Gas-liquid mixing type electrochemical reaction device, and method for performing oxidation treatment on etching solution by using same

Abstract

Disclosed in the present invention is a gas-liquid mixing type electrochemical reaction device for performing oxidation treatment on an etching solution. The gas-liquid mixing type electrochemical reaction device comprises an electrolytic cell, which mainly consists of an electrolytic cell body, an electrolytic anode, an electrolytic cathode and an electrolytic power supply, wherein the electrolytic anode is connected to a positive electrode of the electrolytic power supply, and the electrolytic cathode is connected to a negative electrode of the electrolytic power supply, characterized in that the electrolytic cell comprises at least one electrolytic-cell gas-liquid mixer and an electrocatalytic component, which form a gas-liquid mixing type electrolytic cell; and an outlet of the electrolytic-cell gas-liquid mixer faces or is located in the electrolytic cell body for bringing a gas-liquid mixture, which is obtained after an electrolytic solution in the electrolytic cell is mixed with a reaction gas, into contact with the electrocatalytic component. Further disclosed in the present invention is a method for performing oxidation treatment on an etching solution by using the device.

Description

A gas-liquid mixed electrochemical reaction device and a method for oxidizing etching liquid thereof Technical Field

[0001] The invention belongs to the technical field of electrochemical reactions, and in particular relates to a gas-liquid mixed electrochemical reaction device and a method for oxidizing an etching solution thereof. Background Art

[0002] In the circuit board manufacturing industry, acidic copper chloride etching solutions or alkaline cupric ammonium chloride etching solutions are commonly used to etch circuit boards to create circuit patterns. The main components of acidic copper chloride etching solutions are hydrochloric acid and cupric chloride, with cupric chloride acting as a copper etching agent. To improve etching performance, chloride salts such as ferric chloride and ammonium chloride are commonly added to the acidic etching solution, and other etching additives may also be added. When the acidic copper chloride etching solution contains ferric chloride, the copper etching agents therein are cupric chloride and ferric chloride; the copper etching agents cupric chloride and ferric chloride react with copper to produce cuprous chloride and ferrous chloride, respectively. In order to maintain the continuous etching ability of the acidic etching solution, hydrochloric acid and an oxidizing agent need to be added to the acidic etching solution to oxidize and regenerate the cuprous chloride and ferric chloride in the acidic etching solution to produce cupric chloride and ferric chloride copper etching agents. Commonly used oxidizing agents include hydrogen peroxide and sodium chlorate. The specific chemical reactions that occur during the etching process of the acidic copper chloride etching solution are as follows:

[0003] Copper etching reaction of copper etching agent: CuCl2+Cu→2CuCl FeCl3+Cu→FeCl2+CuCl

[0004] Oxidation regeneration copper etching agent reaction: 2CuCl+2HCl+H2O2→2CuCl2+2H2O 6CuCl+6HCl+NaClO3→6CuCl2+NaCl+3H2O 6FeCl2+6HCl+NaClO3→6FeCl3+NaCl+3H2O

[0005] The main components of alkaline cuprammonium chloride etching solution are ammonia water, ammonium chloride, and cuprammonium chloride. It may also contain ammonium carbonate and other etching additives. The cuprammonium chloride (Cu(NH3)4Cl2) is the copper etchant. During the etching process, the copper etchant (Cu(NH3)4Cl2) reacts with copper to etch the circuit pattern, forming a monovalent copper-ammonium complex (Cu(NH3)2Cl), which loses its etching ability. To achieve continuous etching production, a spray mist is typically mixed with oxygen in the air during a spray process, allowing it to react with ammonium chloride, ammonium carbonate, and ammonia water to oxidize and regenerate the copper etchant. The specific chemical reactions that occur in the alkaline cuprammonium chloride etching solution during the etching process are as follows:

[0006] Copper etching reaction between copper etching agent and copper: Cu(NH3)4Cl2+Cu→2Cu(NH3)2Cl

[0007] Oxidation regeneration copper etching agent reaction:

[0008] The existing alkaline etching solution oxidation regeneration process uses oxygen in the air as an oxidant during the spraying process, so the chemical reaction efficiency of the regenerated copper etching agent is low and cannot meet the production efficiency requirements when etching thick copper plates.

[0009] In the industry, the etching liquid in the etching machine is called etching working liquid, the solution added to the etching machine as raw material replenishment during the etching process is called etching sub-liquid, and the etching liquid overflowing from the etching machine is called etching waste liquid.

