WO2022022461A1

WO2022022461A1 - Method and apparatus for regeneration and reuse of alkaline etching waste liquid

Info

Publication number: WO2022022461A1
Application number: PCT/CN2021/108441
Authority: WO
Inventors: 叶涛; 叶旖婷
Original assignee: 叶涛
Priority date: 2020-07-28
Filing date: 2021-07-26
Publication date: 2022-02-03
Also published as: CN115135806B; CN115135806A; TW202204692A

Abstract

A method for regeneration and reuse of an alkaline etching waste liquid, comprising the following steps: using an electrolytic reaction tank, wherein an electrolytic separator is arranged in the electrolytic reaction tank to form an anode zone and a cathode zone, the electrolytic separator, by means of the action of an electric field force, is capable of effectively reducing, or even preventing, migration of anions in a catholyte to the anode zone, the anode zone and the cathode zone are respectively filled with an anolyte and the catholyte, the anolyte is an aqueous solution of a carbon dioxide generating raw material or an aqueous solution of the carbon dioxide generating raw material and ammonia, and the catholyte is an alkaline etching waste liquid or a mixed solution of the alkaline etching waste liquid with water and/or an alkaline etching sub-liquid and/or a regenerated etching sub-liquid; and supplementing the anolyte with the carbon dioxide generating raw material in an electrolysis process. The method does not need to introduce an organic extractant, and can effectively reduce or even eliminate the reaction of ammonia and chlorine in the anolyte during the electrolysis process, and avoid the loss of ammonia and chloride ions.

Description

Method and equipment for regeneration and reuse of alkaline etching waste liquid

technical field

The invention belongs to the technical field of alkaline etching waste liquid treatment, and particularly relates to a method and equipment for regeneration and reuse of alkaline etching waste liquid.

Background technique

Etching is an important step in the existing printed circuit board (PCB) fabrication process. Etching refers to chemically etched and removed copper etchant that is not needed on the copper-clad substrate to form the desired circuit pattern.

Alkaline cupric ammonium chloride etching solution (hereinafter referred to as "alkaline etching solution") is one of the most common circuit board etching solutions at present. Its main components are copper salt, ammonium chloride and ammonia water, and carbonate is optional. And other optional additives, the carbonate is usually ammonium carbonate and/or ammonium bicarbonate. In order to keep the composition of the etching solution stable, it is necessary to continuously add supplementary solution in the copper etching production to maintain the etching production. The replenishing solution is usually an aqueous solution of ammonia and/or ammonium chloride and/or ammonium salt and/or additives, and the replenishing solution containing more than one component is collectively referred to as an alkaline etching sub-liquid in the industry. During the etching process, the alkaline etchant is etched through the reaction of the divalent cupric chloride ammonium complex Cu(NH ₃ ) ₄ Cl ₂ and metal copper to generate the monovalent cupric ammonium complex Cu(NH ₃ ) ₂ At the same time, by participating in the reaction with oxygen, the monovalent cupric ammonium chloride complex is oxidized and regenerated into a divalent cupric chloride ammonium complex. The etching chemical reaction regeneration equation is as follows:

Cu+Cu(NH ₃ ) ₄ Cl ₂ →2Cu(NH ₃ ) ₂ Cl;

2Cu(NH3)2Cl ₊ 4NH4Cl ₊ _2NH3 +1/2O2 _→ 2Cu( _NH3 ₎ _4Cl2 ₊ _H2O .

Due to the addition of supplementary liquid during the etching process, it is inevitable that the etching liquid in the etching tank will increase and overflow the tank, and the alkaline etching liquid or the alkaline etching liquid that has overflowed outside the etching tank is generally called in the industry. Alkaline etching waste liquid; and the copper ion concentration of the alkaline etching waste liquid is usually 30-200g/L, and the pH value is 7.0-9.5.

For circuit board production plants using alkaline etching production process, a large amount of alkaline high copper ion concentration etching waste liquid needs to be treated every day. At present, in addition to selling the waste liquid to environmental protection companies for treatment, some manufacturers use equipment to extract copper from it in the factory and regenerate and recycle the waste liquid. That is, the remaining part of the copper-containing waste liquid after copper extraction is Add chlorine salt and/or ammonia and/or additives and/or clean water according to process requirements to obtain alkaline etching regeneration sub-liquid, which is reused in alkaline etching production. In the prior art, there are two methods for the regeneration and reuse of the alkaline etching waste liquid in the factory, the first one is the extraction and electrolysis method, and the second one is the direct electrolysis method. The first extraction and electrolysis method is to first use an extractant to extract the copper in the alkaline etching waste liquid for phase-separation treatment, and then use sulfuric acid to back-extract to obtain a copper sulfate solution, and then conduct electrolysis to extract copper. Because the whole process of extraction and electrolysis is complicated and tedious and there is a lot of ammonia nitrogen pollution, and the alkaline etching regeneration sub-liquid prepared by regeneration has an organic extractant that acts as a corrosion inhibitor, when it is reused in the etching production line, it will affect the etching process. Production quality and production efficiency, so in recent years, a second type of direct electrolysis method has emerged in the industry to regenerate copper from alkaline etching waste liquid.

The direct electrolysis method breaks the complex structure of the copper ammonia complex through electrochemical reaction, reduces the copper ions in the copper ammonia complex to metallic copper on the electrolysis cathode, and generates ammonium chloride and ammonia water, accompanied by water. The electrolytic reaction produces oxygen and hydrogen ions. Therefore, a large amount of ammonia gas will escape during the electrolysis process of the direct electrolysis method. The overall reaction equation of the electrochemical reaction is as follows:

Cu( _NH3 ) _4Cl2 ₊ _3H2O →Cu+2NH4Cl ₊ _2NH4OH + ₁ /2O2↑.

In the direct electrolysis method, both the electrolytic anode and the electrolytic cathode are usually immersed in the alkaline etching waste solution for electrochemical reaction, and the anolyte is an alkaline solution, so people in the industry mostly use low-cost conductive graphite materials. Overcome the disadvantage that titanium-coated anodes are easy to fall off in alkaline solutions. Due to the large resistance of graphite, a large amount of heat is generated during the electrolysis process and conducted into the electrolyte to increase the temperature of the solution. However, since the alkaline etching waste liquid contains a large amount of ammonia water and/or inorganic ammonium salts, it is easily decomposed to generate ammonia gas when heated. At the same time, the charged ions in the electrolyte will be attracted and migrated by the attraction of the electric field during electrolysis, that is, the ammonium ions in the alkaline etching waste liquid will accumulate near the electrolytic cathode and the chloride ions will accumulate near the electrolytic anode. Therefore, chlorine gas will be produced on the electrolysis anode, and the chlorine gas continuously produced around the anode will chemically react with ammonia water, and the reaction equation is 2NH ₃ +3Cl ₂ =N ₂ ↑+6HCl. Therefore, the use of the second direct electrolysis method will continuously decompose and decompose the NH ₃ component of the alkaline etching waste liquid during the regeneration process, resulting in an increase in the regeneration cost of the waste liquid. In addition, the amount of ammonia gas generated under the high temperature operation of the electrolyte solution is large, and it is still faced with great difficulties in the existing process technology to collect it for recycling.

The above-mentioned two existing technologies for recycling and regenerating alkaline etching waste liquid still have deficiencies and need to be further improved.

SUMMARY OF THE INVENTION

The first object of the present invention is to provide a method for regeneration and reuse of alkaline etching liquid, which does not need to introduce an organic extractant that affects the regeneration and use quality of alkaline etching liquid, and can effectively reduce or even eliminate anodes in the electrolysis process. The ammonia gas in the electrolyte reacts with the chlorine gas to avoid the loss of ammonia and chloride ions.

The second object of the present invention is to provide a device used in the method for regenerating and reusing the alkaline etching waste liquid.

In order to realize the above-mentioned first purpose, the technical scheme adopted in the present invention is:

A method for regeneration and reuse of alkaline etching waste liquid, comprising the following steps: using an electrolytic reaction tank, wherein an electrolytic separator is arranged in the electrolytic reaction tank to form an anode area and a cathode area, and the electrolytic separator can act on an electric field force. It can effectively reduce or even prevent the anions in the catholyte from migrating to the anode area; the anode area and the cathode area are respectively filled with anolyte and catholyte; the anolyte is an aqueous solution of carbon dioxide generating raw materials, or carbon dioxide generating An aqueous solution of raw materials and ammonia, the carbon dioxide generating raw material is a substance that generates carbon dioxide under electrolysis conditions or that generates carbon dioxide due to the rise in the temperature of the electrolyte during the electrolysis process; the catholyte is alkaline etching waste liquid, or it is mixed with water and/or a mixture of alkaline etching sub-liquid and/or regeneration etching sub-liquid;

The regeneration of the alkaline etching waste liquid is carried out by electrified electrolysis, and the carbon dioxide generating raw material is continuously or intermittently supplemented to the anolyte during the electrolysis process.

All alkaline etching waste liquids with a pH value of 6.8 to 10.0 and a copper ion concentration of 2 to 200 g/L are suitable for the method of the present invention. When the catholyte is a mixed solution of alkaline etching waste liquid and water and/or alkaline etching sub-liquid and/or regeneration etching sub-liquid, the copper ion concentration of the catholyte is greater than or equal to 2 g/L.

During the electrolysis process, the electrolytic cathode is electrolytically decomposed into metallic copper. Because the alkaline etching waste liquid is electrolyzed in the cathode area and effectively prevents the chloride ions in the alkaline etching waste liquid from migrating from the cathode area to the anode area, avoiding the situation that a large amount of chloride ions and ammonia exist in the anode area at the same time, Prevent chloride ions from electrolyzing at the electrolytic anode to generate a large amount of chlorine gas and chemically react with ammonia water to cause loss; at the same time, due to carbon dioxide generation raw materials will generate carbon dioxide during the electrolysis process, plus the oxygen generated on the electrolytic anode, so that the anolyte has a relatively high concentration of chlorine gas. There are many air bubbles to generate slight pressure on the separation between the anode area and the cathode area, thereby effectively reducing the leakage of catholyte from the cathode area into the anode area through the gap between the two areas in the electrolysis reaction tank. In addition, the carbon dioxide gas generated due to the existence of carbon dioxide generating raw materials in the anode area can be reused in electrolysis or etching production, so as to realize the environmental protection and recycling of raw materials.

The electrolytic separator is a cation exchange membrane and/or a bipolar membrane, so as to effectively prevent the chloride ions of the alkaline etching waste liquid in the catholyte from entering the anode region and form chlorine gas through electrochemical reaction. In the above, the shortcoming of ammonia production raw material loss caused by the reaction of chlorine gas and ammonia in the alkaline etching waste liquid in the regeneration and reuse process of the alkaline etching waste liquid is overcome, and the problem of generating nitrogen trichloride explosives is avoided.

The purpose of separating carbon dioxide gas from the anolyte during the electrolysis process is to fill the anolyte to generate carbon dioxide generating raw materials, participate in the preparation of an alkaline etching sub-liquid and generate additives therein, and participate in the preparation of a regeneration etching sub-liquid and generate additives therein. , one or more of the etching solution absorbed in the etching sub-liquid, the regeneration etching sub-liquid, and the etching solution absorbed in the etching production line, so that it can be reused.

The carbon dioxide generating raw materials are formic acid, sodium formate, potassium formate, ammonium formate, calcium formate, oxalic acid, potassium oxalate, potassium hydrogen oxalate, sodium oxalate, sodium hydrogen oxalate, ammonium oxalate, carbonic acid, potassium carbonate, sodium carbonate, ammonium carbonate, carbonic acid At least one of potassium bicarbonate, sodium bicarbonate and ammonium bicarbonate.

The total mass percentage of carbon dioxide generating raw materials in the anolyte solution does not exceed 90%. When the total mass percentage of carbon dioxide generating raw materials in the anolyte exceeds 90%, the temperature control requirements of the electrolyte are relatively high. Otherwise, due to the unstable temperature of the electrolyte, the solubility of carbon dioxide generating raw materials will change, which will easily lead to some carbon dioxide. The crystallization of raw materials occurs, thereby affecting the electrolysis effect.

The source of the ammonia can be ammonia and/or ammonia water; the mass percentage of ammonia in the anolyte is not more than 28%. When the anolyte contains ammonia, the part of the carbon dioxide gas generated in the anode zone that dissolves in the anolyte reacts with the ammonia in the anolyte to generate ammonium carbonate and/or ammonium bicarbonate and continue to exist in the anolyte, Reduces the rate of loss of carbon dioxide-generating raw materials in the anolyte. When the mass percentage of ammonia in the anolyte exceeds 28%, a large amount of ammonia gas will volatilize and escape from the anolyte due to the high ammonia concentration, so the technological requirements for gas absorption are also high. Inadequate gas absorption reaction will result in loss of raw materials and even pollution of the production environment.

Preferably, the mass percentage of ammonia in the anolyte is not more than 25%.

Preferably, the carbon dioxide generating raw material in the anolyte is at least one of formic acid, ammonium formate, oxalic acid, ammonium oxalate, carbonic acid, ammonium carbonate, and ammonium bicarbonate. Since hydrogen ions can combine with hydroxide ions in alkaline etching waste liquid to form water, and ammonium ions are cations originally in alkaline etching waste liquid, these two cations enter from the anolyte during the electrolysis process. There is no accumulation of impurities in the catholyte, and the electrolyzed catholyte is formulated as a regenerated etching sub-liquid and reused in alkaline etching production without affecting the performance of the etching solution.

More preferably, the carbon dioxide generating raw material in the anolyte is at least one of ammonium carbonate, ammonium bicarbonate and ammonium formate, and the total mass percentage of the carbon dioxide generating raw material in the anolyte does not exceed 80%. Wherein, when the anolyte contains ammonium carbonate and/or ammonium bicarbonate, it can be combined with free ammonia in the anolyte and/or additionally added free ammonia by feeding carbon dioxide gas into the anolyte To achieve the regeneration of ammonium carbonate and/or ammonium bicarbonate, it is beneficial to easily control the concentration of each component in the anolyte under the premise of reducing production costs.

The inventors found that although both carbonate ions and bicarbonate ions undergo a reversible hydrolysis equilibrium reaction in an aqueous solution, under the action of an electric field, the equilibrium will be broken and the carbonate ions and bicarbonate ions will continue to be hydrolyzed. When the anolyte contains carbonate ions and/or bicarbonate ions, carbonate ions and bicarbonate ions undergo a hydrolysis reaction in the anolyte to generate hydroxide ions. At the same time, the generated hydroxide ions will undergo an electrochemical reaction on the electrolytic anode to generate oxygen, thereby continuously promoting the hydrolysis of carbonate ions and carbonate ions until they become carbonic acid and decompose into water and carbon dioxide gas. The specific chemical reaction formula is shown below.

Hydrolysis of carbonate and/or bicarbonate ions:

CO ₃ ^2- +H ₂ O→HCO ₃ ^- +OH ^- ;

HCO ₃ ^- +H ₂ O→H ₂ CO ₃ +OH ^- ;

H ₂ CO ₃ →H ₂ O+CO ₂ ↑.

Electrochemical reactions that occur at the electrolytic anode when hydroxide ions are present in the anolyte:

4OH ^- -4e ^- → 2H ₂ O+O ₂ ↑.

When the anolyte contains formate ions and/or oxalate ions, the formate ions and oxalate ions lose electrons on the electrolytic anode to form free radicals during the electrolysis process, and then the carboxyl groups are dissociated and converted into carbon dioxide gas to escape. The specific chemical reaction formula is shown below.

HCOO ^- -2e ^- →H ⁺ +CO ₂ ↑;

^- OOC-COO ^- -2e ^- → 2CO ₂ ↑.

When the electrolysis separator is a cationic membrane, the electrochemical reaction formula that occurs in the electrolysis cathode region during the electrolysis process of the present invention is as follows (M+ is the cation in the anolyte):

Cu(NH ₃ ) ₄ Cl ₂ +2M ⁺ +4H ₂ O+2e ^- →Cu+2M ⁺ Cl ^- +4NH ₄ OH;

Cu( _NH3 )2Cl+M ⁺ +2H2O ₊ e- ^→ Cu+M ₊ ^Cl- ⁺ _2NH4OH .

When the electrolysis separator is a bipolar membrane, the electrochemical reaction formula that occurs in the electrolysis cathode region during the electrolysis process of the present invention is as follows:

Cu(NH ₃ ) ₄ Cl ₂ +2H ⁺ +2H ₂ O+2e ⁻ →Cu+2NH ₄ Cl+2NH ₄ OH;

Cu( _NH3 )2Cl+H ⁺ ₊ _H2O +e- ^→ Cu+ _NH4Cl ₊ 2NH4OH.

As a preferred embodiment of the present invention: the pH value of the anolyte is controlled to be equal to or greater than 5, so as to avoid the accidental leakage of the catholyte into the anolyte, the chloride ions and ammonia brought by the anolyte are at pH values In lower cases, nitrogen trichloride explosives are produced.

As another preferred embodiment of the present invention: during the electrolysis process, at least one of the copper ion concentration in the anolyte solution, the chloride ion concentration in the anolyte solution, and the chlorine gas concentration in the gas separated from the anolyte solution is subjected to Detection, in order to monitor the accidental leakage of catholyte in real time to prevent the formation of nitrogen trichloride explosives.

In the electrolysis process, the method for supplementing the carbon dioxide generating raw material to the anolyte is to directly add the carbon dioxide generating raw material to the anolyte, and/or pass carbon dioxide gas to the anolyte to generate carbon dioxide generating raw material through the reaction in the anolyte; Described carbon dioxide gas is the carbon dioxide gas separated out from the anolyte in the electrolysis process, commercially available carbon dioxide gas products, carbon dioxide gas released by thermal decomposition of carbonic acid, carbon dioxide gas released by thermal decomposition of carbonate, bicarbonate. Carbon dioxide gas released by thermal decomposition, carbon dioxide gas released by thermal decomposition of oxalic acid, carbon dioxide gas released by thermal decomposition of oxalate, carbon dioxide gas released by thermal decomposition of formic acid, carbon dioxide gas released by thermal decomposition of formate At least one of carbon dioxide gas, carbon dioxide gas released by the reaction of carbonate and inorganic acid, and carbon dioxide gas released by the reaction of bicarbonate and inorganic acid.

