CN1896324A - Extraction of copper from waste etching liquid in chloride system circuit board - Google Patents
Extraction of copper from waste etching liquid in chloride system circuit board Download PDFInfo
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- CN1896324A CN1896324A CNA2006100361448A CN200610036144A CN1896324A CN 1896324 A CN1896324 A CN 1896324A CN A2006100361448 A CNA2006100361448 A CN A2006100361448A CN 200610036144 A CN200610036144 A CN 200610036144A CN 1896324 A CN1896324 A CN 1896324A
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Abstract
The extraction of copper from waste etching solution of circuit boards in chloride system includes: a electrolysis device containing a electrolytic vessel divided into cathode region and anode region by diafragm material, addition of waste etching solution into the cathode region, addition of chloride salts and elementary substance or compound accessory ingredient which reacts with chlorine as conducting medium, deposition of copper on the cathode and reaction of accessory ingredient with chlorine to form stable chloride in the anode region. Because the individual electrolytic vessel is divided into cathode region and anode region by slightly permeable diafragm, the electrodeposition of copper will progress equably in a large range of cathode current density, corresponding reactions of chlorine from electrolysis with added Mg, Al, Zn, Fe etc. will also occurs in the anode region avoiding the emission of chlorine above the anode.
Description
Technical field
The present invention relates to a kind of extracting method of copper, the method for copper is extracted in galvanic deposit in particularly a kind of chloride system circuit board spent etching solution.
Background technology
Every liter contains the copper of 100g to 120g of having an appointment in the non-renewable spent etching solution of chloride system circuit board, only the copper content of such spent etching solution of Guangdong Province's generation every month has 5000 tons approximately, reclaim these copper and carry out recycle, very great economic worth is arranged, and it is existing to extracting in this chloride system circuit board spent etching solution in the method for copper, it mainly is to be separated into diaphragm material in the electrolyzer of cathodic area and positive column, be connected with negative pole end with the positive terminal of dc output power respectively with cathode terminal by positive terminal, spent etching solution behind the connection loop in the electrolysis treatment electrolyzer, in the separate out amount of energising initial stage copper on negative electrode seldom, after the significant period of time of switching on, because joule heating effect makes after the remarkable rising of spent etching solution temperature, copper is just accelerated at the negative electrode speed of separating out, copper in spent etching solution is almost completely separated out, if the cupric ion in the supposition this moment spent etching solution all exists with the valence state of divalence, the efficient that its faraday direct current is imitated is below 70%, meanwhile, there is corresponding chlorine to separate out on the anode, according to Theoretical Calculation, every galvanic deposit goes out the copper of 100kg, separate out the chlorine of 111.6kg on anode, the volume under its standard state is 35.26m
3, deal carefully with so a large amount of chlorine and environment is not caused secondary pollution, be the thing that part extremely expends investment, and have the handling problem of waste liquid.At these problems, Chinese patent application ZL97121340.2 discloses a kind of regeneration CuCl
2The apparatus and method of etchant, it mainly is to carry out in two electrolyzers, first electrolyzer reverts to monovalence copper with cupric, second electrolyzer just arrives copper with the monovalence copper reduction, meanwhile, it also must add the solution of the univalent copper ion of higher concentration simultaneously to the positive column of two electrolyzers, be oxidized to cupric anodic reaction to keep monovalence copper, and it needs to charge into nitrogen (N above the cathodic area simultaneously
2) be oxidized to cupric to prevent monovalence copper, to the electroplating additive of cathodic area interpolation 10～25ppm, though it can obtain cupric chloride (CuCl easily
2) regeneration soln and make CuCl
2The etchant reproducible utilization has also been avoided the generation of poisonous fume chlorine, but it is just to CuCl
2Etchant carries out manipulation of regeneration, can not handle non-renewable spent etching solution, thereby can't obtain the recycling of metallic copper, and exist spent etching solution all the time in this manipulation of regeneration and make the metallic copper of the high shortage of valency form waste.Chinese patent ZL00117945.4 discloses a kind of method and system that reclaims and remove copper from liquid simultaneously, it mainly is to handle at the micro-etching agent of the sulfate system that contains various organic complexing agents, what at first separate out in the processing because of this sulfate system is the handling problem that there is not poisonous chlorine in oxygen, that is to say that its micro-etching agent that has solved sulfate system handles, mainly be in anode, to handle the sulfate system micro-etching agent simultaneously in this patent application, its two cupric ion or univalent copper ion, greatly reduce galvanic current faraday efficient so virtually and have increased the cost of handling greatly under cathodic deposition by passing cationic membrane.