[0010] As can be seen from the above, the oxidation and regeneration reaction step of the copper etching agent in the etching solution is a very important step for continuous etching processing, which directly affects the production efficiency and etching quality of the etching process. For acidic copper chloride etching solution, the copper etching agent is subjected to oxidation and regeneration reaction by adding hydrogen peroxide and / or sodium chlorate solution as oxidants. Although the speed of generating the copper etching agent in this way can meet the production process requirements, because liquid oxidants are added, and a large amount of hydrochloric acid needs to be added to the etching solution to maintain the acidity of the etching solution during the etching process, the copper ion concentration in the acidic copper chloride etching working solution is difficult to further increase to improve the etching quality, and it will also lead to the production of more acidic copper chloride etching waste liquid. For acidic copper chloride etching waste liquid, the existing technology uses the oxalic acid method to extract copper and recycle it. The oxalic acid method specifically mixes oxalic acid with the acidic copper chloride etching waste liquid to generate a copper salt precipitate, and returns the filtrate whose main component is hydrochloric acid to be used in the etching production. However, the large amount of etching waste liquid generated by the use of liquid oxidants has caused an imbalance in the recycling of the oxalic acid method. That is, the hydrochloric acid filtrate obtained after copper extraction after solid-liquid separation cannot be fully recycled due to its excessive volume, making it difficult to promote the oxalic acid method.

[0011] The process problems that exist respectively in the oxidation and regeneration process for above-mentioned existing acidic copper chloride etching solution and alkaline copper chloride ammonia etching solution can be solved by electrochemical oxidation method. Electrochemical oxidation method can accelerate the regeneration of the etching copper agent in the alkaline copper chloride ammonia etching solution, and reduce or even completely exempt the liquid oxidant in the oxidation and regeneration reaction of acidic copper chloride etching solution, so that etching process is improved. However, if the electrolytic cell of prior art is adopted, copper is electrolyzed by its electrolytic cathode and oxidized and regenerated by its electrolytic anode to obtain the etching copper agent, its equipment investment is quite large, and the maintenance cost is high. Therefore, it is necessary to optimize the electrochemical oxidation scheme to overcome the equipment investment problem.

[0012] Summary of the Invention

[0013] The first object of the present invention is to provide a gas-liquid hybrid electrochemical reaction device for oxidizing etching solutions. This device utilizes a gas-liquid hybrid electrolytic cell to improve the gas solubility and mass transfer properties of the reactants. The electrocatalytic action of the device can be used to oxidize and regenerate copper-corroding agents in the etching solution and / or waste etching solution. A second object is to provide a method for oxidizing etching solutions using the aforementioned gas-liquid hybrid electrochemical reaction device.

[0014] The first object of the present invention is achieved through the following technical solutions.

[0015] A gas-liquid mixing electrochemical reaction device for oxidizing an etching solution, comprising an electrolytic cell mainly composed of an electrolytic cell body, an electrolytic anode, an electrolytic cathode, and an electrolytic power supply, wherein the electrolytic anode is connected to the positive electrode of the electrolytic power supply, and the electrolytic cathode is connected to the negative electrode of the electrolytic power supply; the electrolytic cell is characterized in that it includes at least one electrolytic cell gas-liquid mixer and an electrocatalytic component, forming a gas-liquid mixing electrolytic cell; the outlet of the electrolytic cell gas-liquid mixer is oriented toward or located in the electrolytic cell body, and is used to bring the gas-liquid mixture obtained by mixing the electrolyte in the electrolytic cell with the reaction gas into contact with the electrocatalytic component; the electrocatalytic component adopts any one or more of the following methods:

[0016] Electrocatalytic method (1): at least one electrocatalytic component is provided in the electrolytic cell body, and the outlet of the electrolytic cell gas-liquid mixer faces the electrocatalytic component and / or the electrolytic cathode;

[0017] Electrocatalytic method (2): Improve the electrocatalytic performance structure of the electrolytic cathode, or improve the electrocatalytic performance structure of both the electrolytic anode and the electrolytic cathode; that is, the electrolytic cathode or the electrolytic anode and the electrolytic cathode are two or more parallel-connected electrodes, and the outlet of the electrolytic tank gas-liquid mixer faces the electrolytic cathode with improved electrocatalytic performance structure or the electrolytic anode and the electrolytic cathode with improved electrocatalytic performance structure;

[0018] Electrocatalytic method (3): The electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode is improved, and the angle ɑ formed by a part or the whole of at least one of the electrolytic anode and the electrolytic cathode and the straight line of the gas-liquid mixture ejected from the outlet of the electrolytic tank gas-liquid mixer is greater than 0° and less than 90°, and the outlet of the electrolytic tank gas-liquid mixer is oriented toward the electrolytic cathode with improved electrocatalytic performance structure or toward the electrolytic anode and electrolytic cathode with improved electrocatalytic performance structure.

[0019] The electrolytic cell gas-liquid mixer described in the present invention has an inlet and at least two outlets, or has a structure with a liquid inlet, an air inlet and an outlet. When the electrolytic cell gas-liquid mixer has an inlet and at least two outlets, the outlet extends into the electrolytic cell body and is used to dispersely input the reaction gas or gas-liquid mixture into the electrolyte in the electrolytic cell for gas-liquid mixing; when the electrolytic cell gas-liquid mixer has a liquid inlet, an air inlet and an outlet, the liquid inlet is connected to the electrolytic cell body by a pipeline, and the outlet is directed toward or extends into the electrolytic cell body, and is used to input the electrolyte in the electrolytic cell into the gas-liquid mixer so that it is mixed with the reaction gas entering the gas-liquid mixer and then returned to the electrolytic cell.