In the scheme of using the carbon dioxide gas from the anolyte solution to generate carbon dioxide generating material in the anolyte solution, when the anolyte solution contains ammonia, the carbon dioxide gas from the anolyte solution is separated from the anolyte solution and the carbon dioxide gas in the anolyte solution is used. Ammonia is combined to generate carbon dioxide to generate feedstock ammonium carbonate and/or ammonium bicarbonate. In other solutions, since ammonia is involved in the preparation process of the etching sub-liquid or the regenerated etching sub-liquid, and the overflow of the catholyte, the prepared etching sub-liquid or the regenerated etching sub-liquid, and the etching production line The etching solution contains ammonia, so in the alkaline etching process that the etching solution contains carbonate, its etching sub-liquid preparation solution, the regeneration etching sub-liquid preparation solution, the overflow of the catholyte solution, and the etching sub-liquid are adopted. , one or two or more of the etchant in the regenerating etching sub-liquid and the etching solution on the etching production line absorb the gas separated from the anolyte, so that the carbon dioxide gas is converted into ammonium carbonate and/or ammonium bicarbonate. in solution. In addition, during the electrolysis process, when the electrolysis reaction of water occurs on the surface of the electrolysis anode, oxygen will be precipitated from the electrolyte in the electrolysis anode area, so the precipitation gas also contains oxygen in addition to carbon dioxide gas, so Said oxygen can increase the oxidation of the above solution.

The present invention can make the following improvements: the catholyte solution after electrolysis is carried out through the electrolysis reaction tank, after supplementing and adjusting the proportion of each component according to the process requirements, it becomes a regenerated etching sub-liquid, and is added to the alkaline etching production line for use; The pH value or the specific gravity value that the described regeneration etching sub-liquid or its mixed solution with the etching sub-liquid is set according to the process of the etching working liquid on the alkaline etching production line is compared with the measured value, and the etching sub-liquid is controlled and added to Alkaline etching production line. The regenerated etching sub-liquid may contain copper ions, but it will not affect the production and use.

Preferably, when the pH value of the etching working liquid on the alkaline etching production line is set to be less than 7.3, the regenerated etching sub-liquid or its mixture with the etching sub-liquid is based on the etching working liquid on the alkaline etching production line. The pH process setting value is controlled and added in real time; when the process setting pH value of the etching working solution on the alkaline etching production line is greater than 8.5, the regenerated etching sub-liquid or its mixed solution with the etching sub-liquid is The specific gravity process setting value of the etching working solution on the alkaline etching production line is controlled and added in real time; when the pH value of the etching working solution on the alkaline etching production line is set in the range of 7.3 to 8.5, the regeneration etching The sub-liquid or its mixed solution with the etching sub-liquid can be controlled and added according to the pH value process parameter or the specific gravity value process parameter of the etching working solution on the alkaline etching production line. This is because when the pH value of the etching working solution in the alkaline etching production line is low, using the pH value process parameters as the addition control of the etching sub-liquid can more effectively keep the concentration of each component of the etching working solution stable. When the pH value set by the etching working liquid on the production line is high, it is more effective to use the specific gravity process parameters as the control of the addition of the etching sub-liquid.

When the anolyte contains ammonium ions and the electrolytic separator is a cation exchange membrane, the ammonium ions in the anolyte will be attracted by the electric field and enter the catholyte through the electrolytic separator. The ammonia concentration in the electrolytic catholyte of the electrolysis will be increased. Therefore, when the electrolytic catholyte that overflows the electrolytic cell after the copper is extracted by electrolysis is used to prepare and produce the regenerative etching sub-liquid, the supplement of the additional ammonia source can be reduced or even eliminated.

The present invention can make the following improvements: for the gas separated from the anolyte in the electrolysis process, first adopt the anolyte and/or the overflow of the anolyte to absorb, and then use the overflow of the catholyte, regenerate the etchant One or more of the etching liquid and the etching liquid on the etching production line absorb the remaining exhaust gas. In this solution, when the anolyte does not contain multivalent metal ions, oxygen will escape again because it cannot be absorbed. At this time, the oxygen can be led into the above-mentioned liquid, and the monovalent copper in it can be used. Ammonium complexes are absorbed. When the anolyte contains ammonia and/or ammonium salts, ammonia gas may also escape from the anode region. Described oxygen and ammonia can be absorbed by one or more of the overflow liquid of catholyte, the regenerated etching sub-liquid, and the etching liquid on the etching production line, so that the above-mentioned solution is oxidatively enhanced and/or the ammonia content is increased. to obtain regeneration conditions.

The present invention can make the following improvements: during the electrolysis process, the electrolyte solution in the electrolysis anode area and/or the electrolysis cathode area is cooled down. Since the electrode anode and the electrolytic cathode and even the electrolyte will heat up during the electrolysis process, the temperature of the electrolyte will rise, and cooling the electrolyte in the electrolysis anode area and/or the electrolysis cathode area can effectively reduce the ammonia volatilization of the electrolyte. and reduce the decomposition of ammonium carbonate and/or ammonium bicarbonate in the electrolyte.

The present invention can make the following improvements: during the electrolysis process, add supplementary ammonia and/or water to the electrolysis anode area of the electrolysis cell to supplement the ammonia lost by volatilization or ion migration of the anolyte during the electrolysis process, and the water Water lost by electrolysis.

The present invention can make the following improvements: during the electrolysis process, adding and supplementing alkaline etching waste liquid to the cathode region, or adding at least one of the alkaline etching waste liquid and water, alkaline etching sub-liquid, and alkaline etching regeneration sub-liquid A kind of mixed solution, and according to the process to maintain a certain concentration of copper ions in the catholyte to maintain the electrochemical reaction of electrolytic copper.

The present invention can make the following improvements: using hydrochloric acid or formic acid solution as the tail gas absorbing liquid, for the etching from the anode area, cathode area, alkaline etching waste liquid to be electrolyzed, overflowed electrolyte, etching sub-liquid, and etching production line One or more of the ammonia-containing tail gas that escapes from the preparation of liquid and regenerative etching sub-liquid is absorbed, so that the generated ammonium chloride or ammonium formate can be recycled.

The present invention can make the following improvements: after the electrolysis operation is completed, the catholyte is drawn out from the cathode area, and the vacant cathode in the cathode area is sprayed with water for cleaning, and then the cathode is taken out to collect metallic copper, It is improved to reduce the environmental pollution of the production workshop caused by the ammonia gas brought out when the cathode is taken out; the water after cleaning the cathode can be used for the preparation of the regenerated sub-liquid and/or the supplementary liquid of the anolyte.

The second object of the present invention is achieved through the following technical solutions:

A device used in the alkaline etching waste liquid regeneration and reuse method, comprising an electrolytic reaction tank, an electrolytic separator, an electrolytic anode, an electrolytic cathode, an electrolytic power source and a carbon dioxide generating raw material supplement device; The electrolysis reaction tank is divided into an anode area and a cathode area; during the electrolysis process, the electrolytic anode and the electrolytic cathode are respectively connected to the positive electrode and the negative electrode of the electrolysis power supply; the carbon dioxide generating raw material supplement device is connected to the anode area.

The electrolytic separator is a material that can effectively prevent anions in the catholyte from migrating to the anode region under the force of an electric field, and is specifically at least one of a cation exchange membrane and a bipolar membrane.

Described carbon dioxide generation raw material replenishment device is the anode electrolysis replenishment solution tank connected with pump and pipeline, solid addition device, the top cover air hood connected with gas drainage pipe arranged in anode area and/or cathode area, connected with At least one of a carbon dioxide gas cylinder with a gas draft tube and a carbon dioxide generating device connected with a gas draft tube, used to supplement the anolyte with carbon dioxide generating raw materials and/or anolyte conditioning solution rich in carbon dioxide generating raw materials and/or Or introduce carbon dioxide gas.

The carbon dioxide generating device is used for chemical reaction to produce carbon dioxide gas; the carbon dioxide gas generating device can generate carbon dioxide gas through acid-base neutralization reaction or thermal decomposition reaction. When the thermal decomposition reaction is used to generate carbon dioxide gas, the carbon dioxide gas generating device is a heating reaction kettle, which is specifically used for carbonic acid, carbonate, bicarbonate, oxalic acid, oxalate, formic acid, formate and the above-mentioned compounds. At least one of the aqueous solutions is heated to decompose to release carbon dioxide gas. The heating reaction kettle is provided with a feed inlet, an air outlet and a cold and hot temperature exchanger, and the air outlet drains the gas escaping from the heating reaction kettle into the anolyte through a gas drainage pipe.

Preferably, at least one of an air pump, a jet suction device, and a centrifugal fan-type suction spray device is added to the gas drainage pipe connected to the carbon dioxide generating raw material supplement device, so that the gas has kinetic energy and goes deep into the liquid. chemical reaction.

The electrolytic anode is at least one of a conductive graphite electrode, a titanium substrate-coated electrode, a platinum-plated electrode and a gold-plated electrode; the electrolytic cathode is made of stainless steel, copper, iron, titanium, platinum, gold, and conductive graphite. at least one of.

Preferably, the electrolytic anode is a titanium substrate coated electrode, and the electrolytic cathode is stainless steel.

The present invention can make the following improvements: the device of the present invention is additionally equipped with a circulating reflux transfer tank, and the circulating reflux transfer tank is connected with the anode area through pipelines and valves and/or pumps to form a circulating flow pipe network, so that the solution between the two tanks is connected. Circular flow.

Preferably, in the circulating flow pipe network, an overflow buffer tank and a pump are added to the pipeline from the anode area to the circulating return transfer tank, and the overflow buffer tank is used to temporarily store the flow from the anode area. The overflowing anolyte is pumped to the circulating return transfer tank according to the process control.

The present invention can make the following improvements: an anolyte supplementary solution preparation tank is added to the device of the present invention for preparing an anolyte supplementary solution rich in carbon dioxide generating raw materials and/or ammonia; the anolyte supplementary solution preparation tank is provided with a pump The pipeline is connected with one of the circulating return transfer tank and the anolyte supplementary liquid tank, so that the anolyte supplementary liquid can be added to the circulating return transfer tank or the anolyte supplementary liquid tank according to the process requirements, so as to more conveniently The anolyte in the electrolytic anode area is adjusted and replenished. Among them, the solvent in the preparation of the anolyte supplementary solution can be selected from an external solution or directly from the anolyte solution from the electrolysis anode area or the solution circulating back into the transfer tank.

Preferably, an anolyte supplementary solution filtration system is added to the device of the present invention, and the anolyte supplemental solution filtration system is arranged between the anolyte supplementary solution preparation tank and the circulating return transfer tank or the anolyte supplemental solution tank.

The present invention can make the following improvements: the carbon dioxide generating raw material supplement device is connected to at least one of the circulating reflux transfer tank and the anolyte supplementary solution preparation tank, so that carbon dioxide generation is directly performed on the anolyte in the circulating reflux transfer tank. Supplementing raw materials, or preparing an anolyte adjustment solution rich in carbon dioxide generating raw materials in the anolyte supplementary solution preparation tank, so as to further stably control the composition of the anolyte in the anode area without interfering with the electrolysis anode area. The electrolysis reaction proceeds.

The present invention can make the following improvements: the device of the present invention is additionally provided with a catholyte overflow storage tank and a catholyte overflow buffer tank, and between the catholyte overflow storage tank and the cathode area, the catholyte overflow buffer tank and the pipeline and The pump is connected, so that the catholyte overflowing from the cathode area overflows into the catholyte overflow buffer tank and is pumped into the catholyte overflow storage tank according to the process requirements.

The present invention can make the following improvements: at least one regeneration sub-liquid preparation tank is added to the device of the present invention, and the regeneration sub-liquid preparation tank is connected with the cathode area or the catholyte overflow storage tank, or through the catholyte overflow buffer tank and pipeline and The pump is connected to the cathode area, and is used to oxidize the monovalent copper ions in the solution by using the catholyte overflowing from the cathode area as a raw material, and adjust and supplement the components according to the process requirements to prepare regeneration etching. sub-liquid. When more than one regenerated sub-liquid preparation tank is set up, even if the solutions in some of the regenerated sub-liquid preparation tanks have been prepared up to the standard, other regenerated sub-liquid preparation tanks can continue to absorb the gas precipitated in the electrolytic cell and prepare them. Avoid wasting the gas continuously released from the electrolytic cell during the electrolytic copper removal process.

Preferably, the regeneration sub-liquid preparation tank is connected with a regeneration sub-liquid storage tank through a pipeline and a pump, and the regeneration sub-liquid storage tank is used to temporarily store the regeneration etching sub-liquid that has been regenerated and prepared according to the process requirements.

More preferably, the regenerated sub-liquid storage tank is connected to the etching liquid cylinder of the etching production line through a pipeline provided with a pump, and the pump is controlled by an automatic detection and control system on the etching production line.

The present invention can make the following improvements: an etching waste liquid storage tank is added to the device of the present invention to temporarily store the etching production waste liquid overflowing from the etching production line; The pipeline is connected, and the pump adds the etching waste liquid to the cathode area to participate in the electrochemical reaction according to the process requirements.

Preferably, the etching waste liquid storage tank is connected to the etching liquid tank of the etching production line through the etching line overflow buffer tank and the pipeline connected with the etching production line, and the pump is connected to the etching liquid cylinder of the etching production line, and the etching production line is connected by the pump and the pipeline provided. The overflowing etching waste liquid is pumped to the etching waste liquid storage tank for storage.

The present invention can make the following improvements: the device of the present invention is additionally equipped with a cold-heat temperature exchanger, which is arranged in at least one of the anode area, the cathode area, the circulating return transfer tank, the regeneration sub-liquid preparation tank and the regeneration sub-liquid storage tank. The thermal decomposition of carbonate or bicarbonate in the electrolyte in the anode area and/or cathode area during electrolysis can be effectively reduced when the cold and heat temperature exchangers are arranged in the anode area and/or the cathode area; When the hot and cold temperature exchanger is arranged in the circulating reflux transfer tank, it can effectively reduce the thermal decomposition of carbonate or bicarbonate contained in the solution in the circulating reflux transfer tank due to excessive temperature, and it is also more conducive to the electrolysis of the electrolysis tank. The temperature control of the regenerated sub-liquid; when the hot and cold temperature exchanger is set in the regenerated sub-liquid preparation tank, it can effectively avoid the temperature change during the preparation of the regeneration sub-liquid from affecting the preparation effect, and at the same time, it can also effectively avoid adding the regeneration etching sub-liquid. When entering the etching production line, the temperature changes and the etching quality is affected; when the hot and cold temperature exchanger is set in the regenerated sub-liquid storage tank, it can effectively avoid the temperature change caused by adding the regenerated etching sub-liquid to the etching production line and affect the etching. quality.

The present invention can make the following improvements: the device of the present invention is equipped with a water-oil separator to separate the organic oil film impurities in the alkaline etching waste liquid, so as to avoid affecting the normal operation of the electrolytic cell; Between it and the etching waste liquid storage tank, or on the liquid pipeline flowing from the etching waste liquid storage tank to the cathode area.

The present invention can make the following improvements: a solid-liquid separator is added to the device of the present invention to remove the solid impurities in the alkaline etching waste liquid or the regeneration sub-liquid and carry out adsorption treatment on the organic impurities, so as to avoid the solid impurities and organic impurities from affecting the electrolysis effect or etching. Effect; the solid-liquid separator is arranged on the liquid pipeline flowing from the regeneration sub-liquid preparation tank to the etching production line, or between the etching production line and the etching waste liquid storage tank, or from the etching waste liquid storage tank On the liquid pipeline that flows to the electrolyzer.

The filter medium in the solid-liquid separator is selected from cotton core, filter cloth, diatomaceous earth, and activated carbon. Preferably, activated carbon is selected as the filter medium in the solid-liquid separator to reduce the COD value in the alkaline etching waste liquid.

The present invention can be improved as follows: the anode area and/or the cathode area are provided with a top cover plate air hood, the top of the top cover plate air hood is provided with a gas drainage pipe, and the anode area and/or the cathode area are The gas precipitated by the electrolyte in the electrolysis process is drained to at least one of the circulating reflux transfer tank, the anolyte supplementary liquid preparation tank, the catholyte overflow storage tank, the regeneration sub-liquid preparation tank, the regeneration sub-liquid storage tank and the etching production line. When the draft pipe leads the gas to the circulating return transfer tank and/or the anode electrolyte supplementary solution preparation tank, it can make the carbon dioxide gas and/or ammonia gas from the anode area and/or the cathode area and the circulating return transfer tank and/or the anode. The solution in the electrolytic replenishing solution preparation tank undergoes a chemical reaction to generate carbonate and/or bicarbonate, so that the carbon dioxide generating raw material and ammonia content in the anolyte can be cyclically replenished. When the drainage tube leads the gas to the catholyte overflow storage tank and/or the regeneration sub-liquid preparation tank and/or the regeneration sub-liquid storage tank, the overflow liquid of the catholyte and/or the regeneration etching sub-liquid can be used to carry out the gas treatment. chemical reaction absorption. When the draft tube leads the gas to the etching production line, the etchant on the etching production line can be used for chemical reaction absorption of the gas. When the anode area and the cathode area are drained to the same place at the same time, the gas drain pipes for draining the gas from the anode area and the cathode area should be separately arranged in the same reaction tank to avoid carbon dioxide gas from the anode area and Ammonia from the cathode zone mixes in the same gas draft tube to form carbonate and/or bicarbonate solids that plug the tube.

Preferably, at least one of an air pump, a jet suction device, and a centrifugal fan-type suction spray device can be added to the gas drainage pipe located at the top of the air extraction hood of the top cover plate, so that the gas has kinetic energy and penetrates deep into the air. chemical reactions in liquids.

The present invention can make the following improvements: the anode area is an anode area square box, and the anode area square box is a box-type structure with a vent hole, so that the electrolytic anode is completely immersed in the electrolyte during the electrolysis process, so The anode area square box is placed in the electrolysis reaction tank, and the side wall of the anode area square box adjacent to the electrolysis cathode is provided with the electrolysis separator, which separates the electrolysis reaction tank into an anode area and a cathode area. One or two or more of the anode zone square boxes are arranged in the electrolysis reaction tank. The exhaust holes of the square box of the anode area are connected by pipes to form a unified discharge pipe, so that the gas precipitated in the whole anode area can be discharged smoothly.

