CN213142227U

CN213142227U - Ion membrane electrolytic cell and copper recovery equipment for regeneration and recycling of acidic etching solution

Info

Publication number: CN213142227U
Application number: CN202021684480.5U
Authority: CN
Inventors: 罗国华; 顾晓聪; 刘碧华
Original assignee: Guangdong Zhending Environmental Technology Co ltd
Current assignee: Guangdong Zhending Environmental Technology Co ltd
Priority date: 2020-08-13
Filing date: 2020-08-13
Publication date: 2021-05-07
Anticipated expiration: 2030-08-13

Abstract

The utility model relates to an electrolysis equipment technical field, concretely relates to ion exchange membrane electrolysis trough and acid etching solution regeneration recycle copper recovery plant, this ion exchange membrane electrolysis trough include the cell body, are equipped with two at least negative plates and at least one positive pole box in the cell body, and the negative plate sets up with positive pole box interval, and positive pole box includes support frame, anode plate and two positive pole ionic membrane, and the anode plate is pegged graft in the support frame, and two positive pole ionic membrane are located the both sides of anode plate, the support frame is made by the titanium net, and the titanium net of support frame both sides passes through the resistance detection device electricity with adjacent negative plate and is connected, and the resistance detection device electricity is connected with audible-visual annunciator. The utility model discloses an ionic membrane electrolytic cell is through adopting resistance detection device to measure the resistance between titanium net and the adjacent negative plate, is less than the setting value when resistance, produces alarm signal, is zero when resistance, can send audible-visual annunciation at this moment, and the operator in time handles, can prevent like this that the ionic membrane from impaling.

Description

Ion membrane electrolytic cell and copper recovery equipment for regeneration and recycling of acidic etching solution

Technical Field

The utility model relates to an electrolysis equipment technical field, concretely relates to ion membrane electrolysis trough and acid etching solution regeneration recycle copper recovery plant.

Background

The ion exchange membrane electrolysis method is a new technology developed on the basis of ion exchange resin, and utilizes the characteristic that the ion exchange membrane has selective permeability to anions and cations to allow ions with one charge to pass through and limit ions with opposite charges to pass through so as to achieve the purposes of concentration, desalination, purification and electrochemical synthesis.

At present, in the etching process of the ionic membrane on the circuit board, the concentration of copper ions in the etching solution can be gradually increased to reduce the etching effect, and the copper ions (Cu) in the etching solution must be used for achieving the best etching effect of the etching solution⁺) Redox number, chloride ion (Cl)^-) And the acid equivalent is kept in a reasonable and stable range, and the continuous addition of the sub-solution is required to replace the waste etching solution which loses the etching capability in order to keep the optimum concentration of the above-mentioned components in the etching solution. In the manufacturing process of the printed circuit board, the recycling and regeneration of the acidic copper chloride etching solution always troubles the enterprises of the printed circuit board, the non-renewable acidic copper chloride etching solution contains about 100 to 130 grams of copper per liter, and the copper content of the waste etching solution generated in every month in Guangdong province is as high as thousands of tons, so that the recycling of the metal copper and the recycling and regeneration of the waste etching solution inevitably have great economic benefit and environmental protection value.

At present, many units for researching and developing copper chloride etching solution electrolysis recovery copper at home and abroad are available, including many scientific research institutions, universities and the like, other problems occur in the use process of the researched and developed equipment, so that the researched and developed equipment cannot be put into industry, if the etching solution cannot be recycled after copper is extracted through electrolysis, the transfer of pollution sources also causes secondary pollution to the environment, meanwhile, chlorine is separated out from an anode in the electrolysis process, according to the theoretical calculation, 111.6kg of chlorine is separated out from the anode every time 100kg of copper is separated out through electrolysis, and the volume of the copper chloride in the standard state is about 35.26m³However, the cost and equipment complexity are increased by properly treating the large amount of chlorine gas generated and the residual waste liquid without causing secondary pollution to the environment.

The on-line regeneration process of the chemical liquid is an on-line regeneration process, namely, electrolytic regeneration equipment is connected with an etching machine in series, and the pair of reactions of regeneration reaction and etching reaction which are mutually reversible are carried out in a circulating mode in turn. The electro-catalytic coating electrode is used as an anode, and the potential difference between the anode and anolyte is used as a reaction driving force, so that cuprous complex ions on the surface of the anode are oxidized into copper complex ions, and the oxidation regeneration of the etching waste liquid is realized; and (3) establishing a copper concentration difference between the anolyte and the catholyte, and under the promotion of electrochemical potential and chemical potential, part of copper ions are transferred to a cathode region, so that the specific gravity of the acidic etching solution is reduced to a certain range, or the specific gravity of the etching solution is adjusted by using the catholyte in an auxiliary way, so that the chemical composition, the oxidation-reduction potential and the specific gravity of the acidic etching waste solution are recovered as before.

By the perfect combination of the device and the process, the economic problem and the environmental protection problem which puzzle the PCB industry for years of waste etching liquid reutilization are finally solved.