[0020] The electrocatalytic components in the electrocatalytic method (1) of the present invention are arranged in the electrolytic cell body and below the electrolyte liquid level, and are used to achieve electrochemical catalytic reaction capability under the action of electric field force. Specifically, the electrocatalytic components are bipolar electrodes and / or insoluble conductors, and the specific number and location of the electrocatalytic components can be determined according to the performance of the process setting.

[0021] The bipolar electrode described in the present invention refers to an insoluble conductor that is disposed between the electrolysis anode and the electrolysis cathode, is not connected to an external power source, and is immersed in the electrolyte. Its shape and size are not limited. During electrolysis, the bipolar electrode is placed in an electric field to undergo an electrochemical reaction with the substance in that position, without the need for direct electrical connection to the electrolysis power source. The end closest to the electrolysis anode acts as a cathode, causing some of the reducible substances in the electrolyte to undergo a reduction reaction, while the end closest to the electrolysis cathode acts as an anode, causing some of the oxidizable substances in the electrolyte to undergo an oxidation reaction. When multiple bipolar electrodes are used, each bipolar electrode is ideally an independent conductor and is not electrically connected to each other. Under the action of the electric field, each bipolar electrode can independently perform its respective function, forming multiple inductive small cathodes and small anodes to enhance the electrocatalytic effect.

[0022] Preferably, as shown in FIG4 , when more than one bipolar electrode is used, the surface portion of the middle portion of the conductor of the bipolar electrode is wrapped with an insulating material to reduce the risk of the bipolar electrodes becoming one large bipolar electrode due to conduction when in contact with each other, thereby reducing the risk of each small bipolar electrode losing its ability to independently perform its electrode catalytic function.

[0023] The insoluble conductor described herein is directly conductively connected to an electrolytic anode or cathode, transforming the anode or cathode into an irregularly shaped electrode. This increases the electrode surface area and promotes the electrochemical reaction between the electrode and the electrolyte, thereby achieving electrocatalysis. The insoluble conductor connected to the electrolytic anode is referred to as an insoluble anode conductor, while the insoluble conductor connected to the electrolytic cathode is referred to as an insoluble cathode conductor.

[0024] The present invention utilizes the characteristics of insoluble conductors to achieve a highly efficient electrocatalytic electrochemical reaction by mixing the reactant gas introduced by the electrolytic cell's gas-liquid mixer with the electrolyte and then spraying it onto the corresponding electrodes and insoluble conductors. As shown in Figure 5, the insoluble conductor is insoluble or poorly soluble in the electrolyte it contacts, and its shape and size are not limited. Preferably, the insoluble conductor is in the form of conductive coils or conductive fragments to increase the surface area of ​​the electrodes modified by the insoluble conductor.

[0025] The present invention uses a gas-liquid hybrid electrochemical reaction device for oxidative regeneration of an acidic copper chloride etching solution or an alkaline copper chloride ammonia etching solution. Therefore, the gas involved in the reaction is an external oxidizing gas, specifically at least one selected from oxygen, air, chlorine, and ozone. Preferably, oxygen is used as the gas involved in the reaction.

[0026] The working principle of the present invention is to use the electrolytic cell gas-liquid mixer to mix the gases involved in the reaction into the electrolyte and contact the resulting gas-liquid mixture with the electrocatalytic components and / or electrolytic cathode in the gas-liquid mixing electrolytic cell, so that the gas-liquid mixture containing the oxidizing gas contacts and reacts with the negatively charged components in the gas-liquid mixing electrolytic cell; the presence of sufficient oxidizing gas in the gas-liquid mixture promotes electrochemical reactions on the negatively charged components, and the resulting electron gain and loss catalyzes active electrochemical reactions on the positively charged components, while preventing the substances in the electrolyte to be treated from repeatedly reacting on the two charge components, causing consumption and reducing efficiency. Compared with liquid oxidants, mixing oxidizing gases with the electrolyte can better produce catalytic effects on electrochemical reactions, is less expensive, and does not increase the amount of electrolyte. During electrolysis, the negatively charged components of the gas-liquid hybrid electrolytic cell are the electrolysis cathode, the end of the bipolar electrode that functions as the cathode, and at least one of the insoluble cathode conductor. The positively charged components are the electrolysis anode, the end of the bipolar electrode that functions as the anode, and at least one of the insoluble anode conductor. That is, to achieve an electrocatalytic effect, during the electrolysis process, the present invention utilizes an oxidizing gas to conduct an electrochemical reaction in the negatively charged components, thereby creating a gas seal. This ensures that the reducing substances to be treated are electrochemically oxidized by the positively charged components and are not reduced by the negatively charged components. During the electrolysis process, components with positive charge play the role of converting electrical energy into chemical energy, oxidizing reducing substances in the electrolyte under electrocatalysis, and also oxidizing oxygen, hydroxide ions, chloride ions, etc. in the electrolyte to produce a large number of superoxide radicals (O2·), hydroxyl radicals (OH·) and / or chlorine radicals (Cl·), chloroxyl radicals (ClO·) and other oxidizing free radicals, so that the substances in the electrolyte that need to be oxidized are quickly oxidized, and the oxidation regeneration of the copper etching agent in the electrolyte is carried out efficiently. When the gas-liquid mixture containing oxidizing gas is sprayed onto the components with negative charge in the electrolysis process, taking the supply of sufficient oxygen as an example, the main electrochemical reaction that occurs is: O2+4H + +4e - →H2O and / or O2+2H2O+4e - →4OH - .