The present invention can make the following improvements: the circulating reflux transfer tank, the anolyte supplementary liquid preparation tank, the catholyte overflow storage tank, the overflow buffer tank, the regeneration sub-liquid preparation tank, the regeneration sub-liquid storage tank, and the etching waste liquid storage tank , the top of at least one of the catholyte overflow buffer tanks is equipped with a gas drainage pipe, and the gas drainage pipe passes gas into the circulating backflow transfer tank, the anolyte supplementary liquid preparation tank, and the catholyte overflow At least one of a storage tank, a regeneration sub-liquid preparation tank, a regeneration sub-liquid storage tank, and an etching production line, and/or the gas drainage pipe is connected with at least one tail gas absorption liquid tank, so that the gas escaping from the above-mentioned device can be cleaned. Absorption treatment. Preferably, a jet suction device and/or a centrifugal fan-type suction spray device are added to the gas drainage pipe to promote the reaction and absorption of the gas by the liquid. Wherein, the drainage pipe passes the gas into the circulating return transfer tank and/or the anolyte supplementary solution preparation tank and/or the catholyte overflow storage tank and/or the regeneration sub-liquid preparation tank and/or the regeneration sub-liquid storage tank And/or etching production lines, it can also be beneficial to production.

The present invention can make the following improvements: the device of the present invention is additionally equipped with an etching supplementary carbon dioxide gas generating device, and the etching supplementary carbon dioxide gas generating device can generate carbon dioxide gas through an acid-base neutralization reaction or a thermal decomposition reaction, and the gas is introduced into the gas through a gas drainage pipe. into at least one of the catholyte overflow storage tank, the regeneration sub-liquid preparation tank, the regeneration sub-liquid storage tank, and the etching production line. The etching supplementary carbon dioxide gas generating device is used for chemical reaction to produce carbon dioxide gas and supplement it into the regenerated etching sub-liquid or the etching production line, so as to reduce or maintain the total volume of the liquid in the process. Wherein, when the thermal decomposition reaction is adopted, the etching supplementary carbon dioxide gas generating device is a heating reactor, which is specifically used for carbonic acid, carbonate, bicarbonate, oxalic acid, oxalate, formic acid, formate and the above-mentioned compounds. At least one of the aqueous solutions is heated to decompose to release carbon dioxide gas. The heating reaction kettle is provided with a feed inlet, an air outlet and a cold and hot temperature exchanger, and the air outlet guides the gas escaping from the heating reaction kettle to a connected container through a gas drainage pipe.

At least one of an air pump, a jet suction device, and a centrifugal fan-type suction spray device is added to the gas drainage pipe of the etched and supplemented carbon dioxide generating device, so that the gas has kinetic energy and goes deep into the liquid for chemical reaction.

The present invention can be improved as follows: an ammonia gas generating device is added to the device of the present invention to provide ammonia gas to the anolyte supplementary solution and/or the anolyte solution and/or the regeneration etching sub-liquid and/or the etching solution. The ammonia gas generating device is a heating reaction kettle, the top of which passes through a gas drainage pipe and an anode area, a circulating return transfer tank, an anolyte supplementary liquid preparation tank, a catholyte overflow storage tank, a regeneration sub-liquid preparation tank, and a regeneration sub-liquid storage tank. At least one of a groove and an etching production line is connected. When in use, the two heating sources are combined by means of external heating, or by adding a solute for dissolving and exothermic reaction and external heating, so that the ammonia in the ammonia-containing solution is volatilized and escaped, and the ammonia gas is introduced into the anode for electrolysis. Absorb in at least one of liquid, anolyte, spillage of anolyte, spillage of catholyte, regeneration etching sub-liquid, etching liquid on the etching production line, and make the ammonia and/or ammonium ion concentration content in the solution To meet the process requirements, it can also maintain the total volume of the treatment liquid so that it does not increase the volume.

Preferably, at least one of an air pump, a jet suction device, and a centrifugal fan-type suction spray device is added to the gas drainage pipe connected to the ammonia gas generating device, so that the gas has kinetic energy and penetrates into the liquid for chemical treatment. reaction.

The present invention can be improved as follows: a temporary storage tank is added to the device of the present invention to temporarily store the liquid to be added to the device of the present invention or the liquid that needs to be temporarily stored in the device of the present invention; With anode area, cathode area, circulating return transfer tank, anode electrolysis replenishing liquid preparation tank, regeneration sub-liquid preparation tank, regeneration sub-liquid storage tank, carbon dioxide generator, etching supplementary carbon dioxide generator, ammonia gas generator, etching waste liquid storage tank at least one connection in the slot.

The present invention can make the following improvements: the device of the present invention is additionally equipped with a solid adding device, which is connected to the anode area, the cathode area, the circulating return transfer tank, the anode electrolyte supplementary liquid preparation tank, the regeneration sub-liquid preparation tank, the regeneration sub-liquid storage tank, and the heating reaction. At least one of the kettles is used for adding solid materials to the above device.

The present invention can make the following improvements: in the anode area, cathode area, circulating return transfer tank, anode electrolyte replenishing solution preparation tank, catholyte overflow storage tank, overflow buffer tank, catholyte overflow buffer tank, regenerator At least one of the liquid preparation tank, the regeneration sub-liquid storage tank, the etching waste liquid storage tank, the carbon dioxide gas generator, the etching supplementary carbon dioxide generator, and the ammonia gas generator is equipped with a detection device; the detection device is selected from hydrometer, photoelectric At least one of colorimeter, liquid level meter, redox potentiometer, pH meter, acidity meter and thermometer, COD detector and chlorine gas detector, used for the process parameter value of the reaction material in the tank and the use effect of the filter medium Perform inspection and process control.

Preferably, an automatic detection and feeding controller is added to the device of the present invention, and the automatic detection and feeding controller responds according to the time program and/or the result of the process parameters measured by the detection device, and controls the electrolysis power supply, the hot and cold temperature exchanger, the pump The opening, closing or size adjustment of at least one of the pump, the solid feeding device, the etching production line, and the valve.

The present invention can make the following improvements: add a cathode water spray storage tank, the cathode water spray storage tank is connected with the cathode area, and before the cathode is taken out, the electrolytic catholyte in the electrolytic cathode area of the electrolytic cell is pumped to the cathode electrolyte to overflow In the storage tank, the cathode is sprayed and washed with water to avoid the ammonia gas polluting the environment when the cathode is taken out.

The present invention can make the following improvements: an anolyte storage tank is added to the device of the present invention, and the anolyte storage tank is connected to the anode area, and the anolyte in the anode area is simultaneously pumped to the anolyte storage tank when the cathode is taken out. In the tank, avoid damage to the separator of the electrolysis tank due to unilateral pressure.

The present invention can make the following improvements: the device of the present invention is additionally equipped with a stirring device, and the stirring device is arranged in the anode area, the cathode area, the circulating return transfer tank, the anolyte supplementary liquid preparation tank, the catholyte overflow storage tank, and the regeneration sub-liquid preparation tank. , regeneration sub-liquid storage tank, etching waste liquid storage tank, carbon dioxide generator, etching supplementary carbon dioxide generator, ammonia generator, temporary storage tank, cathode water spray tank, anolyte storage tank at least one, to Helps maintain uniformity of solution concentration in the above tank. The stirring device is specifically a liquid circulating flow agitator and/or an impeller agitator.

The present invention can make the following improvements: the device of the present invention adds a copper ion concentration detection device to detect the copper ion concentration of the anolyte, and the copper ion concentration detection device is arranged in the circulating backflow transfer tank, overflow buffer tank, In at least one of the anode area and the pipeline through which the anode area flows out of the anolyte. The automatic detection and feeding controller responds according to the detection result of the copper ion concentration detection device. When the detected result of the detection device is greater than the copper ion concentration value set by the process, the automatic detection and feeding controller will issue an equipment failure alarm.

The present invention can make the following improvements: a chlorine gas detector is added to the device of the present invention, and the chlorine gas detector is arranged at the air outlet of the top cover plate air extraction hood of the anode area, or is connected to the gas drainage pipe of the top cover plate air extraction hood or on the gas drainage pipe at the top of the circulating return transfer tank, or on the gas drainage pipe at the top of the overflow buffer tank connected with the anode area; the automatic detection and feeding controller responds according to the detection result of the chlorine detector, when the chlorine gas When the result measured by the detector is greater than the chlorine concentration value set by the process, the automatic detection and feeding controller will issue an equipment failure alarm.

The present invention can be improved as follows: a COD detector is added to the device of the present invention, and the COD detector is arranged at the liquid outlet of the solid-liquid separator, or connected to the flow of the liquid processed by the solid-liquid separator. On the pipeline; the automatic detection and feeding controller responds according to the detection result of the COD detector. When the result measured by the COD detector is greater than the COD value set by the process, the automatic detection and feeding controller will issue a replacement for the solid-liquid separation. Reminder of filter media in the filter.

The present invention has the following beneficial effects:

The regeneration and reuse method of the alkaline etching waste liquid of the present invention can effectively reduce the volatilization of ammonia gas and the generation of chlorine gas in the existing alkaline etching waste liquid electrolysis technology, thereby avoiding waste caused by the decomposition of ammonia gas, and saving ammonia raw materials. cost, and can fundamentally reduce ammonia nitrogen pollution;

The device of the alkaline etching waste liquid regeneration and reuse method of the present invention adopts the electrolysis process of separating the cathode and anode cell regions, which improves the safety of the electrolysis process and has low equipment maintenance cost;

The chemical raw materials used in the alkaline etching waste liquid regeneration and reuse method of the invention are safe and cheap, and have high production economic benefits;

The regeneration etching sub-liquid obtained by the alkaline etching waste liquid regeneration and reuse method of the present invention does not contain other undesirable impurity components, and its etching performance and quality can be fully exerted and improved, so that the etching waste liquid can be effectively reused;

The method for regenerating, reusing, renewing and renewing the alkaline etching waste liquid of the circuit board of the invention can effectively eliminate the cyclic accumulation of organic oil film impurities in the regenerated sub-liquid during the cyclic use, and meet the quality requirements of the cyclic use.

Description of drawings

Fig. 1 is the schematic diagram of the alkaline etching waste liquid regeneration and reuse device of Example 1;

Fig. 2 is the schematic diagram of the alkaline etching waste liquid regeneration and reuse device of embodiment 2;

Fig. 3 is the schematic diagram of the alkaline etching waste liquid regeneration and reuse device of embodiment 3;

Fig. 4 is the schematic diagram of the alkaline etching waste liquid regeneration and reuse device of Example 4;

Fig. 5 is the schematic diagram of the alkaline etching waste liquid regeneration and reuse device of embodiment 5;

Fig. 6 is the schematic diagram of the alkaline etching waste liquid regeneration and reuse device of embodiment 6;

Fig. 6-1 is the structural representation of the square box of the anode area in Example 6;

Fig. 7 is the schematic diagram of the alkaline etching waste liquid regeneration and reuse device of embodiment 7;

Fig. 8 is the schematic diagram of the alkaline etching waste liquid regeneration and reuse device of Example 8;

Fig. 9 is the schematic diagram of the alkaline etching waste liquid regeneration and reuse device of embodiment 9;

10 is a schematic diagram of the alkaline etching waste liquid regeneration and reuse device of Example 10;

FIG. 11 is a schematic diagram of the regeneration and reuse device of alkaline etching waste liquid in Example 11. FIG.

Reference numerals: 11-14-electrolysis anode area, 15-carbon dioxide generating raw material supplement device; 21-22-electrolysis cathode area, 31-36-electrolysis separator, 41-44-electrolysis anode, 51-56-electrolysis cathode, 61-62-electrolysis power supply, 70-circulating return transfer tank, 81-82-anode area top cover plate exhaust pipe cover, 91-92-cathode area top cover plate exhaust cover, 101- anolyte evolved gas drainage pipe, 102～105- Anode area square box gas drainage pipe, 111-112- Cathode area gas drainage pipe, 120- Automatic detection and feeding controller, 121-136- Detection device, 140- Temporary storage tank, 141- Catholyte overflow storage Tank, 142～144-Temporary storage tank, 151～152-Liquid circulating flow agitator, 161～162- Impeller agitator, 171～176-Cold and hot temperature exchanger, 181～186-Jet suction device, 191～194 -Centrifugal fan-type suction and spray device, 200-Alkaline etching production line, 211-213-Solid-liquid separation device, 221-222-Water-oil separation device, 231-232-Exhaust gas absorption tank, 240-242-Heating reaction Kettle, 251～252-Solid Dosing Device, 260-Equipment Failure Alarm, 271～272-Anode Electrolysis Supplementary Solution Preparation Tank, 281-282-Regeneration Sub-Liquid Preparation Tank, 291-Overflow Buffer Tank, 292-Cathode Electrolysis Liquid overflow buffer tank, 293-overflow buffer tank, 300-313 and 1300-1304-pump, 314-319-feeding port, 321-329-1321-exhaust gas discharge port, 330-348-1331-1334-valve , 349-COD detector, 350- pre-configured anolyte, 360- pre-configured catholyte, 371-washing spray pipe, 372-washing spray pipe, 373-washing spray pipe, 380-chlorine gas detector.

detailed description

The present invention will be described below with reference to specific examples. It should be pointed out that the embodiments are only used to further illustrate the present invention, and do not represent the protection scope of the present invention. Non-essential modifications and adjustments made by others according to the present invention still belong to the protection scope of the present invention.

Example 1

As shown in FIG. 1 , the alkaline etching waste liquid regeneration and reuse device used in this embodiment includes an anode area 11, a cathode area 21, an electrolytic separator 31, an electrolytic anode 41, an electrolytic cathode 51, an electrolytic power source 61, and carbon dioxide generation raw material supplement device 15. The electrolytic separator 31 is a bipolar membrane, which separates the electrolytic cell body into an electrolytic anode area 11 and an electrolytic cathode area 21; the carbon dioxide generating raw material supplement device 15 is a commercial carbon dioxide gas connected to the anode area 11 through a gas drainage pipe bottle.

Use the device in Figure 1 to regenerate and reuse the alkaline etching waste liquid:

Step 1: adopt an electrolysis reaction tank, and the electrolysis reaction tank is divided into two types of tank areas, an electrolytic anode area and an electrolytic cathode area by an electrolytic separator;

Step 2: As shown in Table-1, prepare pre-prepared anolyte solution and pre-prepared catholyte solution, and respectively add pre-prepared anolyte solution and pre-prepared catholyte solution to anode area and cathode area;

Step 3: Confirm that the electrolytic anode and the electrolytic cathode have been immersed in the anolyte and catholyte respectively, and the electrolytic anode and the positive electrode of the electrolytic power supply and the electrolytic cathode and the negative electrode of the electrolytic power supply are respectively connected, and the electrolytic power supply is turned on to perform the electrolysis operation.

The pre-prepared catholyte in this embodiment is an alkaline etching waste liquid, wherein the copper ion concentration of the alkaline etching waste liquid is 2 g/L and the pH value is 6.8. During the electrolysis process, carbon dioxide gas is added to the anolyte through the carbon dioxide generating raw material replenishing device 15, so that the carbon dioxide gas and the remaining ammonia after the carbon dioxide generating raw material in the anolyte releases carbon dioxide gas are combined to form ammonium carbonate and ammonium bicarbonate.

During the electrolysis process, the electrolytic anode and the positive electrode of the electrolytic power supply are connected and placed in the solution of the anode area, and carbon dioxide gas is precipitated, the electrolytic cathode and the negative electrode of the electrolytic power supply are connected and placed in the solution of the cathode area, and the Precipitated copper metal.

Example 2

As shown in FIG. 2 , the alkaline etching waste liquid regeneration and reuse device used in this embodiment includes an anode area 11, a cathode area 21, an electrolytic separator 31, an electrolytic anode 41, an electrolytic cathode 51, an electrolytic power source 61, and carbon dioxide generation raw material supplement device, circulating backflow transfer tank 70. The electrolytic separator 31 is a cationic membrane, which separates the electrolytic reaction tank into an anode area 11 and a cathode area 21; the carbon dioxide generating raw material supplement device is a solid feeding device 251; the anode area 11 and the circulating return transfer tank 70 are respectively provided with cold and

hot temperatures Exchangers

171 and 172; between the circulating return transfer tank 70 and the anode area 11, the pipelines provided with the pump 301 and the valve 330 and the independent return pipeline constitute a liquid circulating flow pipe network, so that the solution between the two tanks is circulated flow.

The alkaline etching waste liquid is regenerated and reused by the device shown in Figure 2:

Step 1: adopt an electrolysis reaction tank, and the electrolysis reaction tank is divided into two types of tank areas, an anode area and a cathode area, by an electrolytic separator;

Step 2: As shown in Table-1, prepare a pre-distributed anolyte and a pre-distributed catholyte, and respectively add the pre-distributed anolyte and the pre-distributed catholyte into the anode area and the cathode area;

Step 3: Confirm that the electrolytic anode and the electrolytic cathode have been immersed in the anolyte and catholyte respectively, and the electrolytic anode and the positive electrode of the electrolytic power supply and the electrolytic cathode and the negative electrode of the electrolytic power supply are respectively connected, and the electrolytic power supply is turned on to perform the electrolysis operation. During the electrolysis process, the anode area of the electrolytic cell is directly connected with the circulating return transfer tank for circulation through the pipeline, so that the anolyte is circulated between the two tanks.

The pre-prepared catholyte in this embodiment is a 2:1 mixture of alkaline etching waste liquid and alkaline etching sub-liquid, wherein the copper ion concentration of the alkaline etching waste liquid is 200g/L, the pH value is 8.0, and the etching sub-liquid The pH value of the solution was 9.1, and the copper ion concentration was 60 g/L. During the electrolysis process, ammonium carbonate solid raw material is added to the anolyte by the solid adding device.

