CN101492186A - Method and device for circulation and regeneration of acidic waste etching liquid - Google Patents
Method and device for circulation and regeneration of acidic waste etching liquid Download PDFInfo
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- CN101492186A CN101492186A CNA2009100376019A CN200910037601A CN101492186A CN 101492186 A CN101492186 A CN 101492186A CN A2009100376019 A CNA2009100376019 A CN A2009100376019A CN 200910037601 A CN200910037601 A CN 200910037601A CN 101492186 A CN101492186 A CN 101492186A
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Abstract
The invention relates to a method and a device for recycling acidic waste etching liquid. The method and the device adopt three closed cycles, namely, an acidic waste etching liquid copper separation and component adjustment cycle, a copper extraction agent cycle, and an electrolytic copper extraction and a back extraction agent cycle. The acidic waste etching liquid from which copper is removed by a copper-extraction and back-extraction mechanism is subjected to component adjustment so as to be circularly used by an acid etching machine, the extraction agent is circularly used in the copper-extraction and back-extraction mechanism, the back extraction agent is returned to the copper-extraction and back-extraction mechanism to be circularly used after copper is removed by electrolyzing deposited copper, and electrolytic copper generated by electrolyzing deposited copper can be sold as a commodity. Therefore, in the whole treatment process, the closed cycles of materials are realized with wastewater discharge avoidance, effective copper recovery and recycling use of waste etching liquid and other materials. In addition, the extraction and back extraction of the copper extraction agent are carried out in the copper-extraction and back-extraction mechanism and liquid in a cell flows in an overflow manner without requiring a pump, so the device is convenient in operation and compact in overall structure.
Description
Technical field
The present invention relates to a kind of processing technology field of spent etching solution, especially relate to a kind of circulation regeneration method and device of acidic waste etching liquid.
Background technology
The technological process of production of existing printed circuit board is long, and etching work procedure is the part of proportion maximum in the PCB Production Flow Chart; In etching work procedure, owing to making etching index (comprising speed, lateral erosion coefficient, surface cleaning etc.) too much, dissolved substances when being lower than processing requirement, promptly becomes spent etching solution (comprising acidic etching liquid, alkaline etching liquid and microetch liquid) when etching solution.Acid etching is mainly used in the making of the internal layer circuit figure of multilayer circuit board; In general, every production 1m
2Wiring board need consume etching solution 2～2.5L, also output etching waste liquor 2～2.5L accordingly, and its copper ion concentration very high (reaching 120g/L or higher), the main component of these spent etching solutions has: heavy metal copper, ammonium salt, phosphate radical and contain inorganicss such as iodine compound; Sulfurous organic compound, nitrogen-containing heterocycle compound and contain organism such as cyanogen root organism; Polyoxyethylene compounds, the contour molecular compound of polyvinyl alcohol compounds.The PCB industry is annual to consume more than smart copper 100,000 t, total copper content is more than 50,000 t in the copper-containing wastewater of output, about 100,000 t of ammonium chloride, inorganic and the about 4000t of organophosphorus, the about 1000t of sulfur-bearing nitrogen heterocyclic ring organism, therefore as can be seen: the pollution index of spent etching solution is very high, is typical dangerous liquid refuse; Simultaneously spent etching solution still is a kind of very worthy composite factor, and its resource reclaims and the having a high potential of regeneration.
The acidic waste etching liquid treatment process is mainly contained substitution method, electrolytic process, neutralization precipitation method etc. both at home and abroad; It is not high that substitution method obtains the copper sponge grade, reclaims behind the copper shortcomings such as tail washings copper content height; Though the copper powder purity height that electrolytic process is produced is better than the copper powder that other method is produced on the performance; But electrolytic process produces that the efficient of copper powder is relatively low, and current consumption is higher, and the concentration of heavy metal ion in the waste liquid can not fall very lowly, will carry out the improvement of strictness before the discharging, and electrolytic process is easy to generate chlorine; Neutralization precipitation method Treatment of Copper waste liquid, technology is simple, less investment, but the mother liquor copper content is higher behind the cupric sulphate crystal, needs further to handle, and can not cause serious environmental to pollute to inorganics and the organism recycles such as ammonium salt in the waste water.
