition during described selective electrodeposition, swiftly flowing electrolyte solution can eliminate the unfavorable factor that electrolytic deposition process causes due to concentration polarization phenomenon；Negative electrode can be obtained under the most severe solution condition and separate out copper.
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Cited By (11)
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| CN107299228A (en) * | 2017-05-26 | 2017-10-27 | 昆明理工大学 | A kind of method that zinc hydrometallurgy purification copper ashes extracts metallic copper |
| CN108624885A (en) * | 2017-08-07 | 2018-10-09 | 鲁铭 | A kind of spent acid and the method for alkaline etching liquid processing |
| CN108866550A (en) * | 2018-08-07 | 2018-11-23 | 王海华 | A kind of process flow of interior circulation etching solution production electrolytic copper foil |
| CN109971964A (en) * | 2019-04-25 | 2019-07-05 | 江西自立环保科技有限公司 | A kind of processing method of the high tin high-copper regeneration tin anode mud of high palladium |
| CN110042425A (en) * | 2019-04-23 | 2019-07-23 | 博罗县华盈科技有限公司 | A kind of heavy process for copper of alkaline etching waste liquid for producing direct electrowinning |
| CN111101157A (en) * | 2019-12-27 | 2020-05-05 | 合肥恒力装备有限公司 | Zero-emission treatment process for PCB etching waste liquid |
| CN111501065A (en) * | 2020-04-27 | 2020-08-07 | 阳谷祥光铜业有限公司 | Method for purifying copper electrolyte |
| CN112011781A (en) * | 2019-05-30 | 2020-12-01 | 上海名古屋精密工具股份有限公司 | Process for wet etching of binder phase and method for recovering waste liquid thereof |
| CN112110532A (en) * | 2020-08-13 | 2020-12-22 | 广东臻鼎环境科技有限公司 | Method for treating chloride ions in chlorine-containing solution by using copper powder |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491402A (en) * | 2011-12-05 | 2012-06-13 | 广州科城环保科技有限公司 | Method for producing refined copper oxide by utilizing acidic waste etching solution |
| CN103693673A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Producing method for producing electroplating grade copper sulfate with acid copper-bearing waste etching liquid |
| CN103966607A (en) * | 2013-01-31 | 2014-08-06 | 西安瑞凯电力科技有限公司 | Method for recovering copper and hydrochloric acid from acid etching solution |
| CN104395240A (en) * | 2012-05-24 | 2015-03-04 | 水ｉｎｇ株式会社 | Method and apparatus for recovering copper oxide from copper-containing acidic waste liquids |
-
2015
- 2015-05-29 CN CN201510284808.1A patent/CN106282567A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491402A (en) * | 2011-12-05 | 2012-06-13 | 广州科城环保科技有限公司 | Method for producing refined copper oxide by utilizing acidic waste etching solution |
| CN104395240A (en) * | 2012-05-24 | 2015-03-04 | 水ｉｎｇ株式会社 | Method and apparatus for recovering copper oxide from copper-containing acidic waste liquids |
| CN103966607A (en) * | 2013-01-31 | 2014-08-06 | 西安瑞凯电力科技有限公司 | Method for recovering copper and hydrochloric acid from acid etching solution |
| CN103693673A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Producing method for producing electroplating grade copper sulfate with acid copper-bearing waste etching liquid |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107299228A (en) * | 2017-05-26 | 2017-10-27 | 昆明理工大学 | A kind of method that zinc hydrometallurgy purification copper ashes extracts metallic copper |
| CN108624885A (en) * | 2017-08-07 | 2018-10-09 | 鲁铭 | A kind of spent acid and the method for alkaline etching liquid processing |
| CN108866550A (en) * | 2018-08-07 | 2018-11-23 | 王海华 | A kind of process flow of interior circulation etching solution production electrolytic copper foil |
| CN108866550B (en) * | 2018-08-07 | 2021-01-26 | 王海华 | Process flow for manufacturing electrolytic copper foil by using internal circulation etching solution |
| CN110042425A (en) * | 2019-04-23 | 2019-07-23 | 博罗县华盈科技有限公司 | A kind of heavy process for copper of alkaline etching waste liquid for producing direct electrowinning |
| CN109971964A (en) * | 2019-04-25 | 2019-07-05 | 江西自立环保科技有限公司 | A kind of processing method of the high tin high-copper regeneration tin anode mud of high palladium |
| CN112011781A (en) * | 2019-05-30 | 2020-12-01 | 上海名古屋精密工具股份有限公司 | Process for wet etching of binder phase and method for recovering waste liquid thereof |
| CN111101157A (en) * | 2019-12-27 | 2020-05-05 | 合肥恒力装备有限公司 | Zero-emission treatment process for PCB etching waste liquid |
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Application publication date: 20170104 |