The 'ionic membrane copper electrolysis' process is adopted, and the process is that an anode area and a cathode area of an electrolytic bath are divided into two independent areas by the ionic membrane; the anode area is a waste etching solution regeneration area, and univalent copper ions in the waste etching solution after copper reduction are subjected to electrochemical reaction to generate bivalent copper ions so as to regenerate the waste etching solution; the cathode area is a copper recovery area, ions in the solution are selectively and directionally transferred through an ion diaphragm, and copper ions in the solution are reduced into zero-valent copper through electrons.

However, the conventional apparatus has a problem that the ionic membrane is easily damaged. In the process of copper electroplating, copper plating layers are easy to grow long copper nails, and sharp copper nails are easy to pierce the ion exchange membrane. Ion exchange membranes are unusually expensive and damage to the ion membrane causes significant losses. Meanwhile, the damaged ionic membrane causes mixing of the anolyte and the catholyte, corrosion of the copper plating layer, increase of energy consumption of copper plating and increase of cost.

Disclosure of Invention

In order to overcome the shortcoming and the deficiency that exist among the prior art, the utility model aims to provide an ion membrane electrolysis trough, this ion membrane electrolysis trough can early warning copper nail produce with the harm of prevention copper nail, simple structure, convenient to use, it is with low costs.

Another object of the present invention is to provide a copper recycling apparatus for recycling acidic etching solution.

The purpose of the utility model is realized through the following technical scheme: the utility model provides an ion membrane electrolytic cell, includes the cell body, is equipped with two at least negative plates and at least one positive pole box in the cell body, and negative plate and positive pole box interval set up, and positive pole box includes support frame, anode plate and two positive pole ionic membrane, and the anode plate is pegged graft in the support frame, and two positive pole ionic membrane are located the both sides of anode plate, the support frame is made by the titanium net, and the titanium net of support frame both sides is connected through resistance detection device electricity with adjacent negative plate, and resistance detection device electricity is connected with audible-visual annunciator.

The other purpose of the utility model is realized by the following technical scheme: the ionic membrane copper recovery equipment is the ionic membrane electrolytic cell.

Furthermore, the ionic membrane copper recovery equipment further comprises a circulating tank, an etching production line, an etching waste liquid collecting tank and an etching waste liquid storage tank, wherein the ionic membrane electrolytic tank is communicated with the circulating tank, the circulating tank is communicated with the etching production line, the etching production line is communicated with the etching waste liquid collecting tank, the etching waste liquid collecting tank is communicated with the etching waste liquid storage tank, and the etching waste liquid storage tank is communicated with the ionic membrane electrolytic tank.

Furthermore, the ion membrane electrolytic cell comprises an anode region and a cathode region, the circulating cell comprises an anode circulating cell and a cathode circulating cell, the anode circulating cell is communicated with the anode region, the cathode circulating cell is communicated with the cathode region, and an etching solution parameter monitoring device is arranged on the anode circulating cell.

The beneficial effects of the utility model reside in that: the utility model discloses an ionic membrane electrolytic cell is through adopting resistance detection device to measure the resistance between titanium net and the adjacent negative plate, is less than the setting value when resistance, produces alarm signal, and when resistance be zero, audible-visual annunciator can send audible-visual annunciator, and the operator in time handles, can prevent like this that the ionic membrane from impaling.

The utility model discloses an ion membrane electrolysis trough can produce the harm with the prevention copper nail by the early warning copper nail, simple structure, and convenient to use is with low costs.

The utility model discloses an ionic membrane copper recovery plant adopts ionic membrane electrolysis technology to regenerate etching solution and retrieve copper, this technology is an online regeneration technology, be about to electrolysis regeneration plant and etching machine and establish ties, regeneration reaction and etching reaction this to each other reversible reaction cycle in proper order go on, but regeneration back etching solution cycle use, regeneration liquid medicine stability is good, the etching factor is qualified, can save oxidant 70-90% after the retrieval and utilization, save hydrochloric acid 50-70%, reduce 70% etching waste liquid and discharge, equipment stable performance, the operation is maintained simply, degree of automation is high, after with etching line interconnect, the automatic cycle function, do not influence production in the installation and debugging process, the installation and debugging finishes and can put into use.

Drawings

Fig. 1 is a schematic structural diagram of the ion membrane electrolyzer of the present invention.

The reference signs are: the device comprises a tank body 1, a cathode plate 2, an anode plate 3, an anode ion membrane 4, a titanium mesh 5, a resistance detection device 6 and an audible and visual alarm 7.

Detailed Description

In order to facilitate understanding of those skilled in the art, the present invention will be further described with reference to the following examples and the accompanying fig. 1, which are not intended to limit the present invention.

See figure 1, an ion membrane electrolytic cell, including cell body 1, be equipped with two at least negative plates 2 and at least one positive pole box in the cell body 1, negative plate 2 sets up with positive pole box interval, and positive pole box includes support frame, anode plate 3 and two positive pole ionic membrane 4, and anode plate 3 pegs graft in the support frame, and two positive pole ionic membrane 4 are located the both sides of anode plate 3, the support frame is made by titanium net 5, and the titanium net 5 of support frame both sides is connected through resistance detection device 6 electricity with adjacent negative plate 2, and resistance detection device 6 electricity is connected with audible-visual annunciator 7. The anode ion membrane 4 and the support frame are fastened by titanium screws. The support frame is made of a titanium mesh 5, and is corrosion-resistant, conductive and high in strength.