Summary of the invention
The objective of the invention is at above-mentioned existing problems and deficiency, providing a kind of both can make the acidic waste etching liquid in the circuit board etching operation can recycle, copper in the acidic waste etching liquid can be reclaimed again simultaneously, to reduce quantity of wastewater effluent, increase economic efficiency, and acidic waste etching liquid circulation regeneration method is easily controlled the time in operation.On this basis, further purpose of the present invention provides a kind of acidic waste etching liquid material in the entire treatment process that makes and realizes the closed cycle use, do not have discharge of wastewater, use environmental protection, and the cyclic regeneration device of simple in structure, compact, easy to operate acidic waste etching liquid.
Technical scheme of the present invention is achieved in that
The method of acidic waste etching liquid cyclic regeneration of the present invention is characterized in comprising following circulation step:
Acidic waste etching liquid copper separates and component allotment circulation: the acidic waste etching liquid that acid etching machine carries out being produced after the etching is got to form behind copper extractant extraction copper removal in the mechanism in the copper extracting-back extraction and is carried the copper spent etching solution, carry the copper spent etching solution after carrying out component allotment and making it reach the production necessary requirement, return acid etching machine and recycle;
Copper extractant circulation: get the copper extractant that adds in the mechanism in described copper extracting-back extraction and behind extracting copper, form copper bearing copper extractant, copper bearing copper extractant fully reacts with strippant cupric ion is discharged in the strippant, copper extractant recovers the extraction function unloading copper-loaded back, returns extracting-back extraction and gets in the extraction process of mechanism and recycle;
Copper and strippant circulation are proposed in electrolysis: the strippant of described copper ions recovers the reextraction function after carrying copper through copper electrowinning, return the copper extracting-back extraction and get in the reextraction operation of mechanism and recycle, and the copper that electrolytic deposition extracted is high-purity copper.
The invention still further relates to a kind of cyclic regeneration device that is used for the acidic waste etching liquid of above-mentioned acidic waste etching liquid circulation regeneration method:
The cyclic regeneration device of described acidic waste etching liquid comprises: by acidic waste etching liquid outlet on connecting tube and the etching machine being used for of linking to each other with the copper of acidic waste etching liquid extract with the copper extracting-back extraction of stripping get mechanism, with acid etching machine on etching solution enter the mouth and get etching solution component regulating mechanism that mechanism links to each other, get the copper electrowinning mechanism that mechanism links to each other with described copper extracting-back extraction with described copper extracting-back extraction.
Wherein above-mentioned copper extracting-back extraction is got mechanism and is provided with acidic waste etching liquid inlet, copper extractant inlet, strippant inlet and the outlet of regeneration etching solution, copper extractant outlet and the outlet of cupric strippant, described copper extractant inlet links to each other with the copper extractant outlet by connecting tube, described cupric strippant inlet links to each other with the strippant outlet by described copper electrowinning mechanism, and described regeneration etching solution exports and joins by connecting tube and etching solution component regulating mechanism.
It is box mixing-settler extractor that above-mentioned copper extracting-back extraction is got mechanism.
In the present invention, because acidic waste etching liquid can recycle for etching machine through the component allotment after getting mechanism's copper removal through the copper extracting-back extraction again, copper extractant is got in the mechanism in the copper extracting-back extraction and is recycled, the cupric strippant returns the copper extracting-back extraction after through copper electrowinning part copper removal and gets in the mechanism and recycle, therefore material is realized closed cycle in the entire treatment process, there is not discharge of wastewater, other materials in energy efficient recovery copper and the recycle spent etching solution, significantly reduce the quantity of wastewater effluent of etching work procedure, reduce environmental protection pressure, and three cyclic part non-stop runs have simultaneously reduced treatment operating costs.And the electrolytic copper that copper electrowinning circulation portions branch produces can be used as commodity selling, creates profit.And because the extraction of its copper extractant and the operation of stripping all are to carry out in box mixing-settler extractor, liquid-flow does not need pump by overflow in the groove, so it is not only easy to operate, and its compact overall structure.
The present invention is further illustrated below in conjunction with accompanying drawing.
Description of drawings
Fig. 1 is a process flow diagram of the present invention;
Fig. 2 is the frame structure synoptic diagram of the cyclic regeneration device of acidic waste etching liquid among the present invention;
Fig. 3 gets the structural representation of an embodiment of mechanism for copper extracting-back extraction among Fig. 2.