During the electrolysis process, the electrolytic anode and the positive electrode of the electrolytic power supply are connected and placed in the solution of the anode area, and carbon dioxide gas is separated out, the electrolytic cathode and the negative electrode of the electrolytic power supply are connected and placed in the solution of the cathode area, and the electrolysis Copper metal is deposited on the cathode.

Example 3

As shown in FIG. 3 , the alkaline etching waste liquid regeneration and reuse device used in this embodiment includes an anode area 11, a cathode area 21, an electrolytic separator 31, an electrolytic anode 41, an electrolytic cathode 51, an electrolytic power source 61, and a circulating return transfer tank. 70. The anode area top cover plate exhaust pipe cover 81, the cathode area top cover plate exhaust cover 91, the anolyte precipitation gas drainage pipe 101, the electrolysis cathode area gas drainage pipe 111, the automatic detection feed controller 120, the detection device 121, Detection device 122, catholyte overflow storage tank 141, temporary storage tank 142, liquid circulating flow agitator 151, cold and hot temperature exchanger 171, cold and hot temperature exchanger 172, solid feeding device 251, catholyte overflow buffer Tank 292, pump 301-303, feeding port 314, tail gas discharge port 321-323, valve 330-332, chlorine gas detector 380.

The electrolytic separator 31 is a cationic membrane, which separates the electrolytic reaction tank body into an anode area 11 and a cathode area 21; the anode area 11 and the cathode area 21 are respectively provided with a detection device 121 and a detection device 122, a hot and cold temperature exchanger 171 and a cooling device. Heat temperature exchanger 172; cathode area 21 is provided with circulating liquid flow stirring device 151 and an overflow port, and the overflow port is connected with catholyte overflow buffer tank 292 through pipes; wherein catholyte overflow storage tank 141 and catholyte The liquid overflow buffer tank 292 is connected to the pipeline through the valve 331, the pump 302, and is used for pumping the catholyte overflow liquid to the catholyte overflow storage tank 141 for storing the catholyte overflow liquid for temporary storage. The temporary storage tank 142 is used to store the pre-configured catholyte, which is connected to the cathode area 21 through the valve 332, the pump 303 and the pipeline. The valve 332 and the pump 303 are controlled by the automatic detection and feeding controller 120 to prepare the catholyte. Add to the cathode region 21. The circulating return transfer tank 70 is provided with a tail gas discharge port 321 and a feeding port 314, and is connected with a solid feeding device 251, wherein the feeding port 314 is used for feeding carbon dioxide gas and ammonia water. Between the circulating return transfer tank 70 and the anode area 11, a pipeline with a pump 301 and a valve 330 and an independent return pipeline constitute a liquid circulating flow pipe network, so that the solution between the two tanks circulates. The anode area 11 and the cathode area 21 are respectively provided with top cover plate exhaust pipe covers 81 and 91, and the top cover plate exhaust pipe cover 81 drains the gas extracted from the anode area 11 to the catholyte overflow through the anolyte precipitation gas drainage pipe 101. in storage tank 141. A chlorine gas detector 380 is installed on the anolyte precipitation gas drainage pipe 101 ; the gas extracted from the cathode region 21 is introduced into the circulating return transfer tank 70 through the gas drainage pipe 111 using the top cover plate air extraction hood 91 . The automatic detection and feeding controller 120 automatically adjusts the output current of the electrolysis power source 61 or controls the solids feeding device 251 and/or the execution of the feeding amount according to the process parameter results measured by the detection device 121 of the anode area 11; the automatic detection feeding controller 120 According to the process parameter results measured by the detection device 122 of the cathode area 21, the feeding action control of the pipeline feeding pump 303 between the temporary storage tank 142 and the cathode area 21 is automatically controlled; The obtained process parameter results will issue an alarm in time.

Use the device in Figure 3 to regenerate and reuse the alkaline etching waste liquid:

Step 2: Prepare the pre-prepared anolyte and pre-prepared catholyte as shown in Table-1, add the pre-prepared anolyte to the anode area and the circulating return transfer tank, and add the pre-prepared catholyte to the cathode area ;

Step 3: Confirm that the electrolytic anode and the electrolytic cathode have been immersed in the pre-prepared anolyte solution and the pre-prepared catholyte solution, respectively, and the electrolytic anode and the positive electrode of the electrolytic power supply and the electrolytic cathode and the negative electrode of the electrolytic power supply are respectively connected, and then the electrolytic power supply is closed for electrolysis.

During the electrolysis process, the anode area and the circulating return transfer tank are connected to the circulating pipeline network, so that the anolyte liquid circulates between the two tanks; the gas produced in the anode area is led to the catholyte overflow temporary storage tank for absorption; The draft tube introduces the ammonia gas precipitated in the cathode area into the solution in the circulating reflux transfer tank. In addition, ammonium carbonate, ammonium bicarbonate and ammonium formate mixed solids are added to the anode area through the solid feeding device, and ammonia water and carbon dioxide gas are added to the other feeding port of the circulating reflux transfer tank to supplement the carbon dioxide generating raw materials of the anolyte. Supplementary pre-prepared catholyte is added to the cathode area to maintain a certain concentration of copper ions in the catholyte to maintain the electrolytic copper reaction on the electrolytic cathode.

The pre-prepared catholyte in this embodiment is a 3:1 mixture of alkaline etching waste liquid and alkaline regeneration etching sub-liquid, wherein the pH value of the alkaline etching waste liquid is 9.3 and the copper ion is 130g/L; The pH value of the solution was 9.8, and the copper ion concentration was 42 g/L.

Example 4

As shown in FIG. 4 , the alkaline etching waste liquid regeneration and reuse device used in this embodiment includes an anode area 11, a cathode area 21, an electrolytic separator 31, an electrolytic anode 41, an electrolytic cathode 51, an electrolytic power source 61, and a circulating return transfer tank. 70. Solid feeding device 251, catholyte overflow buffer tank 292, catholyte overflow storage tank 141 and

temporary storage tanks

142, 143; the electrolytic separator 31 is a bipolar membrane, which separates the electrolytic reaction tank into an anode area 11 and cathode area 21; anode area 11 and cathode area 21 are respectively provided with

detection devices

121, 122 and cold and

hot temperature exchangers

171, 172; cathode area 21 is provided with circulating liquid flow stirring device 151 and overflow port, cathode area 21 The overflow port is connected with the catholyte overflow buffer tank 292 through a pipeline; wherein the catholyte overflow storage tank 141 is connected with the catholyte overflow buffer tank 292 through the valve 331, the pump 302 and the pipeline. It is used for pumping the catholyte overflow to the catholyte overflow storage tank 141 for storing the catholyte overflow for temporary storage. The temporary storage tank 142 is an etching waste liquid storage tank for storing alkaline etching waste liquid, which is connected to the water-oil separator 221 through the pipeline of the valve 332 and the pump 303; the water-oil separator 221 is connected to the temporary storage tank through the pump 304 The tanks 143 are connected to each other, and the alkaline etching waste liquid after the separation treatment of the oil phase is pumped to the temporary storage tank 143 for temporary storage. The temporary storage tank 143 is connected to the solid-liquid separator 211 through the valve 333 and the pipeline of the pump 305 . The outlet of the solid-liquid separator 211 is connected with the cathode area 21 through a pipeline, and the pump 305 is controlled by the automatic detection feeder 120 to add the pre-prepared catholyte into the cathode area 21 . In addition, a COD detector 349 is installed on the feeding pipeline leading from the temporary storage tank 143 to the cathode area 21 for the pre-distributed catholyte to detect the COD value of the pre-distributed catholyte. When the COD value is higher than the process setting value An alarm is issued to remind that the filter medium in the solid-liquid separator 211 needs to be replaced, so that the adsorption performance of the organic impurities in the alkaline etching waste liquid can be improved after the replacement. The top of the circulating return transfer tank 70 is provided with a tail gas port 321, a feeding port 314 and a solid feeding device 251, and between the circulating return transfer tank 70 and the electrolytic anode area 11 of the electrolytic cell, there are

pumps

301 and 300 respectively. The pipeline of the valve 330 and the independent return pipeline constitute a liquid circulating flow pipe network, so that the solution between the two tanks can be mixed in a circulating flow; , the top cover plate exhaust pipe covers 81 and 91 are respectively provided with an anolyte precipitation gas drainage pipe 101 and a cathode area gas drainage pipe 111; the cathode area gas drainage pipe 111 drains the gas precipitated in the cathode area to the catholyte overflow storage tank 141 reacts and absorbs, and the anolyte precipitation gas drainage pipe 101 diverts the gas precipitated in the anode area to the catholyte overflow liquid storage tank 141 for reaction and absorption. The anode region 11 and the cathode region 21 are respectively provided with a detection device 121 and a detection device 122 . The electrolysis power supply 61 is connected to the automatic detection and feeding controller 120 . The automatic detection and feeding controller 120 automatically adjusts the electrolysis current according to the process parameter results measured by the detection device 121 and/or adds solid material to the solid feeding device 251 and/or performs feeding control of liquid material through the feeding port 314. The automatic detection and feeding controller 120 automatically controls the pipeline feeding pump 305 between the temporary storage tank 143 and the cathode area 21 according to the results of the process parameters measured by the detection device 122 of the cathode area 21 for additional feeding, so that the electrolysis cathode area is supplemented with copper ions solution. In addition, the COD detector 349 is input and connected to the automatic detection and feeding controller 120, and according to the data detected by the COD detector 349, the automatic detection and feeding controller 120 judges to issue an alarm to replace the filter medium to the equipment failure alarm 260 connected to it.

The alkaline etching waste liquid is regenerated and reused by the device shown in Figure 4:

Step 3: Confirm that the electrolytic anode and the electrolytic cathode have been immersed in the anolyte and catholyte, respectively, and the electrolytic anode is connected to the positive electrode of the electrolytic power supply and the electrolytic cathode to the negative electrode of the electrolytic power supply respectively, and then the electrolytic power supply is closed to perform the electrolysis operation.

During the electrolysis process, the anode area is connected with the circulating return transfer tank as a circulation channel through valves, pipes and pumps, so that the anolyte can be circulated; and a solid feeding device and a feeding port are arranged in the circulating return transfer tank to circulate backflow. Carbon dioxide is added to the transfer tank to generate raw materials, and at the same time, pre-prepared catholyte is added to the cathode area.

All the precipitated gas in the anode area and the cathode area is led to the catholyte overflow liquid storage tank 141 for reaction absorption. The pre-prepared catholyte added to the cathode area is first processed by the water-oil separator and the solid-liquid separator to remove the organic oil film before being put into the electrolytic cell, so that the catholyte contains less organic impurities and affects the electrolysis cathode. Electrodeposition copper reaction.

Wherein, the pre-prepared catholyte in this embodiment is an alkaline etching waste liquid, wherein the copper ion concentration of the alkaline etching waste liquid is 30 g/L and the pH value is 10.0. The anolyte is supplemented with pre-formed anodes containing ammonia and carbon dioxide generating raw materials formic acid, potassium formate, sodium formate, calcium formate, ammonium formate, oxalic acid, potassium oxalate, sodium oxalate, potassium hydrogen oxalate, sodium hydrogen oxalate and ammonium oxalate Electrolyte.

Example 5

As shown in FIG. 5 , the alkaline etching waste liquid regeneration and reuse device used in this embodiment includes anode area square boxes 11-14, cathode area 21, electrolytic separators 31-36, electrolytic anodes 41-44, and electrolytic cathodes 51- 53. Electrolysis power supply 61, circulating return transfer tank 70, cathode area top cover air extraction plate 91, anolyte precipitation gas drainage pipe 101, cathode area gas drainage pipe 111, automatic detection and feeding controller 120, detection devices 121-124, Catholyte overflow storage tank 141, temporary storage tank 142, liquid circulating flow agitator 151, impeller agitator 161, jet suction device 181, centrifugal fan suction spray device 191, centrifugal fan suction spray device 192 , solid-liquid separator 211, tail gas absorption liquid tank 231, anolyte supplementary liquid preparation tank 271, overflow buffer tank 291, catholyte overflow buffer tank 292, pumps 300-305, feeding port 314, tail gas discharge port 321 ~326, valve 330~335.

The anode area square boxes 11 to 14 are in the form of square boxes of non-conductive and water-impermeable material and contain electrolytic anodes therein, and the anode area square boxes 11 to 14 are placed in the electrolysis reaction tank. In the hexahedrons of the square boxes 11 to 14 in the anode area, an electrolytic separator is used to separate the anode area and the cathode area on the box surface facing the electrolytic cathode outside the box, and the inner area of the square box is used as the anode area. The area outside the square box in the electrolysis reaction tank is: The cathode area 21, the electrolysis separators 31 to 36 are all cation exchange membranes; the anode area square boxes 11 to 14 and the electrolysis cathodes 51 to 53 are arranged at intervals from left to right, and are placed in the electrolysis reaction tank to form an anode. zone and cathode zone of the electrolysis reactor. The solutions in the square boxes 11 to 14 in the anode area are merged into the overflow buffer tank 291 through the pipeline, and the overflow buffer tank 291 is connected with the circulating return transfer tank 70 through the valve 332, the pump 302 and the pipeline as a single channel; The tank 70 is connected with the square boxes 11 to 14 of the anode area through the pipelines provided with the pump 303, the valve 333 and the solid-liquid separation device 211 respectively to form a return channel, so that the solution in each anode area is circulated with the solution in the circulating return tank 70. Fluid mixing. The circulating return transfer tank 70 is provided with a detection device 122 , and is connected with a jet air suction device 181 and a centrifugal fan-type air suction spray device 191 . The overflow buffer tank 291 is provided with a detection device 123, and the top of the overflow buffer tank 291 is also provided with an anolyte precipitation gas drainage pipe 101 to introduce the gas in the tank into the circulating return transfer tank through a centrifugal fan-type suction spray device 191. In the solution of 70; the anolyte supplementary solution preparation tank 271 is connected with the circulating return transfer tank 70 as a circulating loop for providing carbon dioxide generating raw materials, and the solution solvent in the tank is taken from the solution in the circulating reflux transfer tank 70, and its tank The detection device 121 , the impeller agitator 161 , and the solid feeding device 251 and the feeding port 314 are connected thereon. The cathode area 21 is provided with a detection device 124, a circulating liquid flow stirrer 151 and an overflow port, and the catholyte overflow buffer tank 292 is connected with the cathode area 21 through the overflow port. The catholyte overflow storage tank 141 is connected to the catholyte overflow buffer tank 292 through pipes, valves 334 and pumps 304, and temporarily stores the catholyte overflow. The temporary storage tank 142 stores the pre-prepared catholyte solution, and the temporary storage tank 142 is connected to the cathode region 21 by being provided with a valve 335, a pump 305 and a pipeline. The cathode area 21 is provided with a top cover air extraction hood 91, and the top of the top cover air extraction hood 91 is provided with a drainage pipe 111 to drain the gas separated from the cathode area into the solution of the circulating return transfer tank 70 through the jet air suction device 181; The tops of the transfer tank 70, the catholyte overflow storage tank 141, the temporary storage tank 142, the catholyte overflow buffer tank 292 and the anolyte supplementary liquid preparation tank 271 are respectively provided with a tail gas discharge port 321, a tail gas discharge port 322, and a tail gas discharge port. 323, the tail gas discharge port 324, the tail gas discharge port 325, the above-mentioned tail gas discharge port is respectively connected with the air inlet of the tail gas treatment system through the gas drainage pipe, and the tail gas treatment system in this device is the centrifugal fan type suction spray device 192 and the tail gas The combination of the absorption liquid tank 231; the electrolysis power supply 61 is connected with the automatic detection and feeding controller 120, and the automatic detection and feeding controller 120 automatically controls the pump 300 according to the process parameter results measured by the detection device 122 installed on the circulating return transfer tank 70. And the action of the valve 330 , the pre-prepared anolyte that has been prepared in the anolyte replenishing solution preparation tank 271 is added to the circulating return transfer tank 70 . The automatic detection and feeding controller 120 controls the feeding and feeding action of the solid feeding and feeding 251 and controls the pump 301 and the valve 331 to transfer from the circulating backflow according to the detection result of the detection device 121 installed on the anolyte replenishing solution preparation tank according to the process program. The solution from the tank 70 is taken into the anolyte replenishing solution preparation tank 271 for preparation. The output current of the electrolysis power supply is automatically adjusted or shut down according to the results of the process parameters measured by the detection device 124 of the cathode area 21, and/or according to the feeding threshold control method of the copper ion concentration set by the process or according to the time program. The feeding pump 305 between the storage tank 142 and the cathode region 21 performs feeding. At the same time, the detection device 123 installed on the overflow buffer tank 291 can reflect various process data of the anolyte during the electrolysis process. When the value is set, it will alarm and/or stop immediately.

Use the device shown in Figure 5 to regenerate and reuse the alkaline etching waste liquid:

During the electrolysis process, the anolyte flows into the overflow buffer tank through the pipeline, and then circulates and mixes with the circulating return transfer tank to create conditions. The ammonia gas precipitated in the cathode area is used as the raw material for the production of carbon dioxide for the synthesis reaction. The pre-prepared anolyte is added in the anolyte supplementary solution preparation tank to the circulating reflux transfer tank by adding the pre-prepared anolyte to supplement the carbon dioxide generating raw material and water. Supplementary pre-prepared catholyte is added to the cathode area to maintain a certain concentration of copper ions in the catholyte to maintain the electrolytic copper reaction on the electrolytic cathode.

Wherein, the pre-prepared catholyte in this embodiment is an alkaline etching waste liquid, wherein the pH value of the alkaline etching waste liquid is 7.8 and the copper ion is 120 g/L.

During the electrolysis process, a plurality of electrolytic anodes are connected to the positive electrodes of the electrolytic power supply and placed in the solution of the square box of each anode area in the electrolysis reaction tank, so that the anolyte is released into carbon dioxide gas, and the negative electrodes of the multiple electrolytic cathodes and the electrolytic power supply are in phase. Connected and placed in solution in the cathode region, and copper is continuously electro-deposited on multiple cathodes.

