WO2017041471A1

WO2017041471A1 - Resource-saving acidic etching waste solution reuse and recovery system

Info

Publication number: WO2017041471A1
Application number: PCT/CN2016/077065
Authority: WO
Inventors: 韦建敏; 吴梅; 赵兴文; 张晓蓓; 张小波
Original assignee: 成都虹华环保科技股份有限公司
Priority date: 2015-09-09
Filing date: 2016-03-23
Publication date: 2017-03-16

Abstract

A resource-saving acidic etching waste solution recycling and recovery system comprises: an etching solution treatment system; a chlorine gas recycling system; and a recovered solution reuse system. The etching solution treatment system comprises an etching production line (1); a mother liquor storage tank (2); an electrolytic cell; and a dissolution and absorption system (6). The electrolytic cell comprises a cathode compartment (3) and an anode compartment (5). The mother liquor storage tank (2), the cathode compartment (3), the anode compartment (5) and the dissolution and absorption system (6) sequentially communicate with each other. The etching production line (1) respectively communicates with the mother liquor storage tank (2) and the dissolution and absorption system (6). The chlorine gas recycling system comprises a gas-scrubbing system (7) and a tail-gas treatment system (8). The recovered solution reuse system comprises a recovered solution storage tank (10) and a recovered solution treatment system (11). The anode compartment (5), the gas-scrubbing system (7) and the tail-gas treatment system (8) sequentially communicate with each other. The acidic etching waste solution reuse and recovery system is configured to treat an acidic etching waste solution, and can perform an off-line production operation, save costs and resources, and prevent environmental pollution.

Description

Description: The invention relates to an acid etching waste liquid recycling system capable of saving resources

[0001] The present invention relates to a waste liquid processing system, and more particularly to an acid etching waste liquid recycling system that can save resources.

Background technique

[0002] The acidic etching solution is an etching liquid for fine circuit fabrication of a printed circuit board and fabrication of an inner layer of a multilayer board.

With the rapid development of the modern electronics industry, the number of circuit board manufacturers has increased rapidly. The industrial wastewater of such enterprises is seriously polluted by the environment, and the copper ion content of such industrial wastewater is very high. Therefore, the wastewater and waste liquid generated by the circuit board production enterprises are high. The serious environmental pollution and waste of resources have been increasingly concerned by the society. In order to avoid waste and protect the environment, it is necessary to recycle and reuse the acidic etching solution.

[0003] The regeneration of acid etching old liquid is mainly converted into an acidic solution of suitable specific gravity, transparency and high oxidation-reduction potential by chemical and electrochemical methods to maintain stable and rapid etching of the printed circuit board. Chemical regeneration is the main method for the regeneration of acidic copper chloride etching solution. The principle is to discharge a certain proportion of the old liquid (high specific gravity), add a certain amount of liquid (low specific gravity), or add a certain amount of water. , to adjust the specific gravity of the etching solution. The oxidizing agent in the same sputum liquid oxidizes the monovalent copper ion to the divalent copper ion, or the oxidizing agent is separately added to increase the oxidation-reduction potential of the etching liquid, thereby restoring the original performance of the etching liquid. Common oxidants are air, oxygen, chlorine, ozone, sodium hypochlorite, sodium chlorate, hydrogen peroxide, and the like. However, the total copper is increasing, and finally it is necessary to exclude a part of the acidic etching liquid to maintain a certain total copper concentration, which not only pollutes the environment, but also causes a large amount of waste of copper and acid; electrochemical regeneration method is an online regeneration method. Metallic copper with commercial value can be produced by electrolysis, but chlorine gas is generated at the same time to form a polluted exhaust gas, which not only pollutes the environment but also causes waste.

[0004] Chinese Patent Application No. 2010205671550, discloses a copper ion acid etching solution regeneration system, which is used for online processing of an acidic etching solution, which is limited by the etching line production time, and can only be etched with Simultaneous production, and the exhaust gas treatment device inside the system consumes the chlorine inside the system. Although it is environmentally friendly, it causes waste of resources, causing the loss of chlorine inside the system, and additional acid solution is needed to ensure the efficiency of the etching solution. technical problem

[0005] It is an object of the present invention to overcome the shortcomings of the prior art and to provide a resource-saving acidic etching waste liquid recycling system.

Problem solution

Technical solution

[0006] The object of the present invention is achieved by the following technical solutions: A resource-saving acidic etching waste liquid recycling system, including an etching liquid processing system, a chlorine gas recovery system and a regenerating liquid circulation system, and an etching liquid processing system including an etching production line a mother liquor storage tank, an electrolysis tank and a dissolution absorption system, the electrolysis tank comprises a cathode tank, a membrane and an anode tank, the mother liquor storage tank, the cathode tank, the anode tank, the dissolution absorption system are sequentially connected, and the etching production line is respectively connected with the mother liquid storage tank and the dissolution absorption system Connected, the dissolution absorption system is in communication with the etching line;

[0007] The chlorine gas recovery system includes a scrubbing system and an exhaust gas treatment system, and the anode tank, the scrubbing system, and the exhaust gas treatment system are sequentially connected;

[0008] The regeneration liquid circulation system includes a regeneration liquid storage tank and a regeneration liquid treatment system, and the anode tank, the regeneration liquid storage tank, the reconditioning liquid treatment system, and the etching production line are sequentially connected.