[0027] The present invention utilizes externally input gas as the source of the gas participating in the reaction. The externally input oxidizing gas originates from outside the gas-liquid hybrid electrolytic cell. Specifically, the gas inlet of the gas-liquid mixer of the electrolytic cell is connected to a gas source outside the gas-liquid hybrid electrolytic cell. The gas participating in the reaction is introduced, mixed with the electrolyte within the electrolytic cell, and then sprayed onto the electrolytic electrodes and / or electrocatalytic components within the electrolytic cell to perform an electrochemical reaction. The electrolytic power supply of the gas-liquid hybrid electrolytic cell applies a voltage between the electrolytic anode and the electrolytic cathode equal to or lower than the decomposition voltage of the electrolyte to perform the electrolysis operation.

[0028] The electrolyte decomposition voltage value, taking etching liquid as an example, is the voltage value at the critical point where the voltage applied by the electrolytic power supply between the electrolytic anode and the electrolytic cathode in the electrolytic cell under static conditions just causes the electrolytic anode to electrolyze a very small amount of oxidizing gas into the electrolyte, or the electrolytic cathode to electrolyze a very small amount of metallic copper into the electrolyte. However, in actual measurements, since the measured liquid is etching liquid, if the trace metallic copper electrolyzed at the cathode is quickly corroded and dissolved by the etching liquid, it will be difficult to observe with the naked eye. Therefore, the oxidizing gas electrolyzed at the anode end is used to determine the electrolyte decomposition voltage value. The electrolyte decomposition voltage value is related to many factors, such as the chemical properties of the electrolyte, electrolyte concentration, viscosity, temperature, the amount of gas involved in the reaction, the distance between the cathode and the cathode, and the materials selected for the cathode and the cathode.

[0029] In order to prevent electrolytic gas from being deposited on the electrolytic anode and / or electrolytic cathode of the gas-liquid hybrid electrolytic cell, the voltage value applied by the electrolytic power supply between the electrolytic anode and the electrolytic cathode during operation is required to be less than or equal to the electrolyte decomposition voltage value. However, in the present invention, when there is sufficient oxidizing gas to participate in the electrochemical reaction at the negatively charged component, making it difficult for the positively charged component to be sealed by the oxidizing gas to electrolyze copper metal, the voltage value applied by the electrolytic power supply between the electrolytic anode and the electrolytic cathode of the gas-liquid hybrid electrolytic cell can be slightly higher than the electrolyte decomposition voltage value. When the voltage value applied by the electrolytic power supply between the electrolytic anode and the electrolytic cathode is adjusted to be higher, the reducibility of the electrolytic cathode or the oxidizing property of the electrolytic anode will become stronger under the above conditions. Therefore, under the safety of the electrolytic cell reaction, the voltage value applied by the electrolytic power supply between the electrolytic anode and the electrolytic cathode can be set to be higher than the electrolyte decomposition voltage value to increase the electrochemical reaction speed.

[0030] The material of the electrolytic cell body in contact with the electrolyte is selected from a polymer resin material, or other materials coated with an insulating anti-corrosion coating or lined with an insulating anti-corrosion material. Preferably, when the electrolyte temperature is high, the material of the electrolytic cell body is selected from polytetrafluoroethylene.

[0031] The surface of the electrolytic anode is selected from at least one material selected from the group consisting of gold, platinum, a gold-platinum alloy, a titanium-based coated insoluble anode, and graphite. The shape and size of the electrolytic anode are not limited. The surface of the electrolytic cathode is selected from at least one material selected from the group consisting of gold, platinum, titanium, copper, an alloy containing at least one of the above metals, and graphite. The shape and size of the electrolytic cathode are not limited.

[0032] The surface material of the bipolar electrode is at least one of gold, platinum, gold-platinum alloy, and conductive graphite.

[0033] When the insoluble conductor contacts the electrolytic anode, it becomes the insoluble anode conductor, and its surface is made of at least one material selected from the group consisting of gold, platinum, a gold-platinum alloy, a titanium-coated insoluble anode, and graphite. Preferably, the material of the insoluble anode conductor is the same as that of the electrolytic anode. When the insoluble conductor contacts the electrolytic cathode, it becomes the insoluble cathode conductor, and its surface is made of at least one material selected from the group consisting of gold, platinum, titanium, copper, alloys of these metals, and graphite. Preferably, the surface of the insoluble cathode conductor is made of titanium and / or copper.