Example 6

As shown in FIG. 6 , the alkaline etching waste liquid regeneration and reuse device used in this embodiment includes anode area square boxes 11-14, cathode area 21, electrolytic separators 31-36, electrolytic anodes 41-44, and electrolytic cathodes 51- 53. Electrolysis power supply 61, circulating return transfer tank 70, cathode area top cover plate air extraction hood 91, anode electrolysis anolyte precipitation gas drainage pipe 101, anode area square box gas drainage pipes 102-105, cathode area gas drainage pipe 111, Automatic detection and feeding controller 120, detection devices 121-125, catholyte overflow storage tank 141, temporary storage tank 142, impeller stirrer 161, impeller stirrer 162, hot and cold temperature exchanger 171, jet absorption device 181-183, Centrifugal fan-type suction and

spray devices

191 and 192, solid-

liquid separators

211 and 212, tail gas absorption liquid tank 231, ammonia gas generating device,

solid feeding devices

251 and 252, equipment failure alarm 260, anolyte supplementary solution preparation Tank 271, overflow buffer tank 291, catholyte overflow buffer tank 292, pumps 300-306, feeding

ports

314 and 315, tail gas discharge ports 321-327, valves 330-335, pumps 300-305.

The anode area square boxes 11 to 14 are in the form of square boxes of non-conductive and water-impermeable material and contain electrolytic anodes therein, and the anode area square boxes 11 to 14 are placed in the electrolysis reaction tank. In the hexahedrons of the square boxes 11 to 14 in the anode area, an electrolytic separator is used to separate the anode area and the cathode area on the box surface facing the electrolytic cathode outside the box, and the inner area of the square box is used as the anode area. The area outside the square box in the electrolysis reaction tank is: The cathode area 21, the electrolysis separators 31 to 36 are all cation exchange membranes; the anode area square boxes 11 to 14 and the electrolysis cathodes 51 to 53 are arranged at intervals from left to right, and are placed in the electrolysis reaction tank to form an anode. zone and cathode zone of the electrolysis reactor. The solutions in the square boxes 11 to 14 in the anode area are merged into the overflow buffer tank 291 through the pipeline. The overflow buffer tank 291 is connected to the circulating return transfer tank 70 through the valve 332 and the pump 302 as a passage, and the circulating return transfer tank 70 passes through the valve. 333. The pump 303 and the solid-liquid separator 211 are respectively connected with the square boxes 11 to 14 in the anode area to form a liquid circulating flow pipe network, so that the liquid in the square boxes 11 to 14 in the anode area and the solution in the circulating return tank 70 are circulated and mixed. . The circulating return transfer tank 70 is provided with a jet absorption device 182, a centrifugal fan-type suction and spray device 191, a detection device 123, a hot and cold temperature exchanger 171, and a feeding port 315, and the automatic detection feeding controller 120 is equipped with the pump 302 and the feeding port 315. 303 feeding control to supplement and adjust the electrolytic anolyte. The overflow buffer tank 291 is provided with a detection device 124. The detection device 124 includes a photoelectric colorimeter and/or a hydrometer to measure the copper ion concentration of the anolyte. When the copper ion concentration of the anolyte is higher than the process setting value , it means that the electrolytic separator is damaged or there is a problem with the machine, and the liquid interpenetration between the cathode and anode cells occurs. The automatic detection and feeding controller 120 sends an alarm to the equipment failure alarm 260 and suspends production. The anolyte supplementary liquid preparation tank 271 is connected to the circulating return transfer tank 70 through the

valves

330 and 331, the

pumps

300 and 301 and the solid-liquid separation device 212 as the anolyte supplementary liquid filtering system, and the top of the anolyte supplementary liquid preparation tank 271 is also connected. A solid adding device 252 , a detection device 122 , an impeller agitator 162 and a jet suction device 181 are provided. The ammonia gas generating device is specifically a heating reaction kettle 240, and the ammonia gas in the heating reaction kettle 240 is introduced into the anode electrolyte replenishing solution preparation tank 271 to react with ammonium bicarbonate and ammonium carbonate solution; the heating reaction kettle 240 is provided with The detection device 121 and the impeller agitator 161 , the solid feeding device 251 and the feeding port 314 . Wherein the solid feeding device 251 is for feeding solid ammonium chloride, and the solid feeding device 252 is for feeding solid ammonium bicarbonate and ammonium carbonate mixture. The cathode area 21 is provided with a detection device 125, a liquid circulating flow agitator 151 and an overflow port, and the catholyte overflow buffer tank 292 is connected with the cathode area 21 through the overflow port; A valve 334, a pump 304 and a pipeline are connected to the catholyte overflow storage tank 141, and the catholyte overflow storage tank 141 is used for temporarily storing the catholyte overflow. The anode area square boxes 11 to 14 are provided with anode area gas drainage pipes 102 to 105 at the top, and the specific anode area square box structure is shown in Figure 6-1. The catholyte overflow storage tank 141 is provided with a jet suction device 183 on the top of the tank to suck most of the gas precipitated in the anode tank area into the solution in the tank. The temporary storage tank 142 is used as an etching waste liquid storage tank for temporarily storing the alkaline etching waste liquid flowing out of the production line, and is connected to the feeding port of the cathode area. The tops of the anolyte supplementary liquid preparation tank 271, the circulating return transfer tank 70, the catholyte overflow buffer tank 292, the catholyte overflow storage tank 141 and the temporary storage tank 142 are respectively provided with a tail gas discharge port 322, a tail gas discharge port 323, The tail gas discharge port 324, the tail gas discharge port 325, and the tail gas discharge port 326 are connected with the air inlet of the tail gas treatment system through the gas drainage pipe. The tail gas treatment system in this device is a centrifugal fan-type suction spray device 192 and tail gas absorption liquid Tanks 231 are combined into a system to treat exhaust. The electrolysis power source 61 is connected to the automatic detection and feeding controller 120 . In addition, the automatic detection feeding controller 120 automatically controls the heating capacity of the heating reaction kettle 240 and the feeding of the solid feeding device 251 according to the result of the process parameters measured by the detection device 121 of the heating reaction kettle 240 and/or is thrown into the hydroxide through the feeding port 311 Sodium solution. The automatic detection feeding controller 120 automatically controls the feeding control of the sodium bicarbonate and ammonium carbonate mixture in the solid feeding device 252 to the pump 301 according to the detection result of the detection device 122; automatic detection feeding The controller 120 automatically controls the pump 300 according to the detection data of the detection device 123 to add the supplementary solution of the anolyte into the circulating return transfer tank 70 . The automatic detection and feeding controller 120 automatically adjusts the output current of the electrolysis power supply 61 or shuts down and/or controls the feeding pump between the temporary storage tank 142 and the cathode area 21 according to the process parameter results measured by the detection device 125 of the electrolysis cathode area 21 Pu 305 increase the dosage per unit time.

Use the device in Figure 6 to regenerate and reuse the alkaline etching waste liquid:

During the electrolysis process, the anolyte is circulated and mixed between the anode area, the overflow buffer tank and the circulating return transfer tank. A small part of the carbon dioxide gas and oxygen gas produced from the anode area and separated out from the overflow buffer tank is led to the circulating return transfer tank through the overflow buffer tank for reaction and absorption. The ammonia gas overflowed from the cathode area is introduced into the circulating reflux transfer tank for the synthesis reaction of ammonium carbonate and/or ammonium bicarbonate, and the supplementary liquid is added to the circulating reflux transfer tank as an external method. To the anolyte supplementary solution preparation tank, add and add the preparation supplementary liquid raw material, wherein utilize the heating reactor to produce ammonia gas to synthesize ammonia water in the anolyte solution preparation tank. In this way, the volume increase of the anolyte during production can be reduced without directly supplementing the ammonia water. At the same time, most of the gas generated in the anode area is taken and led to the catholyte that temporarily stores the catholyte and overflows into the storage tank for reaction and absorption. Adding and supplementing alkaline etching waste liquid to the cathode area 21 to maintain a certain copper ion concentration of the catholyte to maintain the electrolytic copper reaction on the electrolytic cathode;

The pre-prepared catholyte in this embodiment is an alkaline etching waste liquid, wherein the pH value of the alkaline etching waste liquid is 7.1 and the copper ion is 60 g/L. In this embodiment, the anolyte supplementary solution preparation tank and the ammonia gas generating device are added to prepare the anolyte supplementary solution. The heating reaction kettle is filled with ammonium chloride solution, the solid feeding device is equipped with solid sodium hydroxide, and the solid feeding device in the anolyte supplementary solution preparation tank is equipped with ammonium bicarbonate. During the electrolysis process, the anolyte supplementary solution is added to the circulating return transfer tank. The supplementary solution is mainly prepared from the reactants of ammonium bicarbonate, ammonia gas and part of the anolyte solution. The ammonia gas is produced from the ammonium chloride in the heating reaction kettle. It is heated and reacted with sodium hydroxide mixture.

During the electrolysis process, a plurality of electrolytic anodes are connected to the positive electrodes of the electrolytic power supply and placed in the solution of the square box of each anode area in the electrolysis reaction tank, so that the anolyte is released into carbon dioxide gas, and the negative electrodes of the multiple electrolytic cathodes and the electrolytic power supply are in phase. It is connected and placed in the solution of the cathode area, and copper is continuously electro-deposited on a plurality of cathodes and the electrolytic copper is recovered by stripping out the cathodes.

Example 7

As shown in FIG. 7 , the alkaline etching waste liquid regeneration and reuse device used in this embodiment includes anode area square boxes 11-13, cathode area 21, electrolytic separators 31-36, electrolytic anodes 41-43, and electrolytic cathodes 51- 54. Electrolysis power supply 61, circulating return transfer tank 70, cathode area top cover plate air extraction hood 91, anolyte precipitation gas drainage pipe 101, anode area square box gas drainage pipes 102-104, cathode area gas drainage pipe 111, automatic Detection and feeding controller 120, detection devices 121-129, catholyte overflow storage tank 141,

temporary storage tanks

142 and 143, liquid circulating flow agitators 151-152, impeller agitator 161, hot and

cold temperature exchangers

171 and 172, Jet suction devices 181-187, centrifugal fan suction spray device 191, alkaline etching production line 200, solid-liquid separation device 211, water-oil separation device 221, tail gas absorption liquid tank 231, tail gas absorption liquid tank 232, carbon dioxide generation device, ammonia gas generating device,

solid feeding devices

251 and 252, regeneration sub-liquid preparation tank 281, overflow buffer tank 291, catholyte overflow buffer tank 292, pump 300~pump 309, feeding port 314~318 , Tail gas discharge port 321~329, valve 300~341.

The square boxes 11 to 13 in the anode area are in the form of square boxes made of non-conductive and water-impermeable material, and are respectively equipped with electrolytic anodes 41 to 43, and the square boxes 11 to 13 in the anode area are placed in the electrolysis reaction tank. In the hexahedron of the square boxes 11 to 13 in the anode area, an electrolytic separator is used as the separation between the anode area and the cathode area on the box surface facing the electrolytic cathode outside the box, and the inner area of the square box is used as the anode area. The area outside the square box in the electrolysis reaction tank is: The cathode area 21, the electrolysis separators 31 to 36 are all cation exchange membranes; the electrolysis cathodes 51 to 54 and the anode area square boxes 11 to 13 are arranged at intervals from left to right, and are placed in the electrolysis reaction tank to form an anode. zone and cathode zone of the electrolysis reactor. The square boxes 11 to 13 in the anode area, the overflow buffer tank 291 and the circulating return transfer tank 70 are connected by the pump 300 and the valve 330 to form a liquid circulation pipeline, and the circulating return transfer tank 70 is connected by the valve 331, the pump 301, the solid-liquid The separators 213 are respectively connected with the square boxes 11 to 13 of the anode area to form a return pipeline, so that the solutions between the three tanks are circulated and mixed. The circulating return transfer tank 70 is provided with a detection device 123 , a cold and hot temperature exchanger 173 ,

jet suction devices

181 and 182 , a feeding port 314 and an exhaust port 323 . The overflow buffer tank 291 is provided with the detection device 124 . Heating reactor 241 is used as carbon dioxide generator and etching supplementary carbon dioxide generator simultaneously, heating reactor 242 is used as ammonia gas generator, and the gas generated by heating reactor 241 in the kettle is controlled by process program to open

valves

339 and 341 and use respectively. The jet suction devices 181 and 187 introduce the gas into the solution in the circulating reflux transfer tank 70 and the solution in the regenerating sub-liquid preparation tank 281, and the gas generated in the heating reactor 242 is controlled by the process program to open the valve 340 respectively. And use the jet suction device 182 to introduce the gas into the solution in the circulating reflux transfer tank 70 . The absorption liquids of the two tail gas

absorption liquid tanks

231 and 232 all use formic acid, and the ammonia gas produced by heating the reactor 242 is controlled by the valve 341 and the absorption liquids in the two tail gas

absorption liquid tanks

231 and 232 are stored in the temporary storage tank 143. The reaction in the tank is prepared to obtain a high-concentration ammonium formate and ammonia water mixture. The top of the temporary storage tank 143 is also provided with a jet suction device 185, which introduces ammonia gas into the liquid in the tank according to the process control. The circulating reflux transfer tank 70 is connected with the temporary storage tank 143, and the mixed reuse liquid of ammonium formate and ammonia water obtained from the temporary storage tank 143 is added to the circulating reflux transfer tank 70 by adding the mixed reuse liquid of ammonium formate and ammonia water obtained from the temporary storage tank 143 as a raw material for carbon dioxide generation and ammonia. Replenish. The heating reaction kettle 241 is provided with a detection device 121 , a circulating liquid flow stirring device 151 , a feeding port 314 and a tail gas discharge port 321 . The heating reaction kettle 242 is provided with a detection device 122 , an impeller stirring device 161 , a feeding port 315 and a tail gas discharge port 322 . The cathode area 21 is provided with a detection device 125, a liquid circulating flow agitator 152 and an overflow port. The overflow port of the cathode area 21 sends the overflow liquid into the catholyte overflow buffer tank 292 through a pipeline, and the catholyte liquid overflows. The buffer tank 292 is connected to the catholyte overflow storage tank 141 through the valve 332 and the pump 302 . The catholyte overflow storage tank 141 is connected with the regeneration sub-liquid preparation tank 281 through the pipeline provided with the valve 333 and the pump 303; The pipes of the pump 304 and the solid-liquid separation device 212 are connected to the alkaline etching production line 200 . The alkaline etching production line 200 is connected to the temporary storage tank 142 through the water-oil separation device 221, the pipelines and valves 335 of the solid-liquid separation device 211, and the pump 305, so that the etching waste liquid produced by the production line 200 is sent to be used as etching waste. It is temporarily stored in the temporary storage tank 142 of the liquid storage tank. The temporary storage tank 142 is connected with the cathode area 21 through the valve 336 , the pump 306 and the pipeline, and the pump 306 is controlled by the automatic detection and feeding controller 120 to perform the action of adding the alkaline etching waste liquid to the cathode area 21 . The regenerated sub-liquid preparation tank 281 is provided with a feeding port 317, and is also equipped with two independent

jet suction devices

183 and 184. Among them, the jet suction device 183 absorbs the exhaust gas of the three-slot tail gas B1 for the exhaust gas of the circulating backflow transfer tank 70, the gas discharged from the square boxes 11 to 13 in the anode area, and the exhaust gas of the overflow buffer tank 291; The gas, the catholyte overflow storage tank 141 and the catholyte overflow buffer tank 292 are used for the absorption treatment of the three-tank tail gas B2. The top of each anode area square box 11 to 13 are respectively provided with electrolytic anode area square box gas drainage pipes 102 to 104, and the gas in the anode area square box 11 to 13 is respectively introduced into the regeneration sub-liquid preparation tank through the jet suction device 183 In the solution of 281; the cathode area 21 is provided with a top cover air extraction hood 91, and the top of the top cover air extraction hood 91 is provided with an electrolysis cathode area gas drainage pipe 111 from the cathode area. into the liquid in the preparation tank 281 of the regenerated sub-liquid. The detection device 127 installed on the regeneration sub-liquid preparation tank 281 is used for detection when the regeneration etching sub-liquid is prepared according to the process. The tops of the regeneration sub-liquid preparation tank 281, the temporary storage tank 142 and the temporary storage tank 143 are respectively provided with a tail gas discharge port 326, a tail gas discharge port 327 and a tail gas discharge port 328; The exhaust gas as exhaust gas C is connected with the air inlet of the exhaust gas treatment system in series through the gas draft pipe. The exhaust gas treatment system in series is the combination of the centrifugal suction spray device 191 and the exhaust gas absorption liquid tank 231, and the combination of the jet suction device 185 and the exhaust gas absorption liquid tank 232. In the exhaust gas treatment system in series, the centrifuge type suction The air outlet of the centrifugal fan of the spray device 191 is connected to the air inlet of the jet air suction device 185 . The ammonia tail gas absorption liquid in the two tail gas

absorption liquid tanks

231 and 232 adopts formic acid solution. The electrolysis power supply 61 is connected with the automatic detection feed controller 120, and the automatic detection feed controller 120 controls the temperature of the heating reaction kettles 241 and 242 to change the reaction speed and/ Or as a feed supplement. The automatic detection and feeding controller 120 automatically adjusts the output current of the electrolysis power supply 61 according to the process parameter results measured by the detection device 125 of the cathode area 21, and/or controls the flow of the alkaline etching waste liquid in the temporary storage tank 142 through the pump 306. In the cathode region 21 for additional injection. The automatic detection feeding controller 120 controls the feeding pump 304 between the regeneration sub-liquid preparation tank 281 and the alkaline etching production line 200 according to the process parameter results measured by the detection device 128 of the alkaline etching production line 200, so that it is directed to the alkaline etching production line. 200 additional doses of the prepared regenerated etching sub-liquid to maintain normal etching production. For the addition of the regeneration sub-liquid to the alkaline etching production line 200, the pH value process parameters of the etching working solution in the tank tank of the alkaline etching production line 200 can be used as the process investment control point, that is, the pH value investment control point is set. When the pH is set to 7.3, the etching working solution will consume ammonia in the continuous copper-dissolving reaction as the etching process proceeds, resulting in the constant reduction of the pH value of the etching working solution. The controller 120 will automatically control the pump 304 to add the prepared regenerated etching sub-liquid to the alkaline etching production line 200 .