[0009] The membrane is a membrane, a cationic membrane or an anionic membrane.

[0010] The cathode tank obtains electrolytic copper by electrolysis.

[0011] An ion concentration detecting device is disposed in the electrolytic cell.

[0012] The regenerative liquid processing system is provided with an acidity detecting device.

[0013] The apparatus and piping in the system are made of an acid-resistant, alkali-resistant, corrosion-resistant material.

Advantageous effects of the invention

Beneficial effect

[0014] The present invention has the following advantages:

[0015] 1. The system is used for processing acid etching waste liquid, and the etching liquid can be recycled and recycled in the same manner as the metal copper is extracted, so that the etching liquid processing can be performed offline, the processing efficiency is improved, and the reasonable distribution is facilitated. Resources enable dynamic balancing of etching and etching solutions, avoiding waste of resources and achieving sustainable production

[0016] 2. By using acid concentration technology to separate the regeneration liquid into a high acidity solution and a low acidity solution, high acidity The solution is directly returned to the etching line for recycling. The low acidity solution is formulated into an oxidant and then returned to the etching line. No waste liquid is generated during the entire cycle to achieve true zero emissions.

[0017] 3. By the invention, the electrolytic chlorine gas can be recovered, and the chlorine gas is dissolved in the production line to react with the cuprous ions to form divalent copper ions, and the regenerated etching liquid is directly returned to the production line for recycling, if not and etching. Through the production line linkage, the electrolyzed chlorine gas can be washed and further processed to produce valuable products containing chlorine, so as to avoid polluting the environment, wasting resources, recycling chlorine and water in the system, and reducing the addition of additives or oxidants. Reduced production costs and saved resources.

Brief description of the drawing

DRAWINGS

1 is a schematic structural view of a resource-saving acid etching waste liquid recycling system;

[0019] In the figure, 1-etching line, 2-mother liquid storage tank, 3-cathode tank, 4-film, 5-anode tank, 6-dissolving absorption system, 7-gas scrubbing system, 8-exhaust gas treatment system, 9 - Electrolytic copper, 10-regenerant storage tank, 11-regeneration liquid treatment system.

Embodiments of the invention

[0020] The present invention will be further described below with reference to the accompanying drawings, and the scope of protection of the present invention is not limited to the following

[0021] As shown in FIG. 1, a resource-saving acidic etching waste liquid recycling system includes an etching liquid processing system, a chlorine gas recovery system, and a regenerating liquid circulation system, and the etching liquid processing system includes an etching production line and a mother liquid storage tank. 2. Electrolyzer and dissolution absorption system 6, the electrolytic cell comprises a cathode tank 3, a membrane 4 and an anode tank 5, the mother liquor storage tank 2, the cathode tank 3, the anode tank 5, the dissolution absorption system 6 are sequentially connected, and the etching production line 1 and the mother liquid are respectively The storage tank 2 is in communication with the dissolution absorption system 6, and the dissolution absorption system 6 is in communication with the etching line 1;

[0022] The chlorine gas recovery system includes a scrubbing system 7 and an exhaust gas treatment system 8, and the anode tank 5, the scrubbing system 7 and the exhaust gas treatment system 8 are sequentially connected;

The regenerating liquid circulation system includes a regenerant liquid storage tank 10 and a regenerating liquid processing system 11, and the anode tank 5, the regenerant liquid storage tank 10, the regenerating liquid processing system 11, and the etching production line 1 are sequentially connected.

[0024] In the embodiment, the membrane 4 is a membrane, a cation membrane or an anion membrane, and which specific filtration membrane can be selected according to specific production conditions. [0025] In the embodiment, the cathode tank 3 obtains electrolytic copper 9 by electrolysis, thereby balancing the copper ions in the liquid, ensuring the benefit of the etching liquid, and avoiding the environmental pollution caused by the loss of copper in the ion form. Copper metal can be used as a commodity of commercial value.

[0026] In the embodiment, an ion concentration detecting device is disposed in the electrolytic cell, and the ion concentration in the liquid is detected by the ion concentration detecting device, and the resource is appropriately allocated according to the detected information, and the flow rate is regulated, so that the etching is performed. It can achieve dynamic balance with etchant treatment, which is conducive to the realization of continuous production.

[0027] In the embodiment, the regeneration liquid processing system 11 is provided with an acidity detecting device. The regenerating liquid processing system 11 separates the high acidity liquid and the low acidity liquid by concentration, and can be detected by the acidity detecting device. The specific value to the acidity can be used as an etchant to be utilized when the acidity reaches the desired level.