Summary of the invention
The objective of the invention is existence at the problems referred to above, a kind of that can normally carry out at ambient temperature, faraday galvanic current efficient height is provided, can obtain simultaneously three kinds of valuable products particularly can obtain high-purity copper and do not have poisonous chlorine and galvanic deposit chloride system circuit board that waste liquid produces in non-renewable spent etching solution in the extracting method of copper.
The objective of the invention is to be achieved through the following technical solutions:
The extracting method of copper in the chloride system circuit board spent etching solution comprises:
(1) provide a kind of electrolyzer, it comprises that one is separated into the two-part electrolytic vessel in cathodic area and positive column by diaphragm material, wherein with the low metallic substance of perveance as negative electrode, with the high material of perveance as anode;
(2) in the cathodic area of above-mentioned electrolytic vessel, add chloride system circuit board spent etching solution to be processed, in the positive column of above-mentioned electrolytic vessel, add the simple substance or the mixture Synergist S-421 95 that can form chemical reaction, and in described positive column, add the muriate salt as conducting medium with chlorine;
(3) anode of above-mentioned electrolytic vessel and negative electrode are communicated with the positive terminal of dc electrolysis power supply and negative pole end respectively form the galvanic circle and above-mentioned chloride system circuit board spent etching solution is carried out normal temperature electrolysis treatment below 45 ℃, and by this electrolysis treatment deposited copper on negative electrode, the chemical reaction that carries out simple substance or mixture Synergist S-421 95 and chlorine in the positive column forms stable muriate.
Wherein above-mentioned diaphragm material employing ionic membrane or micropore ceramics or millipore filtration or other have the filter membrane of little penetrating quality.Above-mentioned negative electrode adopts stainless steel or pure titanium or titanium alloy or the low metallic substance of other perveance.Above-mentioned anode adopts graphite or is that matrix is coated with the single-element of platinum or iridium or ruthenium or rhodium or palladium or the precious metal oxide coating or the high material of other perveance of its combination with the titanium.Above-mentioned muriate salt is Repone K or sodium-chlor or calcium chloride or the high chloride salt of other perveance.Above-mentioned Synergist S-421 95 adopt magnesium or aluminium or zinc or iron or its combination or other easily and chlorine carry out simple substance or its mixture of chemical reaction.
The present invention is because single cell body is separated into the cathodic area with little osmotic membrane in employing and the positive column only adds non-renewable spent etching solution afterwards and do not add spent etching solution in the positive column in the cathodic area, only in the positive column, add potassium, sodium, the muriate salt of elements such as calcium is made conducting medium, and in conducting medium, add magnesium, aluminium, zinc, the simple substance of elements such as iron or mixture, thereby guarantee under quite broad cathode current density, the electrodeposition process of copper can both stably carry out, calculate with cupric, its faraday galvanic current efficient is greater than 95%, and product copper content is more than 99.5%.And this process can carry out all depositing on negative electrode until the copper in cathodic area at ambient temperature, this moment is because the influence of joule heating effect, the temperature of electrolyzer can rise accordingly to some extent, simultaneously when copper deposits on negative electrode, also can take place in the positive column corresponding reaction make chlorine that electrolysis generates in the positive column and the simple substance of elements such as the magnesium that adds, aluminium, zinc, iron or mixture react and generate the corresponding chlorinated thing, make the top, positive column not have chlorine to overflow, guarantee that effectively there is not the puzzlement of chlorine vent gas treatment in this treatment process.For this reason, after the copper in the spent etching solution is all separated out on negative electrode, can obtain two kinds of products of copper and HCL in the cathodic area, can obtain corresponding chlorinated produce product in the positive column, can make the present invention can guarantee effectively that the operation of acid copper can normally carry out at ambient temperature for this reason, and high faraday galvanic current efficient arranged, and simple substance magnesium that adds in chlorine that generates in anodic reaction and the positive column or aluminium or iron or zinc or its mixture react and generate stable muriate, have eliminated the puzzlement that produces chlorine.Make the present invention become environmentally friendly friendly process, reach purpose of the present invention.