The utility model discloses an ionic membrane electrolytic cell is through adopting resistance detection device 6 to measure the resistance between titanium net 5 and the adjacent negative plate 2, is less than the setting value when resistance, produces alarm signal, and when resistance be zero, audible-visual annunciator 7 sends audible-visual annunciator, and the operator in time handles, can prevent like this that the ionic membrane from impaling.

The design principle of the ion membrane electrolytic cell of the utility model is as follows: when having the copper nail, the distance of ionic membrane and copper nail can diminish, and conventional distance is 40 millimeters, if add a sensor on the ionic membrane, can detect this distance and report to the police, just can accomplish the early warning function. To implement this sensor, various possible ways of photothermal-electromagnetic analysis were analyzed, and it was found that electrical resistance should be achievable and easily achievable. The resistance has a direct relation with the distance, the distance is shortened, and the resistance is reduced. And detecting the change value of the resistance, so that the growth condition of the copper nail can be preliminarily judged. Under the limit condition, the copper nail contacts the ionic membrane, the resistance is zero, and at the moment, the sound-light alarm can be sent out, so that the operator can timely process the ionic membrane. This prevents the ionomer membrane from being punctured.

The titanium mesh 5 is connected to the cathode copper plate, and copper is easily plated on the titanium mesh 5, so that a positive voltage is maintained on the titanium mesh 5 with respect to the cathode. So that no copper is deposited on the titanium mesh 5. For a typical period of time, a positive voltage is maintained with respect to the cathode on the titanium mesh 5. So that no copper is deposited on the titanium mesh 5 and even the copper layer on the titanium mesh 5 will dissolve. The titanium mesh 5 and cathode copper remain connected for a specified test period, such as every 5 minutes for 2 seconds.

The ionic membrane copper recovery equipment is the ionic membrane electrolytic cell.

In this embodiment, the ionic membrane copper recovery equipment further includes a circulation tank, an etching production line, an etching waste liquid collecting tank, and an etching waste liquid storage tank, wherein the ionic membrane electrolytic tank is communicated with the circulation tank, the circulation tank is communicated with the etching production line, the etching production line is communicated with the etching waste liquid collecting tank, the etching waste liquid collecting tank is communicated with the etching waste liquid storage tank, and the etching waste liquid storage tank is communicated with the ionic membrane electrolytic tank.

In this embodiment, the ion membrane electrolytic cell includes an anode region and a cathode region, the circulation tank includes an anode circulation tank and a cathode circulation tank, the anode circulation tank is communicated with the anode region, the cathode circulation tank is communicated with the cathode region, and an etching solution parameter monitoring device is installed on the anode circulation tank.

The structure of the ionic membrane copper recovery device adopted by the utility model is consistent with the structure disclosed in the Chinese invention patent with the application number of 201710030250.3, and is not repeated herein.

The above-mentioned embodiment is the utility model discloses the implementation of preferred, in addition, the utility model discloses can also realize by other modes, not deviating from the utility model discloses any obvious replacement is all within the protection scope under the prerequisite of design.

Claims

1. The utility model provides an ion exchange membrane electrolytic cell, includes the cell body, is equipped with two at least negative plates and at least one positive pole box in the cell body, and negative plate and positive pole box interval set up, and the positive pole box includes support frame, anode plate and two positive pole ionic membrane, and the anode plate is pegged graft in the support frame, and two positive pole ionic membrane are located the both sides of anode plate, its characterized in that: the support frame is made by the titanium net, and the titanium net of support frame both sides is connected through resistance detection device electricity with adjacent negative plate, and resistance detection device electricity is connected with audible-visual annunciator.

2. The utility model provides an acid etching solution regeneration recycles copper recovery plant which characterized in that: the copper recovery plant comprises the ionic membrane electrolysis cell of claim 1.

3. The apparatus for recycling copper from acidic etching solution according to claim 2, wherein: the copper recovery equipment further comprises a circulating tank, an etching production line, an etching waste liquid collecting cylinder and an etching waste liquid storage tank, wherein the ion membrane electrolytic tank is communicated with the circulating tank, the circulating tank is communicated with the etching production line, the etching production line is communicated with the etching waste liquid collecting cylinder, the etching waste liquid collecting cylinder is communicated with the etching waste liquid storage tank, and the etching waste liquid storage tank is communicated with the ion membrane electrolytic tank.

4. The apparatus for recycling copper from acidic etching solution according to claim 3, wherein: the ion membrane electrolytic cell comprises an anode region and a cathode region, the circulating cell comprises an anode circulating cell and a cathode circulating cell, the anode circulating cell is communicated with the anode region, the cathode circulating cell is communicated with the cathode region, and an etching solution parameter monitoring device is arranged on the anode circulating cell.