[0034] The gas-liquid mixture outlet of the electrolytic cell gas-liquid mixer can be designed with the number and shape of nozzles according to the spraying object, so that the gas-liquid mixture ejected from the outlet can effectively and fully contact at least one of the electrocatalytic component and the electrolytic cathode to achieve a better electrocatalytic effect. The electrolytic cell gas-liquid mixer can adopt a bubbling electrolytic cell gas-liquid mixer and / or a vacuum jet electrolytic cell gas-liquid mixer. From the perspective of safe production and gas-liquid mixing effect, it is preferred to adopt a vacuum jet electrolytic cell gas-liquid mixer, or an electrolytic cell gas-liquid mixer that is a combination of a bubbling type and a vacuum jet type as shown in Figure 1 9. The material of the surface of the electrolytic cell gas-liquid mixer that contacts the electrolyte is selected from at least one of titanium, gold, platinum, conductive graphite, fiberglass, and polymer resin materials, and is specifically selected according to the chemical properties of the electrolyte and the gas participating in the reaction.

[0035] The gas-liquid mixed electrolytic tank is connected to one or more tanks in the etching machine and / or etching system through a pipeline.

[0036] The present invention can be improved as follows: the electrolytic cell gas-liquid mixer is electrically connected to at least one of the negative electrode of the electrolysis power supply, the electrolysis cathode, and the connecting conductive wire between the electrolysis power supply and the electrolysis cathode using a conductive connecting wire, and its liquid outlet is directly inserted into the electrolyte, making it an insoluble cathode conductor, serving as an electrocatalytic component to improve catalytic efficiency. This is specifically shown as number 37 in Figure 1.

[0037] The present invention can also be improved as follows: a sealing tank cover with at least one gas outlet is added to the gas-liquid mixing electrolytic cell to seal the electrolytic cell with a hole. The gas outlet of the sealing tank cover is connected to the gas inlet of at least one electrolytic cell gas-liquid mixer and / or other common gas-liquid mixer, or is connected to the atmosphere, so that the gas in the sealed tank area is guided through the sealing cover outlet pipe to the electrolytic cell gas-liquid mixer and / or other exhaust gas treatment device and / or a device for recycling the gas, or is directly discharged through the sealing cover outlet.

[0038] The present invention can also be improved as follows: an adjustable constant voltage electrolysis power supply is used as the electrolysis power supply of the gas-liquid hybrid electrolytic cell to ensure a stable output voltage to meet production safety requirements.

[0039] The present invention can also be improved as follows: the gas-liquid hybrid electrolytic cell adopts a symmetrical three-divided cell zone structure to improve electrical efficiency. Specifically, two electrolytic electrodes of the same polarity are symmetrically arranged in the electrolytic cell body with the electrolytic electrode of the other polarity as the center; as shown in Figure 2, an electrolytic cell adopts an electrolytic anode combination symmetrically with the electrolytic cathode as the center.

[0040] The present invention can also be improved as follows: the aforementioned gas-liquid hybrid electrolytic cell utilizes a circular electrode distribution structure to enhance the efficiency of the electrochemical reaction. Specifically, the gas-liquid hybrid electrolytic cell utilizes a circular or polygonal electrolytic cell body, with an electrolysis anode or electrolysis cathode positioned at the center of the cell body as the central electrode. One or more corresponding electrodes of another type are positioned around the central electrode. The electrolytic cell body 1 shown in FIG3 utilizes a circular electrode distribution structure, wherein the anolyte and catholyte are the same electrolyte. The peripheral electrodes outside the center of the cell body are separated by insulating partitions and connected to their own electrolysis power sources, respectively, using the central electrode. This creates a plurality of independent electrolysis units within the shared central electrode and electrolyte. Each electrolysis unit comprises an electrolysis power source, an electrolysis anode, an electrolysis cathode, an electrocatalytic component, and / or at least one electrolysis electrode with improved electrocatalytic performance. Preferably, the central electrode of the gas-liquid hybrid electrolytic cell with a circular electrode distribution structure serves as the electrolysis anode, allowing the multiple electrolysis cathodes to fully utilize the oxidizing gas for a closed electrochemical reaction.