[0028] In the embodiment, the device and the pipeline in the system are made of acid-proof, alkali-resistant and corrosion-resistant materials, thereby increasing the service life of the system and reducing the difficulty of maintenance.

[0029] The working process of the present invention is as follows: The etching liquid flowing out on the etching line 1 is partially stored in the dissolution absorption system 6 for storage, and the other portion is stored in the mother liquid storage tank 2, and the flow rate is controlled by the mother liquid storage tank 2 to make the mother liquid storage tank 2 The etching solution enters the cathode tank 3. Under the action of electrolysis in the cathode tank 3, cuprous ions are reduced to divalent copper ions, and the divalent copper ions are reduced to electrolytic copper. The remaining unreduced copper ions and other ions enter the anode tank 5 through the membrane 4.

[0030] The working process of the present invention is as follows: The etchant portion flowing out of the etching line 1 enters the dissolution absorbing system 6 for storage, and the other portion enters the mother liquid storage tank 2 for storage, and the flow rate is controlled by the mother liquid storage tank 2 to make the mother liquid storage tank 2 The etching solution enters the cathode tank 3. Under the action of the electrolysis in the cathode tank 3, the cuprous ions are reduced to divalent copper ions, and the divalent copper ions are reduced to electrolytic copper, and the electrolytic copper is washed and washed by the copper washing device 9 . The remaining unreduced copper ions and other ions enter the anode tank 5 through the membrane 4.

[0031] Chloride ions are oxidized to form chlorine gas under the action of electrolysis in the anode tank 5. When the etching line 1 is in production, chlorine gas enters the solvent absorption system 6, and undergoes redox reaction with cuprous ions to obtain copper ions and an acidic liquid. The liquid can be used as an etchant to enter the etching line 1 to complete the production; when the etching line 1 is not produced, the chlorine gas enters the scrubbing system 7 to obtain pure chlorine gas after being removed, and the pure chlorine gas enters the exhaust gas treatment system 8 and is reacted to form a valuable content. Chlorine products. Since the electrolytic reaction in the electrolytic cell is not completely performed, the liquid remaining after the electrolysis contains ions such as copper ions, chloride ions, and hydrogen ions as the regenerating liquid, and the regenerating liquid has weak acidity, and the regenerating liquid enters the regenerating liquid storage tank 10 to be stored, and is regenerated. The storage tank 10 controls the flow rate to be delivered to the regenerating liquid processing system 11, and the regenerating liquid is concentrated in the regenerating liquid processing system 11 to separate the high acidity liquid and the low acidity liquid, and the high acidity liquid is stored as the etching liquid and the low acidity liquid separately. When the etching line 1 is in production, the high acidity liquid can be sent to the etching line 1 for production, and the low acidity liquid can be formulated into a new liquid together with the oxidant, the additive, etc., and slowly added back to the etching line to control the etching liquid. ORP value, which can achieve water recycling

, reduce water loss in the system and reduce resource consumption. Dynamic balancing can be achieved by controlling the degree of electrolysis and the flow of liquid, facilitating automated production and off-line processing of acid etching waste.

Claims

Claim

[Claim 1] A resource-saving acidic etching waste liquid recycling system, comprising: an etching liquid processing system, a chlorine gas recovery system, and a regenerating liquid circulation system, the etching liquid processing system including an etching production line (1), a mother liquid a storage tank (2), an electrolytic cell and a dissolution absorption system (6), the electrolytic cell comprising a cathode tank (3), a membrane (4) and an anode tank (5), a mother liquor storage tank (2), a cathode tank (3), an anode The tank (5) and the dissolution absorption system (6) are sequentially connected, and the etching production line (1) is respectively connected with the mother liquid storage tank (2) and the dissolution absorption system (6), and the dissolution absorption system (6) is connected with the etching production line (1); The chlorine recovery system includes a scrubbing system (7) and an exhaust gas treatment system (8), and the anode tank (5), the scrubbing system (7), and the exhaust gas treatment system (8) are sequentially connected;

The regenerating liquid circulation system includes a regenerant liquid storage tank (10) and a regenerating liquid processing system (11), an anode tank (5), a regenerant liquid storage tank (10), a regenerating liquid processing system (11), and an etching production line (1). .

[Claim 2] A resource-saving acidic etching waste liquid recycling system according to claim 1, wherein the film (4) is a separator, a cation film or an anion film.

[Claim 3] A resource-saving acidic etching waste liquid recycling system according to claim 1, characterized in that: the cathode tank (3) obtains electrolytic copper (9) by electrolysis.

[Claim 4] A resource-saving acidic etching waste liquid recycling system according to claim 1, wherein the electrolytic cell is provided with an ion concentration detecting device.

[Claim 5] A resource-saving acidic etching waste liquid recycling system according to claim 1, wherein: the regeneration liquid processing system (11) is provided with an acidity detecting device.

[Claim 6] A resource-saving acidic etching waste liquid recycling system according to claim 1, wherein: the device and the pipeline in the system are resistant to acid, alkali and corrosion. Made of materials.