CN102286747A - Recycling and regeneration of microetching liquid and recycling system of metal copper - Google Patents
Recycling and regeneration of microetching liquid and recycling system of metal copper Download PDFInfo
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- CN102286747A CN102286747A CN2011102579744A CN201110257974A CN102286747A CN 102286747 A CN102286747 A CN 102286747A CN 2011102579744 A CN2011102579744 A CN 2011102579744A CN 201110257974 A CN201110257974 A CN 201110257974A CN 102286747 A CN102286747 A CN 102286747A
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- regeneration
- negative electrode
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- microetching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses recycling and regeneration of microetching liquid and a recycling system of metal copper. The recycling system comprises a microetching working tank, an electrolysis recycling and regeneration tank and a PLC (Programmable Logic Controller), wherein the electrolysis recycling and regeneration tank is connected with the microetching working tank through an acid-proof pump and a pipeline and controlled by the PLC by using a plate-in signal of a production line; and one or more cylindrical electrolysis tanks are arranged in the electrolysis recycling and regeneration tank. In comparison with the flat-plate electrolysis recycling equipment, the system of the invention has the function of total sealing, does not discharge any waste water, waste gas or waste substances, can regenerate microetching waste liquid and return the microetching waste liquid to the microetching tank for use and provide stable microetching effect, has better property, improves the current efficiency of cathode electrolysis and prolongs the use of an anode.
Description
Technical field
The present invention relates to the recovery system of metallic copper in the circulation and regeneration technology of micro-etched waste liquid in a kind of printed circuit board industry and the waste liquid.
Background technology
Basis as electronic industry, information industry and household electric appliances, recent two decades comes the printed electronic circuit board industry of one of heavy polluted industry to shift to China one after another, make the printed electronic circuit board industry of China keep 10～12% annual growth rate in recent years always, more than 5000 families of the big small business of printed circuit board are arranged at present, annual production reaches 1.2 hundred million square metres, occupies the whole world second.In the printed circuit board manufacture craft, micro-etching solution mainly is that microetch is carried out on the copper surface, with cleaning and alligatoring copper surface, helps to improve the bonding force of copper surface and dry film, wet film, prepreg and anti-solder ink etc.
Method commonly used at present is to adopt Sodium Persulfate or dioxysulfate aqueous systems micro-etching solution, by the acid in the micro-etching solution Copper Foil is corroded and copper ion releasing, carrying out along with microetch, the concentration of cupric ion rises, so micro-etching solution is through after a while, when copper ion concentration rises to 40～50 grams every liter the time, the microetch ability must be changed fresh micro-etching solution worse and worse.Method for treating waste liquid now is a neutralizing treatment, and wherein copper content is lower, and handling with traditional method does not have benefit to say, does not therefore have unit to be ready to reclaim.Common way is the waste water processing station that is discharged to circuit board plant, add alkali and become copper mud, become and transfer to special environmental protection company behind the solid waste and handle, so both increased the cost for wastewater treatment of company, also increased solid waste and gross contamination emission, not only wasted starting material, handled the metallic copper in the waste liquid is cheap, simultaneously environmental protection is caused certain harm, also do not meet the environmental requirement of national energy-saving and emission-reduction, cleaner production.
Summary of the invention
The object of the present invention is to provide a kind of cyclic regeneration of micro-etching solution of novel texture and the recovery system of metallic copper, for handling the totally-enclosed system that micro-etched waste liquid designs, do not have any waste water, waste gas and waste discharge specially, use drum type brake electrolysis design, superior performance, long service life.
The cyclic regeneration of a kind of micro-etching solution that the present invention proposes and the retrieving arrangement of copper, comprise microetch work nest, electrolytic recovery and regeneration tank, PLC controller, described electrolytic recovery and regeneration tank link to each other with pipeline by acidproof pumping with the microetch work nest, and the PLC controller adopts production line entering plate signal control electrolytic recovery and regeneration tank; The inside of described electrolytic recovery and regeneration tank is provided with one or more electrolyzers cylindraceous.
Described electrolyzer cylindraceous comprises anode and negative electrode, and this anode adopts the drum type brake design, is base material with the titanium, and internal layer is coated with the single precious metal oxide coating of ruthenium or iridium; This negative electrode is arranged in the anodic cylinder.