[0041] The present invention can also be improved as follows: an electrolyte ion current interrupter is added to cut off the path of the ion flow in the electrolyte that does not flow through the electrolytic anode and electrolytic cathode during the electrolysis operation, thereby avoiding the formation of a closed loop circuit with the electrolytic power supply and the loss of useless work. In addition, the use of the electrolyte ion current interrupter can electrically separate the electrolytic cell from other equipment, avoiding safety issues in electricity use. There are two methods for setting up the electrolyte ion current interrupter: the first is as shown in Figure 7, a tank equipped with a multi-hole drip-type baffle or a pipe with an increased cross-sectional area equipped with a multi-hole drip-type baffle is used as the electrolyte ion current interrupter, and the electrolyte continuously flowing in the pipe is diverted thereto, thereby cutting off the path of the ion flow in the electrolyte in a drip-type flow manner; the second is as shown in Figure 8, adding at least two ion current interrupter temporary storage tanks as electrolyte ion current interrupters, which are used in a rotating manner to interrupt the ion flow in the electrolyte. Among them, the second method is to install a liquid level meter in the ion flow interruption temporary storage tank to control the pump of each current interruption temporary storage tank, so that the electrolyte in the tank is pumped into the gas-liquid mixed electrochemical reaction device in rotation for chemical reaction between the ion flow interruption temporary storage tanks; the ion flow interruption temporary storage tank that rotates to pump the electrolyte in the tank into the electrolytic tank does not receive the solution overflowing from the electrolytic tank through the control valve, and the overflow liquid of the gas-liquid mixed electrochemical reaction device is drained to another ion flow interruption temporary storage tank for temporary storage, and the electrolyte is pumped into the gas-liquid mixed electrochemical reaction device in rotation by two or more tanks to realize the short-circuit channel of cutting off the ion flow.

[0042] The present invention can also be improved by adopting a vertical structure for the gas-liquid hybrid electrolytic cell, thereby increasing the height of the electrolytic cell. Since the present invention utilizes a gas-liquid hybrid reaction, and the gas moves vertically upward in the electrolyte, increasing the height of the electrolytic cell helps improve reaction efficiency and reduce waste caused by unreacted gas escaping from the gas-liquid hybrid electrolytic cell.

[0043] The present invention can also be improved by adding an ultrasonic generator to the electrolytic cell body and / or the electrolytic cell gas-liquid mixer. This utilizes the ultrasonic cavitation effect to fully disperse and dissolve bubbles in the electrolyte into the solution, thereby improving the efficiency of the oxidation or reduction reaction. Preferably, the ultrasonic generator is installed on the liquid flow pipe of the electrolytic cell gas-liquid mixer. This simple installation structure provides better gas-liquid mixing.

[0044] The present invention can also be improved as follows: two or more gas-liquid mixed electrolyzers are provided and connected to form a combination of two-stage or multi-stage gas-liquid mixed electrolyzers connected in series with gas pipelines, that is, the gas-liquid mixed electrochemical reaction devices of the front and rear stages are connected through gas pipelines, and the reaction gas escaping from the reaction process of the front-stage gas-liquid mixed electrolyzer is collected and drained to the rear-stage gas-liquid mixed electrolyzer for use as a reaction gas raw material, which reduces production costs and reduces pollution.

[0045] The present invention can also be improved as follows: the oxidizing tail gas discharged after the reaction of the gas-liquid mixed electrolytic cell is directly discharged into the spray space of the etching machine through a pipeline, so that the etching working liquid is fully utilized during the absorption in the spray atomization, while reducing the waste gas treatment equipment.

[0046] The present invention can also be improved by adding an insulated bipolar electrode cage or isolation mesh frame. Specifically, during use, multiple bipolar electrodes are separated and fixed in sections using an insoluble insulated bipolar electrode cage or isolation mesh frame. This prevents the bipolar electrodes immersed between the electrolytic anode and the electrolytic cathode from displacement under the impact of the liquid flow and allows them to perform their electrocatalytic function normally. The bipolar electrode cage is shown as 10 in Figure 9 and is made of an insulating through-hole rubber mesh or porous mesh.

[0047] The present invention can also be improved as follows: a chemical reaction tank is added to the device to guide the oxidizing tail gas generated in the device through a pipeline into the chemical reaction tank to react with the stored etching solution, thereby reducing environmental pollution.

[0048] The present invention can also be improved as follows: a temporary storage tank is added to the device for temporarily storing materials, and the temporary storage tank is connected to at least one other tank in the device for liquid flow through a pipeline.

[0049] The present invention can also be improved as follows: an overflow buffer tank is added to the device, which is connected to at least one tank in the device of the present invention to solve the problem of liquid flow between tanks.

[0050] The present invention can also be improved by adding a hot / cold temperature exchanger to the apparatus, disposed in at least one of the gas-liquid hybrid electrolytic cell, the temporary storage tank, and the electrolyte current cutoff tank. The hot / cold temperature exchanger is used to control the temperature of the reaction solution and adjust the temperature of the temporary storage solution, ensuring that the temperature of each solution meets process requirements, thereby achieving safe production and improving reaction efficiency.

[0051] The present invention can also be improved as follows: an automatic detection and feeding controller and a sensor are added to the device, the detection signal output end of the sensor is connected to the detection signal input end of the automatic detection and feeding controller, and the control signal output end of the automatic detection and feeding controller is connected to the control signal input ends of the electrolysis power supply, valves, pumps, ultrasonic generators, hot and cold temperature exchangers, etc. in the device, so that the device performs sampling data processing according to a pre-programmed program during the production process and controls the addition of chemicals during the reaction process so that the reaction liquid meets the process reaction requirements and operates automatically and safely according to the pre-programmed program. The sensor is selected from an oxidation-reduction potentiometer (ORP meter), a pH meter, a liquid level gauge, an acidity meter, a hydrometer, a thermometer, and a chlorine concentration detection alarm, which is installed in at least one of the gas-liquid hybrid electrolytic cell, the temporary storage tank, the overflow buffer tank, the electrolyte ion flow cell, and the production workshop.