Embodiment
As shown in Figure 1, the method for acidic waste etching liquid cyclic regeneration of the present invention comprises following circulation step:
Acidic waste etching liquid copper separates and component allotment circulation: the acidic waste etching liquid that acid etching machine carries out being produced after the etching is got to form behind copper extractant extraction copper removal in the mechanism 2 in the copper extracting-back extraction and is carried the copper spent etching solution, carry the copper spent etching solution after carrying out component allotment and making it reach the production necessary requirement, return acid etching machine 1 and recycle;
The copper extractant circulation: copper extractant is got in described copper extracting-back extraction and is formed copper bearing copper extractant in the mechanism 2 behind the extracting copper, copper bearing copper extractant fully reacts with strippant cupric ion is discharged in the strippant, copper extractant unloads copper-loaded back and recovers the extraction function, returns extracting-back extraction and gets in the extraction process of mechanism 2 and recycle;
Copper and strippant circulation are proposed in electrolysis: the strippant of described copper ions recovers the reextraction function after carrying copper through copper electrowinning mechanism, return the copper extracting-back extraction and get in the reextraction operation of mechanism 2 and recycle, and the copper that electrolytic deposition extracted is high-purity copper.
Wherein above-mentioned copper extractant is selected the organic copper extraction agent for use, and this extraction agent only extracts the selective copper in the acidic waste etching liquid.The ratio of above-mentioned copper extractant and acidic waste etching liquid can be come fixed as the case may be, is generally 2: 1～5: 1.The preferred proportion of above-mentioned copper extractant and acidic waste etching liquid is 3: 1.The principal reaction of extraction is:
Cu
2++ 2RH=CuR
2+ 2H
+(wherein RH is an extraction agent)
Above-mentioned strippant can be selected copper sulfate and vitriolic mixing solutions for use.The ratio of above-mentioned copper bearing copper extractant and strippant can be come fixed as the case may be, is generally 2: 1～5: 1.The preferred proportion of copper bearing copper extractant and strippant is 3: 1.The principal reaction of stripping is:
CuR
2+ H
2SO
4=CuSO
4+ 2RH (wherein RH is an extraction agent)
The component allotment of above-mentioned regeneration etching solution is to replenish part acid etching salt in the regeneration etching solution.
In sum, because acidic waste etching liquid can recycle for acid etching machine 1 through the component allotment after getting mechanism's 2 copper removals through the copper extracting-back extraction again, extraction agent also can be got in the mechanism 2 in the copper extracting-back extraction and recycle, the cupric strippant is being got in the mechanism 2 and is being recycled through returning the copper extracting-back extraction behind the copper electrowinning copper removal, the electrolytic copper that copper electrowinning produced can be used as commodity selling, create profit, so material is realized closed cycle in the entire treatment process, there is not discharge of wastewater, other materials in energy efficient recovery copper and the recycle spent etching solution, significantly reduce the quantity of wastewater effluent of etching work procedure, reduce environmental protection pressure, and three cyclic part non-stop runs have simultaneously reduced treatment operating costs.
As Fig. 2-shown in Figure 3, the cyclic regeneration device of acidic waste etching liquid of the present invention, comprise: the copper of acidic waste etching liquid is extracted and the copper extracting-back extraction of stripping is got mechanism 2 by acidic waste etching liquid outlet 11 on connecting tube and the acid etching machine 1 being used for of linking to each other, with the etching solution inlet 12 etching solution component regulating mechanisms 6 that link to each other on the acid etching machine 1, be used for extracting the copper electrowinning mechanism 4 of cupric strippant copper, wherein said copper extracting-back extraction is got mechanism 2 and is provided with acidic waste etching liquid inlet 21, copper extractant inlet 22, strippant inlet 23 and propose copper spent etching solution outlet 24, copper extractant outlet 25 and cupric strippant outlet 26, described copper extractant outlet 25 links to each other with copper extractant inlet 22 by connecting tube, described strippant outlet 26 links to each other with strippant inlet 23 by described copper electrowinning mechanism 4, and the described copper spent etching solution of carrying exports 24 and joins by connecting tube and etching solution component regulating mechanism 6.For making structure of the present invention more reliable and make each cycling mechanism Control Circulation automatically, further making