The alkaline etching waste liquid is regenerated and reused by the device shown in Figure 7:

During the electrolysis process, the anolyte solution is connected by a circulating pipeline among the anode area, the overflow buffer tank and the circulating return transfer tank, so that the solutions in the three tanks are circulated and mixed. The carbon dioxide in the anolyte is supplemented by chemical reaction between the anolyte and the ammonia gas and carbon dioxide gas produced by the reaction in the two heating reactors, and the mixed solution of ammonium formate and ammonia water that is fed into the circulating reflux tank. Raw materials and ammonia are generated. The gas precipitated in the cathode area and the anode area, the tail gas of the circulating back transfer tank, the overflow liquid buffer tank and the electrolytic catholyte overflow liquid storage tank are all led to the regeneration sub-liquid preparation tank for reaction and absorption. The pre-prepared catholyte solution, that is, the alkaline etching waste solution, is added to the cathode area 21 to maintain a certain concentration of copper ions in the catholyte solution to maintain the electrolytic copper reaction on the electrolytic cathode.

The pre-prepared catholyte in this embodiment is an alkaline etching waste liquid, wherein the pH value of the alkaline etching waste liquid is 7.3 and the copper ion is 80 g/L.

Example 8

As shown in FIG. 8 , the alkaline etching waste liquid regeneration and reuse device used in this embodiment includes anode area square boxes 11-14, cathode area 21, electrolytic separators 31-36, electrolytic anodes 41-44, and electrolytic cathodes 51- 53. Electrolysis power supply 61, circulating return transfer tank 70, cathode area top cover plate air extraction hood 91, anolyte precipitation gas drainage pipe 101, cathode area gas drainage pipe 111, automatic detection and feeding controller 120, detection devices 121-124 , catholyte overflow storage tank 141,

temporary storage tanks

142 and 143, liquid circulating flow agitator 151, impeller agitator 161, jet suction device 181, centrifugal fan

suction spray device

191 and 192, solid-liquid separation device 211, exhaust gas absorption tank 231, overflow buffer tank 291, catholyte overflow buffer tank 292, pump 300~310, feeding

ports

314 and 315, exhaust gas discharge port 321~327, valve 330~340, water washing spray Tubes 371-373.

Electrolysis separators 31 to 36 are bipolar membranes that separate the electrolysis cell body into an electrolysis anode region and an electrolysis cathode region. During the electrolysis process, the membrane surface of the bipolar membrane to release [OH] ^- ions should face the electrolysis anode in the anode electrolysis cell area, while the membrane surface of the bipolar membrane releasing H+ ions should face the direction of the electrolysis cathode. The square boxes 11 to 14 in the anode area are in the form of square boxes of non-conductive and water-impermeable material and are respectively equipped with electrolytic anodes 41 to 44, and the square boxes 11 to 14 in the anode area are placed in the electrolysis reaction tank. In the hexahedron of the square boxes 11 to 14 in the anode area, an electrolytic separator is used for the box surface facing the electrolytic cathode outside the box, which is used as a separator between the anode area and the cathode area, and the inner area of the square box is used as the anode area. The outer area is the cathode area 21; the anode area square boxes 11 to 14 and the electrolytic cathodes 51 to 53 are arranged at intervals from left to right, and are placed in the electrolytic reaction tank to form an electrolytic reaction tank separated into an anode area and a cathode area.

The anode area square boxes 11 to 14, the overflow buffer tank 291 and the circulating return transfer tank 70 are connected to form a liquid circulation pipeline through the pipeline connection of the valve 332 and the pump 302, and the circulating return transfer tank 70 passes through the valve 337, the pump 307, The solid-liquid separation device 211 is respectively connected with the square boxes 11 to 14 of the anode area to form a return pipeline, so that the anolyte can circulate in the above three tanks. The circulating return transfer tank 70 is provided with a detection device 122, as well as a jet suction device 181 and a centrifugal fan-type suction spray device 191; the overflow buffer tank 291 is provided with a detection device 123, and the top of the overflow buffer tank 291 is also The anolyte precipitation gas drainage pipe 101 is provided, and the gas precipitated in the tank is introduced into the solution of the circulating return transfer tank 70 through the centrifugal fan-type suction spray device 191; 330 provides the carbon dioxide generating raw material to the circulating return transfer tank 70 , and the solution solvent in the anolyte supplementary solution preparation tank 271 is drawn from the circulating return transfer tank 70 . The anolyte supplementary solution preparation tank 271 is provided with a detection device 121, a stirring device 161, and a solid adding device 251. Solid oxalic acid is loaded in the solid feeding device 251 . The cathode area 21 is provided with a cathode area top cover plate air extraction hood 91, and the top of the cathode area top cover plate air extraction hood 91 is provided with a cathode area gas drainage pipe 111, and the gas precipitated from the cathode area 21 is drained through the jet suction device 181 into the circulating reflux transfer tank 70 solution. The cathode area 21 is provided with a detection device 124, a liquid circulating flow agitator 151 and an overflow port. The catholyte overflow buffer tank 292 is connected to the cathode region 21 through the overflow port. Catholyte overflow storage tank 141 is connected to catholyte overflow buffer tank 292 through valve 334 and pump 304 for storing catholyte overflow. The temporary storage tank 142 stores the pre-prepared catholyte solution, that is, the alkaline etching waste liquid; The gas outlet of the circulating return transfer tank 70, the catholyte overflow storage tank 141, the temporary storage tank 142, the catholyte overflow buffer tank 292 and the anolyte supplementary liquid preparation tank 271 respectively pass through the gas drainage pipe and the air intake of the exhaust gas treatment system. The ports are connected and treated with exhaust gas. The tail gas treatment system of the device is a combination of a centrifugal fan-type suction spray device 192 and a tail gas absorption liquid tank 231, wherein the absorption liquid in the tail gas absorption liquid tank 231 is hydrochloric acid, which reacts with the tail gas to generate ammonium chloride for recycling. into the preparation of the regeneration sub-liquid. The automatic detection and feeding controller 120 automatically controls the pump 300 according to the process parameter results measured by the detection device 122 installed on the circulating return transfer tank 70, and adds the supplementary solution of the prepared anolyte to the circulating return transfer tank. 70 in. The automatic detection and feeding controller 120 automatically executes and controls the feeding operation of the solid adding and controlling device 251 according to the real-time detection results of the detection device 121 on the anolyte replenishing solution preparation tank 271 and/or extracts the circulating backflow through the valve 331 and the pump 301 The solution in the transfer tank is prepared in the anolyte replenishing solution preparation tank 271 . The electrolytic power source 61 is connected with the automatic detection and feeding controller 120, and the automatic detection and feeding controller 120 adjusts or shuts down the output current of the electrolytic power source 61 according to the process parameter results measured by the detection device 124 of the cathode area 21, and/or according to The feeding threshold control method of the copper ion concentration of the catholyte solution set by the process or automatically controls the feeding pump 305 between the temporary storage tank 142 and the cathode area 21 according to the time program to add alkaline etching waste liquid to the cathode area 21 middle.

Use the device shown in Figure 8 to regenerate and reuse the alkaline etching waste liquid:

During the electrolysis process, the anolyte circulates among the three types of tanks: the anode area, the overflow buffer tank and the circulating return transfer tank. The anolyte in the circulating return transfer tank is connected to the carbon dioxide gas from the electrolysis anode area of the electrolysis tank and the ammonia gas from the electrolysis cathode area as the synthesis reaction raw materials for carbon dioxide generation raw materials. Add oxalic acid and water to the circulating return transfer tank, and add alkaline etching waste liquid to the cathode area to maintain a certain copper ion concentration in the catholyte to maintain the electrolytic copper reaction on the electrolytic cathode.

The pre-prepared catholyte in this embodiment is an alkaline etching waste liquid, wherein the pH value of the alkaline etching waste liquid is 7.5 and the copper ion is 100 g/L.

Step 4: After the electrolytic copper desorption is completed, the cathode is first washed and sprayed with water, and the cathode can be taken out from the electrolytic cell after the spraying process and then subjected to copper stripping and recovery treatment. Specifically: after the electrolytic copper desorption operation is completed, the electrolyte in the square box of the anode area is firstly pumped into the circulating return transfer tank 70 through the valve 338 and the pump 308 for temporary storage, and the electrolyte in the cathode area is passed through the valve 333. , pump 303 to the catholyte overflow liquid storage tank 141 for temporary storage. Then, the clean water stored in the temporary storage tank 143 is poured into the cathode area 21 of the electrolytic cell through the valve 340 and the pump 310 to immerse the cathode for cleaning and/or spray and clean the electrolytic cathode with water. After cleaning the electrolysis cathode, the water in the cathode area 21 is pumped back to the temporary storage tank 143 through the valve 339 and the pump 309 for temporary storage for next use. The electrolytic catholyte will be refilled into the electrolytic cathode tank through the control valve 336 and the pump 306; The automatic detection and feeding controller 120 will automatically reconnect the electrolysis power supply and continue to work after the result of the system detection according to the program meets the technological requirements.

The copper ammonia solution attached to the cathode can be taken out from the electrolytic cell and then stripped for copper recovery, which can reduce the ammonia pollution of the working environment. During the washing process, the electrolytic solution in the square box of the anode area of the electrolytic cell is extracted, and corresponding measures are taken to minimize the chance that the electrolytic separator is easily damaged by unilateral hydraulic pressure after extraction of the catholyte.

Example 9

As shown in FIG. 9 , the alkaline etching waste liquid regeneration and reuse device used in this embodiment includes two electrolysis reaction tanks with the same structure. Two electrolytic anode area square boxes with anodes are respectively placed in the two electrolytic reaction tanks, and the remaining volume of the electrolytic tank outside the two square boxes is the cathode area. Therefore, there are four electrolytic anode square boxes in two electrolytic cells, and six cathode electrodes; namely, anode area square boxes 11 to 14,

cathode areas

21 and 22, electrolytic separators 31 to 38, and electrolytic anodes 41 to 44 , the electrolysis cathodes 51-56. It also includes electrolysis power sources 61 and 62, circulating return transfer tank 70, cathode area top cover plate air extraction hood 91, cathode area top cover plate air extraction cover 92, anolyte precipitation gas drainage pipe 101, cathode area gas drainage pipe 111, Cathode area gas drainage pipe 112, automatic detection and feeding controller 120, detection devices 121-131, catholyte overflow storage tank 141,

temporary storage tanks

142 and 143, liquid circulating flow agitator 151, liquid circulating flow stirring, 152, impeller Stirrer 161, impeller stirrer 162, hot and cold temperature exchangers 171-175, jet suction devices 181-186, centrifugal fan

suction spray devices

191 and 192, alkaline etching production line 200, solid-liquid separation devices 211- 213, tail gas

absorption liquid tanks

231 and 232,

solid feeding devices

251 and 252, regeneration

sub-liquid preparation tanks

281 and 282, overflow buffer tank 291, catholyte overflow buffer tank 292, overflow buffer tank 293, pump 300-313 and 1301 and 1302, feeding ports 314-318, exhaust ports 321-329 and 1330, valves 330-348 and 1331-1334.

The electrolytic separators 31 to 36 are all cation exchange membranes, the square boxes 11 to 14 in the anode area are in the form of square boxes of non-conductive and impermeable materials, and the electrolytic anodes 41 to 44 are housed therein, and the square boxes 11 to 14 in the anode area are respectively two. The two are placed in two electrolytic reaction tanks. In the hexahedron of the square boxes 11 to 14 in the anode area, an electrolytic separator is used as the separation between the anode area and the cathode area on the box surface facing the electrolytic cathode outside the box, and the space inside the square box is used as the anode area to separate an electrolysis reaction tank into an anode area. 11 to 12 and the cathode area 21, another electrolytic reaction tank is separated into the anode area 13 to 14 and the cathode area 22.

The four anode area square boxes 11 to 14 in the two electrolysis reaction tanks are connected with the overflow buffer tank 291 and the circulating return transfer tank 70 through pipelines to form a liquid channel, and the circulating return transfer tank 70 passes through the valve 334, the pump The pipes 304 and the solid-liquid separator 211 are respectively connected with the square boxes 11 to 14 of the anode area to form a return channel, and the above-mentioned liquid channel and return channel form a circulating flow pipe network of the anolyte. The circulating return transfer tank 70 is provided with a detection device 123 , a cold and hot temperature exchanger 173 and a feeding port 316 . The overflow buffer tank 291 is provided with a detection device 124, and an anolyte precipitation gas drainage pipe 101 is also installed on the top of the overflow buffer tank 291, and the gas in the tank is introduced into the circulating return transfer tank 70 through a centrifugal fan-type suction spray device 191. The two anolyte supplementary

solution preparation tanks

271 and 272 are respectively provided with

detection devices

121 and 122,

impeller stirring devices

161 and 162, and feeding

ports

314 and 315. The tops of the anolyte supplementary

solution preparation tanks

271 and 272 are respectively provided with tail

gas discharge ports

321 and 322, and the precipitation gas is introduced into the solution in the regeneration

sub-liquid preparation tanks

281 and 282 through the jet suction devices 182 to 185 according to the process requirements. The

cathode regions

21 and 22 are respectively equipped with

detection devices

125 and 126, circulating liquid

flow stirring devices

151 and 152. The overflow ports of the

cathode regions

21 and 22 are connected with the catholyte overflow buffer tank 292 through pipelines, and the catholyte overflow buffer tank 292 passes through the valve 335, the pipeline of the pump 305 and the catholyte overflow storage tank 141. Connected and used for temporary storage of catholyte spillage. The catholyte overflow storage tank 141 for temporarily storing catholyte overflow liquid is connected to the regeneration

sub-liquid preparation tanks

281 and 282 through the pipes of

valves

336 and 337 and pumps 306 and 307, respectively, and the process of automatic detection and feeding controller 120 is carried out. Control calls for pumping catholyte overflow into regeneration

sub-liquid preparation tanks

281 and 282. The anolyte supplementary

solution preparation tanks

271 and 272 are respectively connected with the circulating reflux transfer tank 70 as a circulating loop, and the anolyte supplementary

liquid preparation tanks

271 and 272 are prepared in turn, so that the circulating reflux transfer tank 70 can be obtained according to the process without stopping the machine. Requires a supply of prepared anolyte make-up solution. Similarly, the regeneration

sub-liquid preparation tanks

281 and 282 are also used to prepare the regeneration etching sub-liquid in turn. The regeneration etching sub-liquid that has been prepared according to the process requirements is controlled by the pipelines of

valves

342 and 343 and pumps 308 and 309 respectively. The prepared regenerated etching sub-liquid is pumped into the temporary storage tank 142 for temporary storage. The temporary storage tank 142 is equipped with a detection device 130 and a hot and cold temperature exchanger 175 so that the storage liquid can be kept at a constant temperature according to the process, and is connected to the alkaline etching production line 200 through the valve 344, the pump 310, and the pipeline of the solid-liquid separation device 212. connect. A detection device 131 is installed on the alkaline etching production line 200, and the etching waste liquid overflowing from the alkaline etching production line 200 is pumped to the temporary storage for storing the etching waste liquid through the pipeline provided with the water-oil separation device 221 and the solid-liquid separation device 211. in slot 143. The temporary storage tank 143 is respectively connected with the cathode area 21 and the electrolysis cathode area 22 through the pipelines provided with valves 1350 and 1351 and the pump 312, and according to the automatic detection and feeding controller 120, the execution instruction to the pump 312 is issued to alkali etch. The waste liquid is added to the electrolysis cathode area 21 and/or 22. Regeneration

sub-liquid preparation tanks

281 and 282 are respectively provided with

detection devices

128 and 129 , jet suction devices 182 to 185 , feeding

ports

317 and 318 , and exhaust

gas discharge ports

326 and 327 . Among them, the

jet suction devices

182 and 184 control the opening and closing of the

valves

338 and 340 through the automatic detection and feeding controller 120, so that the regeneration

sub-liquid preparation tanks

281 and 282 respectively absorb the B1 gas precipitated by the circulating return transfer tank 70, and the jet suction The

devices

183 and 185 control the opening and closing of the

valves

339 and 341 through the automatic detection and feeding controller 120, so that the regenerated

sub-liquid preparation tanks

281 and 282 can absorb the B2 gas precipitated in other tanks. The regenerated

sub-liquid preparation tanks

281 and 282 utilize the absorbed oxygen, carbon dioxide gas and ammonia gas to make them react in the tank, and additionally add chloride salt and/or additives to obtain a regenerated etching sub-liquid that meets the process requirements .

Cathode regions

21 and 22 are respectively provided with cathode region top cover plate air extraction hoods 91 and 92, and cathode region gas drainage pipes 111 and 112 are respectively provided on the top of cathode region top cover air extraction hoods 91 and 92, which will separate out the two cathode regions. The gas is drained into the circulating return transfer tank 70 through the centrifugal fan-type suction and spray device 191; the tops of the temporary storage tank 142, the temporary storage tank 143, and the regeneration

sub-liquid preparation tanks

281 and 282 are respectively installed with gas drainage pipes, and respectively It is connected with the air inlet of the exhaust gas treatment system in series; the first exhaust gas treatment system is the combination of the centrifugal fan-type suction spray device 192 and the exhaust gas absorption liquid tank 231, and the second exhaust gas treatment system is the jet suction device 186 and the exhaust gas The combination of the absorption liquid tank 232, the exhaust outlet of the first tail gas treatment system is connected with the suction port of the second tail gas treatment device, and the tail gas absorption liquids of the two tail gas

absorption liquid tanks

231 and 232 are all selected for the use of formic acid solution to absorb ammonia. The tail gas makes the solution in the tank generate ammonium formate solution. The automatic detection and feeding controller 120 controls the feeding pump 300 and/or 302 for adding the anolyte supplementary solution according to the process parameter results measured by the detection device 123 of the circulating backflow transfer tank 70, according to the anolyte supplementary

solution preparation tank

271 and 272. The detection results of the

detection devices

121 and 122 automatically adjust the working power of the hot and cold temperature exchangers 171 and/or 172 and control the solid feeding devices 251 and/or 252 for feeding. The automatic detection and feeding controller 120 performs replenishment and preparation according to the detection results of the

detection devices

128 and 129 installed on the regenerated

sub-liquid preparation tanks

281 and 282 according to the process requirements. live. The automatic detection and feeding controller 120 stores the prepared regenerated etching sub-liquid in the temporary storage tank 142 according to the actual measurement results of the detection device 131 installed on the alkaline etching production line 200 according to the process requirements and adds it to the alkaline etching production line 200 to maintain normal operation. Etch production. The automatic detection and feeding controller 120 automatically adjusts or shuts down the output current of the electrolysis power supply 61 and/or 62 according to the process parameter results measured by the

detection devices

125 and 126 of the

cathode areas

21 and 22, and/or controls the temporary storage tank 143 to The switch of the valves 1331 and 1332 between the

cathode areas

21 and 22, and the control of the flow rate or the switch of the feeding pump 312, correspondingly perform the feeding action through the branch pipeline.