Describe composition of the present invention and implementation method in detail below in conjunction with accompanying drawing:
Description of drawings
Fig. 1 is the structural representation of electrolyzer of the present invention.
Embodiment
The extracting method of copper in the chloride system circuit board spent etching solution comprises:
(1) provide a kind of electrolyzer as described in Figure 1, it comprises that one is separated into cathodic area 6 and positive column 5 two-part electrolytic vessels 1 by diaphragm material 2, wherein with the low metallic substance of perveance as negative electrode 4, with the high material of perveance as anode 3;
(2) in the cathodic area 6 of above-mentioned electrolytic vessel 1, add chloride system circuit board spent etching solution to be processed, in the positive column 5 of above-mentioned electrolytic vessel 1, add the simple substance or the mixture Synergist S-421 95 that can form chemical reaction, and in described positive column 5, add the muriate salt as conducting medium with chlorine;
(3) anode 3 of above-mentioned electrolytic vessel 1 and negative electrode 4 are communicated with the positive terminal of dc electrolysis power supply and negative pole end respectively form the galvanic circle and above-mentioned chloride system circuit board spent etching solution is carried out normal temperature electrolysis treatment below 45 ℃, and by this electrolysis treatment deposited copper on negative electrode 4,5 chemical reactions that carry out simple substance or mixture Synergist S-421 95 and chlorine form stable muriate in the positive column.Wherein above-mentioned diaphragm material 2 employing ionic membranes or micropore ceramics or millipore filtration or other have the filter membrane of little penetrating quality, above-mentioned negative electrode 4 adopts stainless steel or pure titanium or titanium alloy or the low metallic substance of other perveance, above-mentioned anode 3 adopts graphite or is that matrix is coated with the single-element of platinum or iridium or ruthenium or rhodium or palladium or the precious metal oxide coating or the high material of other perveance of its combination with the titanium, above-mentioned muriate salt is Repone K or sodium-chlor or calcium chloride or the high chloride salt of other perveance, above-mentioned Synergist S-421 95 adopt magnesium or aluminium or zinc or iron or its combination or other easily and chlorine carry out simple substance or its mixture of chemical reaction.
Embodiment 1: adding cupric in the cathodic area 6 of as shown in Figure 1 electrolyzer is the chloride system circuit board spent etching solution of 105.29g/L, adds the muriate conducting medium in positive column 5.And add after the mixture of zinc and iron, anode 3 in the electrolyzer and negative electrode 4 are connected to form after the loop with the anode and the negative terminal of direct supply, connect the galvanic deposit operation that power supply carries out copper, and envrionment temperature is 28 ℃, and negative electrode 4 current densities are 700A/m
2To 800A/m
2, the electric weight that the galvanic deposit operation feeds is 105.6Ah, the deposited copper amount that obtains on negative electrode 4 is 124g, press cupric and calculate, it is 1.185g that the theory of every Ah is analysed the copper amount, and the galvanic current efficient of Ji Suaning is 99.1% thus, do not have chlorine to separate out on the anode 3, positive column 5 generates new compound.
Embodiment 2: in the electrolyzer identical with embodiment 1, add the compound identical in the positive column 5 with example 1, in cathodic area 6, add new chloride system circuit board spent etching solution, electrode and direct supply connect into after the electrolysis loop, connect electrolysis power, the copper of the operation of acid copper in etching solution is all separated out on negative electrode 4, it is main that etching solution presents limpid color, the electrolysis electricity that accumulative total is passed through is 334.4Ah, cathodic area 6 obtains the deposited copper of 384g, and calculating its faraday galvanic current efficient is 96.9%.
Embodiment 3: form a pot line by 4 monomer electrolyzer polyphones as shown in Figure 1, in the cathodic area 6 of each monomer electrolyzer, add the chloride system circuit board spent etching solution, spent etching solution cupric 114g/L adds the 170L spent etching solution in 4 electrolyzers altogether.In each positive column 5, add potassium, na chloride solution conductivity medium, muriatic concentration is 200g/L to 220g/L, and in each positive column 5, add the compound of zinc and iron, the anode 3 of polyphone electrolyzer is connected with negative terminal with the anode of dc electrolysis power supply respectively with negative electrode 4, connect power supply and carry out the galvanic deposit operation of copper, negative electrode 4 current densities are about 900A/m
2, galvanic deposit proceeds to spent etching solution and is till the limpid transparent color, and total electric weight that accumulative total feeds is 16372Ah, obtains copper products 18.74Kg, and the faraday galvanic current efficient of calculating is 97.2%.