things convenient for its operation, above-mentioned copper extracting-back extraction is got the connecting tube that the acidic waste etching liquid of acidic waste etching liquid inlet 21 and acid etching machine 1 in the mechanism 2 exports between 11 and is provided with acidic waste etching liquid transfer cylinder 5 and control valve 51.The copper extractant outlet 25 that above-mentioned copper extracting-back extraction is got in the mechanism 2 is provided with extraction agent transfer cylinder 3 and control pump 31 or valve with the connecting tube that copper extractant enters the mouth between 22.Above-mentioned copper extracting-back extraction is got the cupric strippant inlet 41 that is provided with in cupric strippant outlet 26 in the mechanism 2 and strippant inlet 23 and the above-mentioned copper electrowinning mechanism 4 and strippant and is exported on the connecting tube between 42 and be respectively equipped with cupric strippant transfer cylinder 8 and strippant transfer cylinder 9, control pump 81,91 or valve.Above-mentioned copper extracting-back extraction is got mechanism 2 and is adopted box mixing-settler extractor to form, and wherein extracting progression is 1～8 grade, and reextraction progression is 1～3 grade.Box mixing-settler extractor as shown in Figure 3, its extraction progression is secondary, reextraction progression is one-level.Be equipped with mixing section 27, clarifying chamber 28, organic phase overflow port 20, water overflow port 20 in each grade extraction tank in this box mixing-settler extractor.It is the blending vat that there is stirrer 61 in mechanism in it that above-mentioned etching solution component is allocated mechanism 6, and the connecting tube of described blending vat and acid etching machine 1 is provided with control valve 62.Above-mentioned copper electrowinning mechanism 4 is an electrolyzer, and described electrolyzer is divided into a plurality of sulculuses, and sulculus is composed in parallel by a plurality of anodes and negative electrode, is connected in series between the sulculus; Anode in the groove is a lead anode, and negative electrode is a copper sheet, low price, and power consumption is low.Also be connected with motor-generator set 7 on the above-mentioned electrolyzer.
Below in conjunction with accompanying drawing principle of work of the present invention is described in further detail:
As shown in Figure 1-Figure 3, start the stirrers that the copper extracting-back extraction gets in the mechanism 2 and stir, effusive acidic waste etching liquid enters the copper extracting-back extraction through acidic etching liquid transfer cylinder 5 and acidic waste etching liquid inlet 21 and gets mechanism 2 from acid etching machine 1.Copper extractant in the copper extractant transfer cylinder 3 enters the copper extracting-back extraction through copper extractant inlet 22 and gets in the mechanism 2, the extraction section of extraction process with mixes mixing section 27 from acidic waste etching liquid inlet 21 acidic waste etching liquids that enter and by stirring the generation extractive reaction so that selective copper is extracted, copper extractant forms copper bearing copper extractant behind extracting copper, enter clarifying chamber 28 after mixing, copper bearing copper extractant and the acidic waste etching liquid layering of carrying behind the copper, the acidic waste etching liquid of carrying behind the copper enters the upper level mixing section by water overflow port 20, again through carry copper spent etching solution outlet 24 enter carry out the component allotment in the component setting device 6 after, the etching work procedure that enters acid etching machine 1 recycles.And copper bearing copper extractant enters next stage mixing section 27 by organic phase overflow port 29.When copper bearing copper extractant overflows to the reextraction section mixing section 27 of reextraction operation by organic phase overflow port 29, the reaction of stripping takes place by mixing in 23 strippants of coming in entering the mouth from strippant, cupric ion is discharged in the strippant, copper extractant after the reextraction and cupric strippant enter clarifying chamber 28, copper extractant and the layering of cupric strippant, copper extractant enters into copper extractant outlet 22 and copper extractant transfer cylinder by organic phase overflow port 29, returns the extraction section that the copper extracting-back extraction gets in the mechanism 2 again and recycles; The cupric strippant enters cupric strippant outlet 26 by water overflow port 20, enter in the copper electrowinning mechanism 4 through cupric strippant transfer cylinder 8 and cupric strippant inlet 41 again, copper electrowinning mechanism 4 electrolysis cupric strippants and make the cupric strippant form electro deposited copper and strippant, strippant enters strippant transfer cylinder 9, returns the copper extracting-back extraction again and gets in the reextraction section of mechanism 2 and recycle.Electro deposited copper reclaims.