[0052] The present invention can also be improved as follows: an air pressure balancing connecting pipe is added between two or more gas-liquid hybrid electrolytic cells, and / or an air pressure balancing connecting pipe is added between the tank areas within the gas-liquid hybrid electrolytic cell, as shown by number 43 in Figure 14, and at least one exhaust port in the gas-liquid hybrid electrolytic cell is directly or indirectly connected to the air duct to achieve balance with the atmospheric pressure; thereby, according to process requirements, the air pressure between the electrolytic cells in two or more gas-liquid hybrid electrolytic cells is balanced, or the pressure in each tank area of ​​the electrolytic cell with filter cloth is balanced through the connection of the air pressure balancing pipe.

[0053] The present invention can also be improved by adding a bubble-containing reaction liquid flow deflector to the gas-liquid hybrid electrolytic cell, with the direction and position of its liquid suction port determined according to the gas-liquid hybrid electrolytic cell design process. Preferably, the bubble-containing reaction liquid flow deflector is located behind the negatively charged component determined by the flow direction of the electrolyte, connected to a liquid flow pump tube agitator, and pumps the unused oxidizing gas back to the first negatively charged electrolytic electrode in a circulating flow form to re-engage the electrochemical reaction. This is shown as number 52 in Figure 13.

[0054] The present invention can also be improved as follows: an environmentally friendly tail gas treatment tank is added to the device, and the tanks escaping tail gas in the device are connected through pipelines to guide the tail gas to the environmentally friendly tail gas treatment tank for environmental treatment.

[0055] The present invention can also be implemented in the following way: an electrolytic cathode filtration device is added, specifically, at least one of a filter bag, a filter screen, and a filter cloth is provided to separate the electrolytic cathode or the electrolytic cathode and the electrolyte electrolytic anode of an insoluble cathode conductor, and the insoluble anode conductor, so as to intercept the copper particles electrolyzed by the electrolytic cathode.

[0056] The present invention can also be improved as follows: under the condition of adding a filter bag as the electrolytic cathode filter device, the gas-liquid mixture is sprayed into the electrolytic cathode filter device to ensure that the oxidizing gas participating in the reaction can undergo a closed electrochemical reduction reaction with the electronegative electrode, thereby avoiding the electrolytic deposition of metallic copper from the electronegative electrode.

[0057] The present invention can also be improved as follows: an auxiliary electrolytic cell is added and separated into an anode cell area and a cathode cell area using an electrolytic cell divider. The anode cell area is used for electrochemical oxidation etching solution, and the cathode cell area is used to produce a solution containing more cuprous chloride or more cuprous chloride and ferrous chloride than the acidic copper chloride etching waste liquid. Preferably, the cathode cell area of ​​the auxiliary electrolytic cell is connected to the gas-liquid hybrid electrolytic cell via a pipeline; when the cathode electrolyte of the auxiliary electrolytic cell is used as the electrolyte of the gas-liquid hybrid electrolytic cell, its electrochemical oxidation efficiency is higher. By combining the work of the auxiliary electrolytic cell with the gas-liquid hybrid electrolytic cell, the oxidation regeneration efficiency of the copper etching agent in the acidic etching working solution is accelerated, and the etching efficiency and quality are improved.

[0058] The present invention can also be improved as follows: an etching liquid mixing exchange tank is added to store oxidized etching liquid for use in the etching machine. The etching liquid mixing exchange tank circulates and exchanges liquid flow with the etching machine, the gas-liquid mixing electrolytic tank, and / or the auxiliary electrolytic tank, and is further connected to at least one of the solid-liquid separator, the liquid flow buffer tank, the temporary storage tank, the waste gas environmental treatment tank, the etching machine, and the chemical reaction tank by a pipeline, and / or is further connected to at least one of another auxiliary electrolytic tank and the gas-liquid mixing electrolytic tank in a one-way manner.

[0059] The present invention can also be improved as follows: a solid-liquid separator is added to separate the etching liquid into solid and liquid to remove solid impurities, and the solid-liquid separator is connected to at least one of the etching machine, the etching liquid mixing exchange tank, the auxiliary electrolytic tank, the gas-liquid mixed electrolytic tank, the temporary storage tank, and the chemical reaction tank through pipelines.

[0060] The second object of the present invention is achieved through the following technical solutions.