Described negative electrode adopts the metallic substance of pure titanium or titanium alloy.
Described negative electrode is pipe or column structure, and adopt in the middle of cathode circular tubes or cylinder and pass the mode that the center of circle is inserted, fixed a dielectric panel, or on cathode circular tubes or cylinder by apply, the mode of fixed insulation layer, be two semicircles with the copper layer of guaranteeing to be deposited on pipe or the cylinder negative electrode, convenience is follow-up can peel off sedimentary copper layer get off from negative electrode at an easy rate.
Described cylindric electrolyzer, clear distance is between 50-100mm between its anode and cathode.
Described ratio of cathodic to anodic area can reach 1: 2 to 1: 5.
The cyclic regeneration of micro-etching solution of the present invention and the recovery system of metallic copper have the following advantages:
1, in contrast to traditional flat electrolytic recovery equipment, system of the present invention is totally-enclosed except taking into account it, does not have any waste water, waste gas and waste discharge, its performance is more superior, long service life can and be returned the microetch groove and use micro-etched waste liquid regeneration, and stable microetch effect is provided;
2, use drum type brake electrolysis design, ratio of cathodic to anodic area can be controlled between 1: 2 to 1: 5, for the system that utilizes molysite corrosion operation, as number of patent application 201110111309.4 " capable of circulation carve treatment agent and treatment system with the copper and copper alloy surface micro etching again ", cooperate equipment design of the present invention, its cathode current density can improve greatly, both can improve the working efficiency that reclaims copper, also can significantly improve its electrolytic efficiency;
3, drum type brake electrolysis of the present invention design, anode can guarantee that because its area design is big its current density is less relatively, so can improve the single metal oxide containing precious metals DSA anodic work-ing life of coating ruthenium or iridium;
4, the negative electrode of design of electrolysis cells of the present invention adopts titanium or titanium alloy material, and utilize insulating material that pipe or column type electro-conductive material are divided into two semicircular cathode planes, conveniently peel off electrolytic deposition metal copper layer thereon, and realize recycling of negative electrode, thereby better create and promoted economic interests and environmental benefit.
Description of drawings
Fig. 1 is the overall work synoptic diagram of the recovery system of the cyclic regeneration of micro-etching solution of the present invention and copper.
Fig. 2 is the structural representation of the recovery system of the cyclic regeneration of micro-etching solution of the present invention and copper.
Fig. 3 is the structural representation of cylinder electrolyzer of the present invention.
Fig. 4 is the structural representation of the negative electrode that can be recycled of the present invention.
10: microetch work nest 20: electrolytic recovery and regeneration tank
21: anode 22: negative electrode
23: plate or insulation coat 30:PLC controller are cut apart in insulation
40: rectifier 50: pumping
Embodiment
As illustrated in fig. 1 and 2, electrolytic recovery of the present invention and regeneration tank 20 link to each other by acid and alkali-resistance pumping 50 and pipeline with microetch work nest 10; Behind the microetch copper, copper content raises the microetch medicament in microetch work nest 10, and working fluid microetch ability reduces and lost efficacy; By pumping 50 working fluid of these inefficacies is squeezed in electrolytic recovery and the regeneration tank 20 again, reduced wherein copper ion concentration and recover its microetch ability, enter microetch work nest 10 once more and carry out the microetch operation, in this way circulation.PLC controller 30 is connected with microetch work nest 10, electrolytic recovery and regeneration tank 20 and rectifier 40, guarantees the stability of total system work.
Shown in Fig. 3 and 4, electrolytic recovery of the present invention and regeneration tank 20 inside are provided with one or more (in an embodiment of the present invention, being provided with four cylinder electrolyzers) electrolyzer cylindraceous.Wherein, anode 21 adopts the drum type brake design, is base material with the titanium, and internal layer is coated with the single precious metal oxide coating of ruthenium or iridium; Negative electrode 22 is arranged in the cylinder of anode 21, adopt the metallic substance of pure titanium or titanium alloy, as shown in Figure 4, on this cathode circular tubes or the cylinder, utilize insulation to cut apart plate (PP, PTFE etc.) 23, insulation coat 23 perhaps directly is set on negative electrode 22 cylinders, pipe or cylinder are divided into two semicircular cathode planes, or other similar mode, guarantee when system's works better, to be deposited on the copper layer semicircular in shape on the negative electrode 22 rather than to be connected to form cylinder, guaranteeing behind the certain thickness metallic copper of deposition, easily the copper layer on the negative electrode 22 is peeled off and negative electrode can continue to recycle.