Claims (13)
1, a kind of circulation regeneration method of acidic waste etching liquid is characterized in that comprising following circulation step:
Acidic waste etching liquid copper separates and component allotment circulation: acid etching machine carry out the acidic waste etching liquid that produced after the etching the copper extracting-back extraction get in the mechanism (2) through form behind the copper extractant extraction copper removal carry copper after spent etching solution, carry behind the copper spent etching solution after carrying out the component allotment and making it reach the production necessary requirement, return acid etching machine (1) and recycle;
The copper extractant circulation: copper extractant is got in described copper extracting-back extraction and is formed copper bearing copper extractant in the mechanism (2) behind the extracting copper, copper bearing copper extractant fully reacts with strippant cupric ion is discharged in the strippant, the copper extractant that unloads after copper-loaded recovers the extraction function, returns the extraction process that extracting-back extraction gets in the mechanism (2) and recycles;
Copper and strippant circulation are proposed in electrolysis: the strippant of described copper ions recovers the reextraction function after carrying copper through electrolytic deposition, return the reextraction operation that the copper extracting-back extraction gets in the mechanism (2) and recycle, and the copper that electrolytic deposition extracted is high-purity copper.
2, the circulation regeneration method of acidic waste etching liquid according to claim 1 is characterized in that the organic copper extraction agent of above-mentioned copper extractant for only the selective copper in the acidic waste etching liquid being extracted.
3, the circulation regeneration method of acidic waste etching liquid according to claim 1, the ratio that it is characterized in that above-mentioned copper extractant and acidic waste etching liquid is 2: 1～5: 1.
4, the circulation regeneration method of acidic waste etching liquid according to claim 1 is characterized in that above-mentioned strippant is copper sulfate and vitriolic mixing solutions.
5, according to the circulation regeneration method of claim 1 or 4 described acidic waste etching liquids, the ratio that it is characterized in that copper bearing copper extractant and strippant is 2: 1～5: 1.
6, a kind of cyclic regeneration device of acidic waste etching liquid is characterized in that comprising: by connecting tube and acid etching machine (1) being used for of going up that acidic waste etching liquid outlet (11) links to each other with the copper of acidic waste etching liquid extract with the copper extracting-back extraction of stripping get mechanism (2), with acid etching machine (1) on etching solution enter the mouth (12) and described copper extracting-back extraction is got etching solution component regulating mechanism (6) that mechanism (2) links to each other, got the copper electrowinning mechanism (4) that mechanism (2) links to each other with described copper extracting-back extraction.
7, the cyclic regeneration device of acidic waste etching liquid according to claim 6, it is characterized in that above-mentioned copper extracting-back extraction gets mechanism (2) and be provided with acidic waste etching liquid inlet (21), copper extractant inlet (22), strippant enters the mouth (23) and proposes copper spent etching solution outlet (24), copper extractant outlet (25) and cupric strippant outlet (26), described copper extractant outlet (25) links to each other with copper extractant inlet (22) by connecting tube, described cupric strippant outlet (26) links to each other with strippant inlet (23) by above-mentioned copper electrowinning mechanism (4), and the described copper spent etching solution of carrying exports (24) and joins by connecting tube and etching solution component regulating mechanism (6).
8, the cyclic regeneration device of acidic waste etching liquid according to claim 7 is characterized in that above-mentioned copper extracting-back extraction gets the connecting tube that the acidic waste etching liquid of acidic waste etching liquid inlet (21) and acid etching machine (1) in the mechanism (2) exports between (11) and be provided with acidic waste etching liquid transfer cylinder (5) and control valve (51).
9, the cyclic regeneration device of acidic waste etching liquid according to claim 7 is characterized in that the copper extractant outlet (25) that above-mentioned copper extracting-back extraction is got in the mechanism (2) is provided with extraction agent transfer cylinder (3) and control pump (31) or valve with the connecting tube that copper extractant enters the mouth between (22).
10,, it is characterized in that above-mentioned copper extracting-back extraction gets that cupric strippant outlet (26) in the mechanism (2) and strippant inlet (23) and above-mentioned copper electrowinning mechanism (4) go up that the cupric strippant that is provided with enters the mouth (41) and strippant exports on the connecting tube between (42) and is respectively equipped with cupric strippant transfer cylinder (8) and strippant transfer cylinder (9), control pump (81,91) or valve according to the cyclic regeneration device of claim 7 or 8 or 9 described acidic waste etching liquids.
11, the cyclic regeneration device of acidic waste etching liquid according to claim 6 is characterized in that it is box mixing-settler extractor that above-mentioned copper extracting-back extraction is got mechanism (2), and wherein extracting progression is 1～8 grade, and reextraction progression is 1～3 grade.
12, the cyclic regeneration device of acidic waste etching liquid according to claim 6, it is characterized in that above-mentioned copper electrowinning mechanism (4) is for being provided with the electrolyzer 4 of a plurality of sulculuses in it, described sulculus is composed in parallel as the anodic stereotype with as the copper sheet of negative electrode by a plurality of, is connected in series between each sulculus.
