CN202272953U

CN202272953U - System for recycling microetching liquid and recovering metallic copper

Info

Publication number: CN202272953U
Application number: CN2011203275027U
Authority: CN
Inventors: 章晓冬; 刘江波
Original assignee: GUANGZHOU SKYCHEM Ltd
Current assignee: Guangdong Tiancheng Technology Co.,Ltd.
Priority date: 2011-09-02
Filing date: 2011-09-02
Publication date: 2012-06-13
Anticipated expiration: 2021-09-02

Abstract

The utility model discloses a system for recycling microetching liquid and recovering metallic copper. The system comprises a microetching operating tank, an electrolytic recovery and regeneration tank and a programmable logic controller (PLC), wherein the electrolytic recovery and regeneration tank is connected with the microetching operating tank by an acid-proof pump and a pipeline; the PLC controls the electrolytic recovery and regeneration tank by using a board incoming signal of a production line; and one or more of cylindrical electrolytic tanks are formed inside the electrolytic recovery and regeneration tank. Compared with plate-type electrolytic recovery equipment, the utility model has the advantages that: the system is closed totally, does not discharge waste water, waste gas and wastes, can recycle microetching effluent and return the microetching effluent to the microetching tank to be used and provide a stable microetching effect, has excellent performance, improves the electrolysis current efficiency of a cathode and prolongs the service life of an anode.

Description

The cyclic regeneration of micro-etching solution and the recovery system of metallic copper

Technical field

The utility model relates to the recovery system of metallic copper in circulation and regeneration technology and the waste liquid of micro-etched waste liquid in a kind of printed circuit board industry.

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 peanut of printed circuit board are arranged at present, and YO 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, to clean 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, along with the carrying out of 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, little erosion 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, adds alkali and becomes copper mud, becomes to 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 purpose of the utility model is to provide a kind of cyclic regeneration and recovery system of metallic copper of micro-etching solution of novel texture; 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 utility model proposes and the retrieving arrangement of copper; Comprise little erosion work nest, electrolytic recovery and regeneration tank, PLC unit; Said electrolytic recovery and regeneration tank link to each other with pipeline through acidproof pumping with little erosion work nest, and the PLC unit adopts production line entering plate signal control electrolytic recovery and regeneration tank; The set inside of said electrolytic recovery and regeneration tank has one or more electrolyzers cylindraceous.

Said 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.

Said negative electrode adopts the metallic substance of pure titanium or titanium alloy.

Said 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 through apply, the mode of fixed insulation layer; Copper layer to guarantee to be deposited on pipe or the cylinder negative electrode is two semicircles, and convenience is follow-up can peel off sedimentary copper layer get off from negative electrode at an easy rate.

Said cylindric electrolyzer, clear distance is between 50-100mm between its anode and cathode.

Said ratio of cathodic to anodic area can reach 1: 2 to 1: 5.

The cyclic regeneration of the utility model micro-etching solution and the recovery system of metallic copper have the following advantages:

1, in contrast to traditional flat electrolytic recovery equipment, the system of the utility model 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 little erosion groove and use micro-etched waste liquid regeneration, and stable little erosion 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, is 201110111309.4 " copper and copper alloy surface micro etching treatment agent and the treatment system used again capable of circulation " like number of patent application; The equipment design that cooperates the utility model; Its cathode current density can improve greatly, both can improve the working efficiency that reclaims copper, also can significantly improve its electrolytic efficiency;

3, the utility model drum type brake electrolysis 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 the utility model design of electrolysis cells 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 above that; And realize recycling of negative electrode, thereby better create and promoted economic interests and environmental benefit.

Description of drawings

Fig. 1 is the overall operation synoptic diagram of recovery system of cyclic regeneration and the copper of the utility model micro-etching solution.

Fig. 2 is the structural representation of recovery system of cyclic regeneration and the copper of the utility model micro-etching solution.

Fig. 3 is the structural representation of the cylinder electrolyzer of the utility model.

Fig. 4 is the structural representation of the said negative electrode that can be recycled of the utility model.