According to specific design, between the anode and cathode of the cylinder electrolyzer of the embodiment of the invention, its clear distance is between 50-100mm, the microetch medicament is made round-robin power by microetch work nest 10 by anti-corrosion pumping 50, bottom by electrolytic recovery and regeneration tank 20 enters cell body, process cyclic regeneration and metallic copper are back to microetch work nest 10 again and work on after being deposited on and being recovered on the negative electrode 22.
Under galvanic effect, the electrolytic reaction of anode and cathode is:
On anode 21 cylindraceous, react: Fe
2+→ Fe
3+O
2-→ O
0
On negative electrode 22 cylindraceous, react: Cu
2+→ Cu
0Fe
3+→ Fe
2+
The cylinder design of electrolysis cells that the present invention adopts, ratio of cathodic to anodic area can reach 1: 2 to 1: 5, and such design can guarantee anodic current density lower (usually at 4-8ASD), and the anodic principal reaction is Fe
2+→ Fe
3+, avoided unnecessary oxygen evolution reaction, also can prolong anodic work-ing life, reduce cost; And at negative electrode, since the cause of difference in Electrode Potential, reaction Fe
3+→ Fe
2+Than Cu
2+→ Cu
0More preferably, use the high cathode current density, just reduced Fe
3+→ Fe
2+This ratio that is reflected in the whole cathodic reaction, thus electrolytic efficiency promoted.
Embodiment (using electrolytic cell assembly cylindraceous)
Micro-etching solution 200L, its copper ion concentration is at 40g/L, and sulfuric acid concentration is 12%.Anode 21 adopts ruthenium-iridium-tantalum coating cylindrical design, and anodic current density is set at 6ASD; Negative electrode 22 adopts pure titanium material semicircular cylinder design, and cathode current density is 18ASD, and ratio of cathodic to anodic area is 1: 3, and Anode-cathode Distance is 80mm; Working temperature is 30 ℃, connects power supply and carries out electrolysis procedure, and the electrolysis electricity that accumulative total is passed through is 1200Ah, and deposited copper weighs 1208.7g on cathode cylinder, and it is 1185g that the theory of every Ah is analysed the copper amount, and calculating its faraday's dc electrolysis efficient thus is 85%.
Comparative example (using traditional flat electrolytic cell assembly)
Similarity condition: micro-etching solution 200L, its copper ion concentration is at 40g/L, and sulfuric acid concentration is 12%.Electrolyzer adopts flat design: positive plate adopts ruthenium iridium coating layer titanium anode, and anodic current density is set at 10ASD; Negative plate adopts pure titanium sheet material, cathode current density is set at 10ASD, ratio of cathodic to anodic area is 1: 1, Anode-cathode Distance is 80mm, and working temperature is 30 ℃, connects power supply and carries out electrolysis procedure, the electrolysis electricity that accumulative total is passed through is 1200Ah, and deposited copper weighs 1066.2g on negative plate, and it is 1185g that the theory of every Ah is analysed the copper amount, and calculating its faraday's dc electrolysis efficient thus is 75%.
By as seen above-mentioned, use cylindric design of electrolysis cells of the present invention, final faraday's dc electrolysis efficient is comparatively obvious than traditional flat electrolyzer increase.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, so every technical solution of the present invention content that do not break away from,, all still belong in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment did according to technical spirit of the present invention.
Claims (6)
1. the recovery system of the cyclic regeneration of a micro-etching solution and metallic copper, comprise microetch work nest, electrolytic recovery and regeneration tank, PLC controller, it is characterized in that: described electrolytic recovery and groove link to each other with pipeline by acidproof pumping with the microetch work nest, and the PLC controller adopts production line entering plate signal control electrolytic recovery and regeneration tank; The inside of described electrolytic recovery and regeneration tank is provided with one or more electrolyzers cylindraceous.
2. the recovery system of the cyclic regeneration of micro-etching solution according to claim 1 and metallic copper, it is characterized in that: described electrolyzer cylindraceous comprises anode and negative electrode, this anode adopts the drum type brake design, is base material with the titanium, and internal layer is coated with the single precious metal oxide coating of ruthenium or iridium; This negative electrode is arranged in the anodic cylinder.