13, the cyclic regeneration device of acidic waste etching liquid according to claim 6, it is characterized in that above-mentioned etching solution component allotment mechanism (6) is the blending vat that device has stirrer (61) in it, and the connecting tube of described blending vat and acid etching machine (1) is provided with control valve (62).
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|---|---|---|---|
| CNA2009100376019A CN101492186A (en) | 2009-03-05 | 2009-03-05 | Method and device for circulation and regeneration of acidic waste etching liquid |
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|---|---|---|---|
| CNA2009100376019A CN101492186A (en) | 2009-03-05 | 2009-03-05 | Method and device for circulation and regeneration of acidic waste etching liquid |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942565A (en) * | 2010-09-03 | 2011-01-12 | 罗光臣 | Regeneration and recovery method for waste red copper |
| CN102674628A (en) * | 2012-05-03 | 2012-09-19 | 波鹰(厦门)科技有限公司 | Sewage treatment and regeneration cyclic utilization device and sewage treatment and regeneration cyclic utilization method |
| WO2012163238A1 (en) * | 2011-05-31 | 2012-12-06 | 无锡尚德太阳能电力有限公司 | Recycling system and method for treating used etching solution |
| CN103233128A (en) * | 2013-05-13 | 2013-08-07 | 陈飙 | Method for recovering copper from acid waste etching solution |
| CN105506728A (en) * | 2014-09-29 | 2016-04-20 | 盛美半导体设备（上海）有限公司 | Recovery device for metal ions in electrochemical polishing solutions |
| CN109536725A (en) * | 2019-01-14 | 2019-03-29 | 北京康普锡威科技有限公司 | Printed plate board etching waste liquor processing method, copper nanoparticle and preparation method thereof |
| CN110453245A (en) * | 2018-05-07 | 2019-11-15 | 卫司特科技股份有限公司 | Copper waste etching solution copper ion handles recovery method |
| CN111270239A (en) * | 2020-03-27 | 2020-06-12 | Tcl华星光电技术有限公司 | Method for recycling copper-containing acidic etching solution |
-
2009
- 2009-03-05 CN CNA2009100376019A patent/CN101492186A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942565A (en) * | 2010-09-03 | 2011-01-12 | 罗光臣 | Regeneration and recovery method for waste red copper |
| CN101942565B (en) * | 2010-09-03 | 2012-09-05 | 罗光臣 | Regeneration and recovery method for waste red copper |
| WO2012163238A1 (en) * | 2011-05-31 | 2012-12-06 | 无锡尚德太阳能电力有限公司 | Recycling system and method for treating used etching solution |
| CN102674628A (en) * | 2012-05-03 | 2012-09-19 | 波鹰(厦门)科技有限公司 | Sewage treatment and regeneration cyclic utilization device and sewage treatment and regeneration cyclic utilization method |
| CN102674628B (en) * | 2012-05-03 | 2013-08-28 | 波鹰(厦门)科技有限公司 | Sewage treatment and regeneration cyclic utilization device and sewage treatment and regeneration cyclic utilization method |
| CN103233128A (en) * | 2013-05-13 | 2013-08-07 | 陈飙 | Method for recovering copper from acid waste etching solution |
| CN105506728A (en) * | 2014-09-29 | 2016-04-20 | 盛美半导体设备（上海）有限公司 | Recovery device for metal ions in electrochemical polishing solutions |
| CN105506728B (en) * | 2014-09-29 | 2019-10-15 | 盛美半导体设备（上海）有限公司 | The device of precipitating metal ion from electrochemical polish liquid |
| CN110453245A (en) * | 2018-05-07 | 2019-11-15 | 卫司特科技股份有限公司 | Copper waste etching solution copper ion handles recovery method |
| CN110453245B (en) * | 2018-05-07 | 2021-12-28 | 卫司特科技股份有限公司 | Method for treating and recovering copper ions in copper etching waste liquid |
| CN109536725A (en) * | 2019-01-14 | 2019-03-29 | 北京康普锡威科技有限公司 | Printed plate board etching waste liquor processing method, copper nanoparticle and preparation method thereof |
| CN111270239A (en) * | 2020-03-27 | 2020-06-12 | Tcl华星光电技术有限公司 | Method for recycling copper-containing acidic etching solution |
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Application publication date: 20090729 |