The alkaline etching waste liquid is regenerated and reused by the device shown in Figure 9:

During the electrolysis process, the four anode box boxes in the two electrolysis reaction tanks are connected with the overflow buffer tank and the circulating return transfer tank by a pipeline, and the circulating return transfer tank is connected with the pipeline through valves, pumps and solid-liquid separators. The four anode area square boxes are connected to form another channel, so that the anolyte is circulated and mixed between the circulating return transfer tank, the overflow buffer tank and the four anode area square boxes. The chemical reaction of the gas from the cathode zone and the anode zone is introduced into the circulating reflux transfer tank for absorption. In addition, the anolyte supplementary solution is additionally input into the circulating return transfer tank. The alkaline etching waste liquid is supplemented to the cathode area to maintain a certain concentration of copper ions in the catholyte to ensure the normal copper electrolysis reaction on the electrolytic cathode.

Step 4: The catholyte that overflows the electrolytic reaction tank after the copper is electrolyzed is formulated into a regenerated etching sub-liquid according to the process requirements, and is added to the alkaline etching production line for repeated use.

The pre-prepared catholyte in this embodiment is an alkaline etching waste liquid, wherein the pH value of the alkaline etching waste liquid is 8.5 and the copper ion is 160 g/L.

Among them, in step 3 of this embodiment, two anolyte supplementary

liquid preparation tanks

271 and 272 are set to prepare the supplementary liquid of the anolyte solution in turn, and the solid adding and

dosing devices

251 and 252 are respectively controlled by the logic program of the process system. The action of the solid mixture of oxalic acid and ammonium carbonate to the anolyte supplementary

solution preparation tank

271 and 272, wherein the solvent part in the anolyte supplementary

solution preparation tank

271 and 272 is taken from the solution in the circulating return transfer tank 70; The supplementary solution of the anolyte is added to the circulating reflux transfer tank 70 according to the process requirements, and the ammonium formate solution produced by the tail gas system tank 231 and the tank 232 is also put into the circulating reflux transfer tank according to the logic program control of the process system. 70 in. The mixed solution of oxalic acid, ammonium carbonate, and ammonium formate reacts chemically with the gas precipitated by the introduction of the anion and cation electrolytes in the circulating reflux transfer tank 70 to obtain a pre-prepared anolyte. The regenerated etching sub-liquid described in step 4 has the same properties as the conventional preparation etching sub-liquid, and is automatically detected and fed according to the process specific gravity setting value of the etching working liquid on the alkaline etching production line and the specific gravity value of the real-time detection result. The controller 120 performs processing and additional control to maintain the normal etching production of the alkaline etching production line.

During the electrolysis process, the

electrolytic anodes

41 and 42 are connected with the positive electrode of the electrolytic power source 61 and placed in the solution of the

square boxes

11 and 12 of the electrolytic anode area of the electrolytic reaction tank. Connected and placed in the solution of the cathode area 21 of the electrolytic reaction tank and continuously precipitated copper; the

electrolytic anodes

43 and 44 are connected with the positive electrodes of the electrolytic power supply 62 and placed in the solution of the anode area

square boxes

13 and 14 of the electrolytic reaction tank Inside, the electrolytic cathodes 54, 55 and 56 are connected to the negative electrode of the electrolytic power source 62 and placed in the solution of the cathode area 22 of the electrolytic reaction tank and copper is continuously deposited.

Example 10

As shown in Figure 10, the alkaline etching waste liquid regeneration and reuse device used in this embodiment includes two electrolysis reaction tanks with the same structure; The space outside the square box of the anode area is the electrolytic cathode area. Therefore, there are four anode square boxes in two electrolysis reaction tanks, and six cathode electrodes, namely anode square boxes 11-14,

cathode areas

21 and 22, electrolytic separators 31-38, and electrolytic anodes 41-44 , the electrolysis cathodes 51-56. The device of this embodiment also includes electrolysis power sources 61 and 62, a circulating return transfer tank 70, a cathode area top cover plate air extraction hood 91, a cathode area top cover plate air extraction cover 92, an anolyte evolved gas drainage pipe 101, and a cathode area. Gas drainage pipe 111, cathode gas drainage pipe 112, automatic detection and feeding controller 120, detection devices 121-135, catholyte overflow storage tank 141, temporary storage tank 142, temporary storage tank 143, liquid circulating flow agitator 151, Liquid circulating flow stirring 152, impeller agitator 161, impeller agitator 162, hot and cold temperature exchangers 171-176, jet suction device 181-185, centrifugal fan suction spray device 191, alkaline etching production line 200, solid Liquid separation devices 211-213, tail gas

absorption liquid tanks

231 and 232,

solid feeding devices

251 and 252, anolyte supplementary

liquid preparation tanks

271 and 272, regeneration

sub-liquid preparation tanks

281 and 282, overflow buffer tank 291, cathodic electrolysis Liquid overflow buffer tank 292, overflow buffer tank 293, pumps 300-313 and 1300-1302, feeding ports 313-319, exhaust ports 321-329 and 1321, equipment failure alarm 260, valves 330-349 and 1330 ~1333.

The four anode area square boxes 11 to 14 in the two electrolysis reaction tanks are connected with the overflow buffer tank 291 and the circulating return transfer tank 70 through pipelines to form a liquid channel, and the circulating return transfer tank 70 passes through the valve 334, the pump The pipes 304 and the solid-liquid separator 211 are respectively connected with the square boxes 11 to 14 of the anode area to form a return channel, and the above-mentioned liquid channel and return channel form a circulating flow pipe network of the anolyte. The circulating return transfer tank 70 is provided with a detection device 123 , a cold-heat temperature exchanger 173 and a tail gas discharge port 323 , the tail gas of which is led to the regeneration sub-liquid preparation tank 281 and/or 282 . The overflow buffer tank 291 is provided with a detection device 124 , and an anolyte precipitation gas drainage pipe 101 is also installed on the top of the overflow buffer tank 291 to lead the precipitation gas to the regeneration sub-liquid preparation tank 281 and/or 282 . The anolyte supplementary

solution preparation tanks

271 and 272 are respectively provided with

detection devices

121 and 122,

impeller stirring devices

161 and 162, feeding

ports

314 and 315, and tail

gas discharge ports

321 and 322, which will be respectively set in the anolyte supplementary

liquid preparation tanks

271 and 162. The exhaust

gas discharge ports

321 and 322 at the top of 272 are respectively introduced into the solutions in the regenerated

sub-liquid preparation tanks

281 and 282 through the

jet suction devices

181 and 183 according to the process requirements; the

cathode regions

21 and 22 are respectively equipped with

detection Devices

125 and 126, circulating liquid

flow stirring devices

151 and 152. The overflow ports of the

cathode regions

21 and 22 are connected with the catholyte overflow buffer tank 292 through pipelines, and the catholyte overflow buffer tank 292 passes through the valve 336, the pipeline of the pump 306 and the catholyte overflow storage tank 141. are connected, and catholyte overflow storage tank 141 serves as a temporary storage tank for catholyte overflow. The catholyte overflow storage tank 141 is connected to the parallel regeneration

sub-liquid preparation tanks

281 and 282 through

valves

337 and 338, pumps 307 and 308 respectively, and the catholyte overflow is pumped to the automatic detection and feeding controller 120 according to the process control requirements of the automatic detection feed controller 120. The regeneration

sub-liquid preparation tanks

281 and 282 are used for preparation. Two sets of anolyte supplementary

liquid preparation tanks

271 and 272 are used for alternate preparation, so that the circulating return transfer tank 70 can obtain the supply of anolyte supplementary liquid prepared according to the process requirements without stopping the machine. Similarly, taking two sets of the regenerating

sub-liquid preparation tanks

281 and 282 is also to prepare the regenerating etching sub-liquid in turn, and the regenerating etching sub-liquid that has been prepared according to the process requirements is controlled by the

valves

343 and 344 and the pump 309 respectively according to the process program. The pipeline of and 310 pumps the prepared regenerated etching sub-liquid to the temporary storage tank 142 for temporary storage. The temporary storage tank 142 is equipped with a detection device 132 and a hot and cold temperature exchanger 176, so that the storage liquid can be treated at a constant temperature according to the process requirements, and the temporary storage tank 142 passes through the valve 345, the pump 311, the pipeline of the solid-liquid separation device 212 and the The alkaline etching production line 200 is connected. A detection device 133 is installed on the alkaline etching production line 200, and the etching waste liquid overflowed by the alkaline etching production line 200 is pumped to the storage alkaline etching through the overflow buffer tank 293, the solid-liquid separation device 213, the valve 346, and the pump 312. In the temporary storage tank 143 of the waste liquid. The temporary storage tank 143 is connected with the D1 inlet of the cathode area 21 and the D2 inlet of the cathode area 22 through the two branch pipes D1 and D2 with the valve 347 and the pump 313 through the two

valves

348 and 1300 respectively, and is controlled according to the automatic detection and feeding. The device 120 sends an execution instruction to the pump 313 to add the alkaline etching waste liquid to the electrolysis cathode regions 21 and/or 22 . Regeneration

sub-liquid preparation tanks

281 and 282 are respectively provided with

detection devices

130 and 131, jet suction devices 181 to 184, feeding

ports

316 and 317, and exhaust

gas discharge ports

326 and 327; two sets of

jet suction devices

181 and 183 are Through process program control,

valves

339 and 341 are opened to allow the regeneration

sub-liquid preparation tanks

281 and 282 to absorb the B1 gas precipitated from the circulating return transfer tank 70, as well as the B1 gas and overflow buffer tank precipitated from the anolyte supplementary

liquid preparation tanks

271 and 272, respectively. The B1 gas separated out by 291; the

cathode regions

21 and 22 of the electrolytic reaction cell are all provided with cathode region top cover plate air extraction hoods 91 and 92, and the top of the cathode region top cover plate air extraction hoods 91 and 92 are respectively provided with cathode region gas The drainage pipes 111 and 112 will lead out the B2 gas separated out from the two cathode regions, as well as the B2 gas separated from the catholyte overflow buffer tank 292 and the catholyte overflow storage tank 141, and use the

jet suction devices

182 and 184 to extract the B2 gas. discharge, and open the

valves

342 and 340 through program control to allow the regeneration

sub-liquid preparation tanks

281 and 282 to do absorption reactions; use the precipitated oxygen, carbon dioxide gas and ammonia gas to react in the regeneration

sub-liquid preparation tanks

281 and 282, and add additional Chloride salts and/or additives are used to obtain regenerated etching sub-liquids that meet process requirements. The exhaust gas from the temporary storage tank 142 and the temporary storage tank 143 and the exhaust gas from the regeneration

sub-liquid preparation tanks

281 and 282 are drained to the air inlets of the two sets of series-connected exhaust gas treatment systems through the centrifugal fan-type suction and spray device. The system is a combination of a centrifugal fan-type suction spray device 191 and an exhaust gas absorption liquid tank 231, the second exhaust gas treatment system is a combination of a jet suction device 185 and an exhaust gas absorption liquid tank 232, and the exhaust gas discharge port of the first exhaust gas treatment system is The suction ports of the second tail gas treatment device are connected, and the absorption liquids of the two tail gas absorption liquid tanks are all reacted with hydrochloric acid and the C tail gas containing ammonia precipitated in the device to obtain ammonium chloride solution and/or its crystals, which are returned to the regeneration

Sub-liquid preparation tanks

281 and 282 are used. The

detection devices

125 and 127 are respectively installed on the pipelines of the

anode regions

11 and 12 flowing out of the anolyte, and are specially used for detecting the copper ion concentration of the anolyte. The automatic detection feeding controller 120 controls the pump 300 and/or 301 to add anolyte supplementary solution to the circulating reflux transfer tank 70 according to the process parameter results measured by the detection device 123 in the circulating reflux transfer tank 70; the automatic detection feeding controller 120 automatically adjust the working power of the cold and

heat temperature exchangers

171 and 172 according to the detection results of the

detection devices

121 and 122 on the anolyte supplementary

liquid preparation tanks

271 and 272, and control the addition of ammonium carbonate material of the

solid addition devices

251 and 252 Action and/or add ammonia water to feed

ports

314 and 315. The automatic detection and feeding controller 120 performs feeding and dispensing according to the detection results of the

detection devices

130 and 131 installed on the regeneration

sub-liquid preparation tank

281 and 282, and controls the pump 309 and/or 310 after the detection result reaches the standard. The regenerated sub-liquid is pumped to the temporary storage tank 142 for temporary storage. The temporary storage tank 142 is provided with a cold and hot temperature exchanger 176 . The automatic detection and feeding controller 120 controls the pump 311 to automatically add the regenerated sub-liquid stored in the temporary storage tank 142 to the production line 200 according to the detection result of the detection device 133 on the alkaline etching production line 200 for normal etching production by Werther. The automatic detection and feeding controller 120 compares the real-time parameter results measured by the

detection devices

126 and 128 of the

cathode regions

21 and 22 with the process setting value, and automatically adjusts the output current of the electrolytic power sources 61 and 62 or shuts down the control, respectively, And/or control the opening and closing of the

valves

348 and 1330 between the temporary storage tank 143 and the

cathode areas

21 and 22 and control the opening and closing of the feeding pump 313 to perform corresponding feeding to the branch pipes D1 and/or D2. The automatic detection and feeding controller 120 according to the detection results of the

detection devices

125 and 127, if the copper ion concentration of the anolyte is greater than the process setting value, the equipment failure alarm 260 will issue an alarm.

Use the device shown in Figure 10 to regenerate and reuse the alkaline etching waste liquid:

During the electrolysis process, the four anode box boxes in the two electrolysis reaction tanks are connected with the overflow buffer tank and the circulating return transfer tank by a pipeline, and the circulating return transfer tank is connected through the pipeline of the valve, pump and solid-liquid separator. It is connected with the four anode area square boxes to form another channel, so that the anolyte is circulated and mixed between the circulating return transfer tank, the overflow buffer tank and the four anode area square boxes. The chemical reaction of the mixed absorption of the gas from the cathode and anode areas is introduced into the circulating reflux transfer tank. In addition, the anolyte supplementary solution is additionally input into the circulating return transfer tank. The alkaline etching waste liquid is supplemented to the cathode area to maintain a certain concentration of copper ions in the catholyte to ensure the normal copper electrolysis reaction on the electrolytic cathode.

Step 4: The catholyte that overflows out of the electrolytic reaction tank after the copper is electrolyzed is formulated into a regenerated etching sub-liquid according to the process requirements, and is added to the alkaline etching production line as a pre-prepared catholyte for repeated use.

The pre-prepared catholyte in this embodiment is an alkaline etching waste liquid, wherein the pH value of the alkaline etching waste liquid is 8.2 and the copper ion is 140 g/L.

Among them, in step 3 of this embodiment, two anolyte supplementary

liquid preparation tanks

271 and 272 are set to prepare the supplementary liquid of the anolyte solution in turn, and the two solid adding

devices

251 and 252 are respectively executed by the logic program control of the process system. The action of dropping the solid of ammonium carbonate into the anolyte supplementary

solution preparation tanks

271 and 272, and the action of dropping into ammonia water from the feeding

ports

314 and 315 respectively; wherein the part of the solvent in the anolyte supplementary

solution preparation tanks

271 and 272 is taken from the circulation The solution in the backflow transfer tank 70; then the supplementary solution of the anolyte prepared in turn is added to the circulating backflow transfer tank 70 according to the process requirements, and the anolyte and its anolyte are introduced in the circulating backflow transfer tank 70 simultaneously. The precipitated gases are mixed together for a chemical reaction to produce the pre-prepared anolyte. The regeneration etching sub-liquid described in step 4 has the same properties as the conventional preparation etching sub-liquid. It is based on the process specific gravity setting value of the etching working solution on the alkaline etching production line and the specific gravity value of the real-time detection result in the automatic detection and feeding controller. 120 for processing and dosing control to maintain the normal etching production of the alkaline etching production line.

During the electrolysis process, the

electrolytic anodes

square boxes

electrolytic anodes

square boxes

Example 11

As shown in FIG. 11 , the alkaline etching waste liquid regeneration and reuse device used in this embodiment includes anode area square boxes 11-14, cathode area 21, electrolytic separators 31-36, electrolytic anodes 41-44, and electrolytic cathodes 51- 53. Electrolysis power supply 61, circulating return transfer tank 70, cathode area top cover air extraction plate 91, anolyte precipitation gas drainage pipe 101, cathode area gas drainage pipe 111, automatic detection and feeding controller 120, detection devices 121-124, Catholyte overflow storage tank 141, temporary storage tank 142, liquid circulating flow agitator 151, impeller agitator 161, jet suction device 181, centrifugal fan

suction spray devices

191 and 192, solid-liquid separator 211, exhaust gas Absorption tank 231, equipment failure alarm 260, anolyte supplementary liquid preparation tank 271, overflow buffer tank 291, catholyte overflow buffer tank 292, pump 300-305, feeding port 314, exhaust gas discharge port 321-326 , valve 330 ~ 335, chlorine detector 380.

The electrolytic separators 31 to 36 are all cationic membranes, and the square boxes 11 to 14 in the anode area are in the form of square boxes made of non-conductive and water-impermeable materials and are respectively equipped with electrolytic anodes 41 to 44 and square boxes 11 to 14 in the anode area. Placed in the electrolysis reaction tank, the hexahedrons of the square boxes 11 to 14 in the anode area are opposite to the electrolytic cathode outside the box. , the area outside the square box in the electrolytic reaction tank is the cathode area 21; the square boxes 11 to 14 of the anode area and the electrolytic cathodes 51 to 53 are arranged at intervals from left to right, and are placed in the electrolytic reaction tank to form an anode area and a cathode. electrolysis reactor in the area.