3. the recovery system of the cyclic regeneration of micro-etching solution according to claim 2 and metallic copper is characterized in that: the metallic substance of described negative electrode pure titanium of employing or titanium alloy.
4. the recovery system of the cyclic regeneration of micro-etching solution according to claim 2 and metallic copper, it is characterized in that: described negative electrode is pipe or column structure, and adopt in the middle of cathode circular tubes or cylinder and pass the mode that the center of circle is inserted, fixed a dielectric panel, or on cathode circular tubes or cylinder by apply, the mode of fixed insulation layer, be two semicircles with the copper layer of guaranteeing to be deposited on pipe or the cylinder negative electrode, convenience is follow-up can peel off sedimentary copper layer get off from negative electrode at an easy rate.
5. the recovery system of the cyclic regeneration of micro-etching solution according to claim 2 and metallic copper, it is characterized in that: described cylindric electrolyzer, clear distance is between 50-100mm between its anode and cathode.
6. the recovery system of the cyclic regeneration of micro-etching solution according to claim 2 and metallic copper, it is characterized in that: described ratio of cathodic to anodic area can reach 1: 2 to 1: 5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102579744A CN102286747A (en) | 2011-09-02 | 2011-09-02 | Recycling and regeneration of microetching liquid and recycling system of metal copper |
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| CN2011102579744A CN102286747A (en) | 2011-09-02 | 2011-09-02 | Recycling and regeneration of microetching liquid and recycling system of metal copper |
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| CN102286747A true CN102286747A (en) | 2011-12-21 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104120428A (en) * | 2014-08-08 | 2014-10-29 | 苏州天承化工有限公司 | Recyclable micro etching chemical treatment agent on surface of copper/copper alloy |
| CN104975295A (en) * | 2014-04-11 | 2015-10-14 | 清英实业有限公司 | Device and method of recycling copper-containing micro-etching waste liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2105486U (en) * | 1991-11-06 | 1992-05-27 | 高晏生 | Sodium hypochlorite generator |
| CN2861181Y (en) * | 2005-11-25 | 2007-01-24 | 叶建均 | Regeneration and copper recovery device for copper chloride acid etching liquid |
| CN1900365A (en) * | 2006-06-27 | 2007-01-24 | 福建师范大学 | Method for preparing ferrate by electric generating method and its special electrolytic bath |
| CN201567161U (en) * | 2009-07-24 | 2010-09-01 | 北方工业大学 | Two-section wireless aluminum electrolysis multi-function crown block aluminum flow-out accuracy control system |
| CN101988199A (en) * | 2009-08-04 | 2011-03-23 | 章晓冬 | Micro-etching solution cyclic regeneration and copper reclamation device |
-
2011
- 2011-09-02 CN CN2011102579744A patent/CN102286747A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2105486U (en) * | 1991-11-06 | 1992-05-27 | 高晏生 | Sodium hypochlorite generator |
| CN2861181Y (en) * | 2005-11-25 | 2007-01-24 | 叶建均 | Regeneration and copper recovery device for copper chloride acid etching liquid |
| CN1900365A (en) * | 2006-06-27 | 2007-01-24 | 福建师范大学 | Method for preparing ferrate by electric generating method and its special electrolytic bath |
| CN201567161U (en) * | 2009-07-24 | 2010-09-01 | 北方工业大学 | Two-section wireless aluminum electrolysis multi-function crown block aluminum flow-out accuracy control system |
| CN101988199A (en) * | 2009-08-04 | 2011-03-23 | 章晓冬 | Micro-etching solution cyclic regeneration and copper reclamation device |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104975295A (en) * | 2014-04-11 | 2015-10-14 | 清英实业有限公司 | Device and method of recycling copper-containing micro-etching waste liquid |
| CN104120428A (en) * | 2014-08-08 | 2014-10-29 | 苏州天承化工有限公司 | Recyclable micro etching chemical treatment agent on surface of copper/copper alloy |
| CN104120428B (en) * | 2014-08-08 | 2016-07-20 | 苏州天承化工有限公司 | A kind of capable of circulation again with the microetch chemical treatment medicament on copper and copper alloy surface |
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Application publication date: 20111221 |