Claims (6)
1, the extracting method of copper in the chloride system circuit board spent etching solution is characterized in that comprising:
(1) provides a kind of electrolyzer, it comprises that one is separated into cathodic area (6) and the two-part electrolytic vessel in positive column (5) (1) by diaphragm material (2), wherein with the low metallic substance of perveance as negative electrode (4), with the high material of perveance as anode (3);
(2) in the cathodic area (6) of above-mentioned electrolytic vessel (1), add chloride system circuit board spent etching solution to be processed, toward the simple substance or the mixture Synergist S-421 95 of the positive column (5) of above-mentioned electrolytic vessel (1) middle adding can formation chemical reaction, and in described positive column (5), add the muriate salt as conducting medium with chlorine;
(3) anode (3) of above-mentioned electrolytic vessel (1) and negative electrode (4) are communicated with the positive terminal of dc electrolysis power supply and negative pole end respectively form the galvanic circle and above-mentioned chloride system circuit board spent etching solution is carried out normal temperature electrolysis treatment below 45 ℃, and go up deposited copper at negative electrode (4) by this electrolysis treatment, the chemical reaction that (5) carry out simple substance or mixture Synergist S-421 95 and chlorine in the positive column forms stable muriate.
2, the extracting method of copper according to claim 1 is characterized in that above-mentioned diaphragm material (2) employing ionic membrane or micropore ceramics or millipore filtration or other have the filter membrane of little penetrating quality.
3, the extracting method of copper according to claim 1 is characterized in that above-mentioned negative electrode (4) adopts stainless steel or pure titanium or titanium alloy or the low metallic substance of other perveance.
4, the extracting method of copper according to claim 1 is characterized in that above-mentioned anode (3) adopts graphite or is that matrix is coated with the single-element of platinum or iridium or ruthenium or rhodium or palladium or the precious metal oxide coating or the high material of other perveance of its combination with the titanium.
5, the extracting method of copper according to claim 1 is characterized in that above-mentioned muriate salt is Repone K or sodium-chlor or calcium chloride or the high chloride salt of other perveance.
6, the extracting method of copper according to claim 1, it is characterized in that above-mentioned Synergist S-421 95 adopt magnesium or aluminium or zinc or iron or its combination or other easily and chlorine carry out simple substance or its mixture of chemical reaction.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2006100361448A CN1896324A (en) | 2006-06-29 | 2006-06-29 | Extraction of copper from waste etching liquid in chloride system circuit board |
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|---|---|---|---|
| CNA2006100361448A CN1896324A (en) | 2006-06-29 | 2006-06-29 | Extraction of copper from waste etching liquid in chloride system circuit board |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101988200A (en) * | 2009-08-04 | 2011-03-23 | 章晓冬 | Cyclic regeneration and metal reclamation equipment for acid chloride-containing etchant |
| CN102560499A (en) * | 2012-02-03 | 2012-07-11 | 昆山市洁驰环保科技发展有限公司 | Device for recycling printed circuit board acidic 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 |
| CN104630825A (en) * | 2015-01-20 | 2015-05-20 | 昆山美源达环保科技有限公司 | Device and process for electrolytically extracting copper in acidic etching liquid |
| CN105132947A (en) * | 2015-09-24 | 2015-12-09 | 苏州市铂瑞工业材料科技有限公司 | Copper-recyclable electrode set |
-
2006
- 2006-06-29 CN CNA2006100361448A patent/CN1896324A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101988200A (en) * | 2009-08-04 | 2011-03-23 | 章晓冬 | Cyclic regeneration and metal reclamation equipment for acid chloride-containing etchant |
| CN102560499A (en) * | 2012-02-03 | 2012-07-11 | 昆山市洁驰环保科技发展有限公司 | Device for recycling printed circuit board acidic 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 |
| CN104630825A (en) * | 2015-01-20 | 2015-05-20 | 昆山美源达环保科技有限公司 | Device and process for electrolytically extracting copper in acidic etching liquid |
| CN105132947A (en) * | 2015-09-24 | 2015-12-09 | 苏州市铂瑞工业材料科技有限公司 | Copper-recyclable electrode set |
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Open date: 20070117 |