10: little erosion work nest 20: electrolytic recovery and regeneration tank

21: anode 22: negative electrode

23: plate or insulation coat 30:PLC unit are cut apart in insulation

40: RF 50: pumping

Embodiment

As illustrated in fig. 1 and 2, said electrolytic recovery of the utility model and regeneration tank 20 link to each other through acid and alkali-resistance pumping 50 and pipeline with little erosion work nest 10; Behind the microetch copper, copper content raises the microetch medicament in little erosion work nest 10, and working fluid microetch ability reduces and lost efficacy; Through 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, get into little erosion work nest 10 once more and carry out the microetch operation, in this way circulation.PLC unit 30 is connected with microetch work nest 10, electrolytic recovery and regeneration tank 20 and RF 40, guarantees the stability of total system work.

The PLC unit 30 of the utility model adopts production line entering plate signal control electrolytic recovery and regeneration tank 20; When production line begins to produce, the entering plate inductor block in little erosion work nest 10 transfers signals to PLC unit 30, and PLC unit 30 is opened the power supply of pumpings 50 and electrolytic recovery and regeneration tank 20, and the electric current of setting with formula begins electrolytic recovery work.

Shown in Fig. 3 and 4, described electrolytic recovery of the utility model and regeneration tank 20 set inside have one or more (in the embodiment of the utility model, 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, adopts the metallic substance of pure titanium or titanium alloy, and is 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 concrete design; Between the anode and cathode of the cylinder electrolyzer of the utility model embodiment; Its clear distance is between 50-100mm, and the microetch medicament is made round-robin power by little erosion work nest 10 through anti-corrosion pumping 50, by the bottom entering cell body of electrolytic recovery and regeneration tank 20; Process cyclic regeneration and metallic copper are back to little erosion 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 utility model 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 ℃, and energized is carried 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 1.185g 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, and cathode current density is set at 10ASD, and ratio of cathodic to anodic area is 1: 1; Anode-cathode Distance is 80mm, and working temperature is 30 ℃, and energized is carried 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 1.185g that the theory of every Ah is analysed the copper amount, and calculating its faraday's dc electrolysis efficient thus is 75%.

By above-mentioned visible, use the cylindric design of electrolysis cells of the utility model, final faraday's dc electrolysis efficient is comparatively obvious than traditional flat electrolyzer increase.

The above; It only is the preferred embodiment of the utility model; Be not that the utility model is done any pro forma restriction; So every the utility model technical scheme content that do not break away from, to any simple modification, equivalent variations and modification that above embodiment did, all still belong in the scope of the utility model technical scheme according to the technical spirit of the utility model.

Claims

1. A recycling system for microetching solution and recovery system for metal copper, comprising a microetching work tank, an electrolytic recovery and regeneration tank, and a PLC controller, characterized in that: the electrolytic recovery and microetching work tank pass through the acid-resistant The pump is connected to the pipeline, and the PLC controller controls the electrolytic recovery and regeneration tank by using the signal from the production line; one or more cylindrical electrolytic tanks are arranged inside the electrolytic recovery and regeneration tank.

2. the recycling system of microetching solution according to claim 1 and the recycling system of metal copper, it is characterized in that: described cylindrical electrolyzer comprises anode and cathode, and this anode adopts cylindrical design, uses titanium as The substrate is internally coated with a single noble metal oxide coating of ruthenium or iridium; the cathode is disposed within the cylinder of the anode.

3. The recycling system of microetching solution and metal copper recovery system according to claim 2, characterized in that: the cathode is made of pure titanium or titanium alloy metal material.

4. The circulation regeneration of microetching liquid according to claim 2 and the recovery system of metal copper are characterized in that: the cathode is a circular tube or cylindrical structure, and is inserted through the center of the circle from the cathode circular tube or cylinder, The method of fixing an insulating material plate, or coating and fixing the insulating layer on the cathode tube or cylinder, to ensure that the copper layer deposited on the tube or cylinder cathode is two semicircles, which is convenient for subsequent The deposited copper layer is easily peeled off from the cathode.

5. The recycling system of microetching solution and metal copper recovery system according to claim 2, characterized in that: the net distance between cathode and anode of the cylindrical electrolytic cell is between 50-100 mm.

6. The microetching liquid circulation regeneration and metal copper recovery system according to claim 2, characterized in that: the cathode-anode area ratio can reach 1:2 to 1:5.