The solutions in the square boxes 11 to 14 in the anode area are merged into the buffer tank 291 through the pipeline, and the overflow buffer tank 291 is connected with the circulating return transfer tank 70 through the valve 332 and the pump 302 pipeline to form a liquid flow channel, and the circulating return transfer The tank 70 is connected with the square boxes 11 to 14 of the anode area in the electrolysis reaction tank respectively by being provided with a pump 303, a valve 333 and a solid-liquid separation device 211 to form a backflow channel, so that the anolyte is in the square box of the anode area and the circulating return transfer tank. 70 for circulating liquid mixing. The circulating return transfer tank 70 is provided with a detection device 122, and is connected with a centrifugal fan-type suction and spray device 191; the top of the overflow buffer tank 291 is also provided with an anolyte precipitation gas drainage pipe 101, and the gas in the tank is passed through the centrifugal fan. The type suction spray device 191 is introduced into the solution of the circulating return transfer tank 70; wherein a chlorine gas detector 380 is installed in the pipeline of the anolyte precipitation gas drainage pipe 101, and the chlorine ion concentration in the anolyte is detected for safe production. Early warning, if the process setting value is exceeded, the equipment failure alarm 260 will issue an alarm prompt. The anolyte supplementary solution preparation tank 271 is used to provide carbon dioxide generating raw materials, and the solvent of the solution in it is extracted from the circulating return transfer tank 70 through the valve 331 and the pump 301, and the anolyte supplementary solution preparation tank 271 is provided with a detection device 121, an impeller The agitator 161, the feeding port 314, and the solid feeding device 251 are connected, wherein the solid feeding device 251 automatically detects the action command issued by the feeding controller 120 according to the process. The cathode area 21 is provided with a detection device 124 and a circulating liquid flow agitator 151, and the cathode area 21 is connected to the catholyte overflow buffer tank 292 through an overflow port. The catholyte overflow storage tank 141 is connected with the catholyte overflow buffer tank 292 through a pipeline provided with a valve 334 and a pump 304, and the catholyte overflow storage tank 141 temporarily stores the catholyte overflow. The temporary storage tank 142 stores the pre-prepared catholyte; the temporary storage tank 142 is connected with the cathode region 21 through a pipeline provided with a valve 335 and a pump 305 . The electrolysis cathode area 21 of the electrolytic cell is provided with a cathode area top cover plate air extraction hood 91, and the top of the cathode area top cover plate air extraction hood 91 is provided with a cathode area gas drainage pipe 111, and the gas separated from the cathode area is sucked through the jet flow Device 181 drains into anolyte make-up tank 271 solution. The tops of the circulating return transfer tank 70, the catholyte overflow storage tank 141, the temporary storage tank 142, the catholyte overflow buffer tank 292 and the anolyte supplementary liquid preparation tank 271 are respectively provided with a tail gas discharge port 321, a tail gas discharge port 322, The tail gas discharge port 323, the tail gas discharge port 324, the tail gas discharge port 325, and the tail gas discharge port 326 are respectively connected to the air inlet of the tail gas treatment system; the tail gas treatment system of the device in this embodiment is a centrifugal fan-type suction jet. The combination of the shower device 192 and the exhaust gas absorption liquid tank 231. The automatic detection and feeding controller 120 automatically controls the pump 300 and the valve 330 according to the process parameter results measured by the detection device 122 installed on the circulating return transfer tank 70, and prepares the well-prepared pre-mixture in the anolyte supplementary solution preparation tank 271. The anolyte is added to the circulating return transfer tank 70. The automatic detection and feeding controller 120 controls the feeding and feeding of the solid feeding and feeding 251 according to the detection result of the detection device 121 installed on the anolyte supplementary liquid preparation tank 271, and controls the pump 301 and the valve 331 from the circulating return transfer tank. The solution is drawn from 70 to the anolyte replenishing solution preparation tank 271 for preparation. The automatic detection and feeding controller 120 automatically adjusts the output current size or switch of the electrolysis power supply 61 according to the process parameter results measured by the detection device 124 of the cathode area 21, and/or according to the process-set copper ion concentration addition and feeding threshold control method Or automatically control the feeding pump 305 between the temporary storage tank 142 and the cathode area 21 to perform feeding action according to the time program. At the same time, the detection device 123 installed on the overflow buffer tank 291 can reflect various process data of the anolyte during the electrolysis process. When the value is set, it will alarm and/or stop immediately.

Use the device shown in Figure 11 to regenerate and reuse the alkaline etching waste liquid:

During the electrolysis process, the anolyte circulates between the square box in the anode area and the circulating return transfer tank, and the carbon dioxide generating raw materials and water are added to the circulating return transfer tank by external means. A mixed solution of alkaline etching waste liquid and water is added to the cathode area to maintain a certain copper ion concentration in the catholyte to maintain the electrolytic copper reaction on the electrolytic cathode. Wherein, the carbon dioxide generating raw material added and supplemented to the anolyte in this embodiment is ammonium formate.

The pre-prepared catholyte in this embodiment is a 8:1 mixture of alkaline etching waste liquid and water, wherein the pH value of the alkaline etching waste liquid is 10 and copper ions are 30 g/L.

During the electrolysis process, a plurality of electrolytic anodes are connected with the positive electrodes of the electrolytic power supply and placed in the solution of each electrolytic anode area square box of the electrolysis reaction tank to make the anolyte release carbon dioxide gas, and the multiple electrolytic cathodes are connected with the negative electrodes of the electrolytic power supply. It is placed in the solution in the cathode area of the electrolysis reaction tank and copper is continuously electro-deposited on a plurality of cathodes.

Table 1

The present invention may be summarized in other specific forms that do not depart from the spirit or main characteristics of the invention. The above-mentioned embodiments of the present invention can only be considered as an illustration rather than a limitation of the present invention. Therefore, any minor modifications, equivalent changes and modifications made to the above embodiments according to the essential technology of the present invention fall within the scope of the technical solutions of the present invention.

Claims

A method for regenerating and reusing alkaline etching waste liquid is characterized in that: using an electrolytic reaction tank, wherein an electrolytic separator is arranged in the electrolytic reaction tank to form an anode area and a cathode area, and the electrolytic separator can act on the force of an electric field. It can effectively reduce or even prevent the anions in the catholyte from migrating to the anode area; the anode area and the cathode area are respectively filled with anolyte and catholyte; the anolyte is an aqueous solution of carbon dioxide generating raw materials, or carbon dioxide generating An aqueous solution of raw materials and ammonia, the carbon dioxide generating raw material is a substance that generates carbon dioxide under electrolysis conditions or that generates carbon dioxide due to the rise in the temperature of the electrolyte during the electrolysis process; the catholyte is alkaline etching waste liquid, or it is mixed with water and/or a mixture of alkaline etching sub-liquid and/or regeneration etching sub-liquid;

The regeneration of the alkaline etching waste liquid is carried out by electrified electrolysis, and the carbon dioxide generating raw material is continuously or intermittently supplemented to the anolyte during the electrolysis process.
The method for regeneration and reuse of alkaline etching waste liquid according to claim 1, wherein the electrolytic separator is a cation exchange membrane and/or a bipolar membrane.
The method for regeneration and reuse of alkaline etching waste liquid according to claim 1, characterized in that: the purpose of separating out carbon dioxide gas from the anolyte in the electrolysis process is to charge the anolyte to generate carbon dioxide generating raw materials, participate in the preparation One or more of etching sub-liquid and generating additives therein, participating in the preparation of regenerating etching sub-liquid and generating additives therein, absorbing in etching sub-liquid, absorbing in regenerating etching sub-liquid, and absorbing in etching liquid on etching production line.
The method for regeneration and reuse of alkaline etching waste liquid according to claim 1, wherein the carbon dioxide generating raw materials are formic acid, sodium formate, potassium formate, ammonium formate, calcium formate, oxalic acid, potassium oxalate, potassium hydrogen oxalate, At least one of sodium oxalate, sodium bicarbonate, ammonium oxalate, carbonic acid, potassium carbonate, sodium carbonate, ammonium carbonate, potassium bicarbonate, sodium bicarbonate, and ammonium bicarbonate; the mass percentage of carbon dioxide generating raw materials in the anolyte The sum does not exceed 90%.
The method for regeneration and reuse of alkaline etching waste liquid according to claim 4, wherein the carbon dioxide generating raw materials in the anolyte are formic acid, ammonium formate, oxalic acid, ammonium oxalate, carbonic acid, ammonium carbonate, hydrogen carbonate at least one of ammonium.
The method for regeneration and reuse of alkaline etching waste liquid according to claim 5, wherein the carbon dioxide generating raw material in the anolyte is at least one of ammonium carbonate, ammonium bicarbonate and ammonium formate, and the The total mass percentage of carbon dioxide generating raw materials in the anolyte does not exceed 80%.
The method for regeneration and reuse of alkaline etching waste liquid according to claim 1, wherein the source of the ammonia is ammonia and/or ammonia water; the mass percentage of ammonia in the anolyte is not more than 28%.
The method for regeneration and reuse of alkaline etching waste liquid according to claim 7, wherein the mass percentage of ammonia in the anolyte is not more than 25%.
The method for regeneration and reuse of alkaline etching waste liquid according to claim 6, wherein the pH value of the anolyte is controlled to be equal to or greater than 5.
The method for regeneration and reuse of alkaline etching waste liquid according to claim 6, characterized in that: in the electrolysis process, the method for supplementing carbon dioxide generating raw materials to the anolyte is to directly add carbon dioxide generating raw materials to the anolyte, and/or Feed carbon dioxide gas into the anolyte to generate carbon dioxide through the reaction in the anolyte and generate raw materials; the carbon dioxide gas is the carbon dioxide gas separated from the anolyte in the electrolysis process, commercially available carbon dioxide gas products, carbonic acid thermal decomposition The carbon dioxide gas released, the carbon dioxide gas released by the thermal decomposition of carbonate, the carbon dioxide gas released by the thermal decomposition of bicarbonate, the carbon dioxide gas released by the thermal decomposition of oxalic acid, the carbon dioxide gas released by the thermal decomposition of oxalate Carbon dioxide gas, carbon dioxide gas released from the thermal decomposition of formic acid, carbon dioxide gas released from the thermal decomposition of formate, carbon dioxide gas released from the reaction of carbonate and inorganic acid, and carbon dioxide gas released from the reaction of bicarbonate and inorganic acid At least one of carbon dioxide gas.
The method for regeneration and reuse of alkaline etching waste liquid according to any one of claims 1-10, characterized in that: the catholyte after electrolysis is carried out in the electrolytic reaction tank, and each component is adjusted according to process requirements. After the ratio, it becomes a regeneration etching sub-liquid, and is added to the alkaline etching production line for use; the regeneration etching sub-liquid or its mixed solution with the etching sub-liquid is set according to the process of the etching working liquid on the alkaline etching production line After comparing the pH value or specific gravity value with the measured value, control the etching sub-liquid and add it to the alkaline etching production line.
The method for regeneration and reuse of alkaline etching waste liquid according to claim 6, characterized in that: for the gas separated from the anolyte in the electrolysis process, firstly adopt the anolyte and/or the overflow of the anolyte After the absorption, one or more of the overflowing liquid of the catholyte, the regeneration etching sub-liquid, and the etching liquid on the etching production line are used to absorb the remaining exhaust gas.
A device used for the regeneration and reuse method of alkaline etching waste liquid according to any one of claims 1-12, characterized in that it comprises an electrolytic reaction tank, an electrolytic separator, an electrolytic anode, an electrolytic cathode, an electrolytic power source and carbon dioxide. A raw material replenishing device; the electrolysis separator separates the electrolysis reaction tank into an anode area and a cathode area; in the electrolysis process, the electrolytic anode and the electrolytic cathode are respectively connected with the positive electrode and the negative electrode of the electrolysis power supply; the carbon dioxide generating raw material replenishing device is connected with The anode region is connected; the electrolytic separator is a material that can effectively prevent anions in the catholyte from migrating to the anode region under the force of an electric field.
The device used in the regeneration and reuse method of alkaline etching waste liquid according to claim 13, characterized in that: the electrolytic separator is at least one of a cation exchange membrane and a bipolar membrane; the carbon dioxide generating raw material is supplemented The device is an anode electrolysis replenishing liquid tank connected with a pump and a pipeline, a solid adding device, a top cover extraction hood connected with a gas drainage pipe, and a carbon dioxide gas connected with a gas drainage pipe arranged in the anode area and/or the cathode area. At least one of a gas cylinder and a carbon dioxide generating device connected with a gas drainage tube, used for supplementing the anolyte with carbon dioxide generating raw materials and/or anolyte adjustment solution rich in carbon dioxide generating raw materials and/or feeding carbon dioxide gas; The carbon dioxide generator is used for chemical reaction to produce carbon dioxide gas; the carbon dioxide gas generator can generate carbon dioxide gas through acid-base neutralization reaction or thermal decomposition reaction; when the thermal decomposition reaction is used to generate carbon dioxide gas, the carbon dioxide gas generator The carbon dioxide gas generating device is a heating reactor, which is specifically used to heat at least one of carbonic acid, carbonate, bicarbonate, oxalic acid, oxalate, formic acid, formate and the aqueous solution of the above-mentioned compound to decompose and release it. Carbon dioxide gas; the heating reaction kettle is provided with a feeding port, a gas outlet and a cold and hot temperature exchanger, and the gas outlet drains the gas escaping from the heating reaction kettle into the anolyte through a gas drainage pipe .
The device used in the method for regenerating and reusing alkaline etching waste liquid according to claim 14, characterized in that: an air pump, a jet air suction device, a centrifugal fan-type air pump are added to the gas drainage pipe connected to the carbon dioxide generating raw material supplement device At least one of the suction and spray devices makes the gas carry kinetic energy to penetrate into the liquid for chemical reaction.
The device used in the regeneration and reuse method of alkaline etching waste liquid according to claim 15, characterized in that: a circulating return transfer tank is added, and the circulating return transfer tank and the anode area pass through pipelines, valves and/or pumps connected to form a circulating flow pipe network, so that the solution between the two tanks can be circulated.
The device used in the regeneration and reuse method of alkaline etching waste liquid according to claim 16, characterized in that: an anolyte supplementary solution preparation tank is added for preparing an anolyte supplementary solution rich in carbon dioxide generating raw materials and/or ammonia The anolyte supplementary solution preparation tank is connected with one of the circulating reflux transfer tank and the anolyte supplementary solution tank through a pipeline provided with a pump, so that the anolyte supplementary solution is added to the described circulating backflow according to the process requirements. In the transfer tank or the anolyte supplementary liquid tank, it is more convenient to adjust and supplement the composition of the anolyte in the anode area of the electrolysis.
The device used in the method for regenerating and reusing alkaline etching waste liquid according to claim 17, characterized in that: at least one of the carbon dioxide generating raw material replenishing device and the circulating return transfer tank and the anolyte replenishing solution preparation tank This kind of connection is used to directly supplement the anolyte with carbon dioxide generating raw materials in the circulating return transfer tank, or prepare an anolyte adjustment solution rich in carbon dioxide generating raw materials in the anolyte supplementary solution preparation tank, so as to further improve the anolyte The anolyte in the zone is subject to constant composition control without interfering with the progress of the electrolysis reaction in the electrolytic anode zone.
The device used in the regeneration and reuse method of alkaline etching waste liquid according to claim 18, characterized in that: a catholyte overflow storage tank is added, and the catholyte overflow storage tank is connected to the cathode area; and at least one regeneration is added. Sub-liquid preparation tank, described regeneration sub-liquid preparation tank is connected with cathode area or catholyte overflow storage tank; described regeneration sub-liquid preparation tank is connected with regeneration sub-liquid storage tank through pipeline and pump; described anode area and/or Or the cathode area is provided with a top cover plate air hood, and the top of the top cover plate air hood is provided with a gas drainage pipe to drain the gas separated from the electrolyte in the anode area and/or the cathode area during the electrolysis process to the circulation. At least one of the backflow transfer tank, the anolyte supplementary liquid preparation tank, the catholyte overflow storage tank, the regeneration sub-liquid preparation tank, the regeneration sub-liquid storage tank and the etching production line; At the same place, the gas drainage pipes for draining the gas from the anode area and the cathode area should be separately arranged in the same reaction tank to avoid the carbon dioxide gas from the anode area and the ammonia gas from the cathode area being in the same gas drainage pipe. The mixing produces carbonate and/or bicarbonate solids that plug the pipes.
The device used in the regeneration and reuse method of alkaline etching waste liquid according to claim 19, wherein the anode area is an anode area square box, and the anode area square box is a box type with a vent hole structure, so that the electrolytic anode is fully immersed in the electrolyte during the electrolysis process, the square box of the anode area is placed in the electrolysis reaction tank, and the side wall adjacent to the square box of the anode area and the electrolytic cathode is provided with the electrolytic partition The electrolytic reaction tank is divided into an anode area and a cathode area; one or two or more of the anode area square boxes are arranged in the electrolytic reaction tank; the exhaust holes of the anode area square box pass through pipes Connect them to form a unified discharge pipeline, so that the gas precipitated in the entire anode area can be discharged smoothly.
The device used in the method for regenerating and reusing alkaline etching waste liquid according to claim 20, characterized in that: an ammonia gas generating device is added for replenishing the anolyte electrolyte and/or the anolyte and/or regenerating the etchant Liquid and/or etching solution provide ammonia gas; the ammonia gas generating device is a heating reactor, the top of which is connected to the anode area through a gas drainage tube, a circulating return transfer tank, an anolyte supplementary solution preparation tank, a catholyte overflow storage tank, At least one of the regenerated sub-liquid preparation tank, the regenerated sub-liquid storage tank and the etching production line are connected; an air pump, a jet suction device, and a centrifugal fan-type suction spray are added to the gas drainage pipe connected with the ammonia gas generating device. At least one of the devices enables the gas with kinetic energy to penetrate deep into the liquid for chemical reaction.