[0061] A method for oxidizing an etching solution using the gas-liquid hybrid electrochemical reaction device comprises the following steps:

[0062] (1) using the gas-liquid mixed electrochemical reaction device in combination with an etching machine during an etching production process to oxidize an etching liquid, wherein the etching liquid is an etching working liquid and / or etching waste liquid; using the etching working liquid and / or etching waste liquid as the electrolyte of a gas-liquid mixed electrolytic cell in the gas-liquid mixed electrochemical reaction device, connecting an electrolysis power supply, and performing an electrochemical oxidation reaction;

[0063] (2) starting at least one electrolytic cell gas-liquid mixer in the gas-liquid mixing electrochemical reaction device, mixing the oxidizing gas with the electrolyte to form a gas-liquid mixture, and contacting the mixture with at least one of the electrolytic cathode and the electrocatalytic component, and utilizing the electrolytic electrode and / or the electrocatalytic component with an improved electrocatalytic structure to exert an electrocatalytic effect on the substances to be treated in the etching working solution and / or the etching waste liquid to regenerate the copper etching agent.

[0064] When electricity is applied for electrolysis, the gas-liquid mixture containing the oxidizing gas is brought into contact with the negatively charged electrode in the gas-liquid hybrid electrolytic cell, causing the oxidizing gas to undergo an electrochemical reaction. The etching working liquid and / or etching waste liquid are brought into contact with the positively charged electrode in the gas-liquid hybrid electrolytic cell to undergo an electrochemical oxidation reaction, while effectively preventing the electrolytic deposition of metallic copper on the electrolytic cathode, the cathode end of the bipolar electrode, and the insoluble cathode conductor.

[0065] The present invention adopts externally input oxidizing gas as the gas source participating in the reaction, and the externally input oxidizing gas comes from the outside of the gas-liquid hybrid electrolytic cell; wherein, the electrolysis power supply of the gas-liquid hybrid electrolytic cell applies a voltage value equal to or lower than the electrolyte decomposition voltage between the electrolysis anode and the electrolysis cathode to perform electrolysis operation.

[0066] In order to prevent electrolytic gas from being deposited on the electrolytic anode and / or electrolytic cathode of the gas-liquid hybrid electrolytic cell, the voltage value applied by the electrolytic power supply between the electrolytic anode and the electrolytic cathode during operation is required to be less than or equal to the electrolyte decomposition voltage value. However, in the present invention, when there is sufficient oxidizing gas to participate in the electrochemical reaction at the negatively charged component, making it difficult for the positively charged component to be sealed by the oxidizing gas to electrolyze copper metal, the voltage value applied by the electrolytic power supply between the electrolytic anode and the electrolytic cathode of the gas-liquid hybrid electrolytic cell can be slightly higher than the electrolyte decomposition voltage value. When the voltage value applied by the electrolytic power supply between the electrolytic anode and the electrolytic cathode is adjusted to be higher, the reducibility of the electrolytic cathode or the oxidizing property of the electrolytic anode will become stronger under the above conditions. Therefore, under the safety of the electrolytic cell reaction, the voltage value applied by the electrolytic power supply between the electrolytic anode and the electrolytic cathode can be set to be higher than the electrolyte decomposition voltage value to increase the electrochemical reaction speed.

[0067] In step (1), the gas-liquid hybrid electrolytic cell used in the present invention is a separator-free electrolytic cell body selected according to the process design, and an electrolytic power supply is used to apply a voltage of the electrolyte decomposition voltage or a value lower than the value to the electrolytic anode and the electrolytic cathode to carry out the electrochemical reaction. When the external oxidizing gas input is sufficient to offset the reducing substances electrolyzed from the electrolytic cathode, the bipolar electrode cathode end, and the insoluble cathode conductor, the electrolytic power supply can be used to apply a voltage slightly higher than the electrolyte decomposition voltage between the electrolytic anode and the electrolytic cathode to improve the efficiency of the electrochemical reaction.

[0068] In step (1), the etching working solution and etching waste liquid are derived from at least one of an acidic copper chloride etching solution without ferric chloride, an acidic copper chloride etching solution containing ferric chloride, and an alkaline ammonia copper chloride etching solution. The etching waste liquid is one or more of an etching waste liquid that has undergone electrochemical reduction and an etching waste liquid that has undergone copper extraction.

[0069] The oxidizing gas described in step (2) is an external input gas, specifically selected from at least one of ozone, oxygen, chlorine and air.

[0070] Conventional methods, where oxidizing gas is directly injected through a gas-liquid mixer into the acidic etching solution in an etching machine to regenerate cuprous chloride or ferrous chloride, are extremely slow under acidic conditions, making it difficult to meet production requirements. The gas-liquid hybrid electrochemical reaction device of the present invention utilizes oxidizing gas to electrocatalytically accelerate the electrochemical oxidation of the etching solution.

[0071] When the etching working solution is an acidic copper chloride etching solution and is used as the electrolyte, taking oxygen as the oxidizing gas as an example, the electrochemical reactions occurring at different components are as follows:

[0072] Components that have negative charge during electrolysis: 2Cu 2+ +O2+4e - →2CuO 4H + +O2+4e - →2H2O

[0073] Components that are positively charged during electrolysis: Cu + -e - →Cu 2+

[0074] When the acidic copper chloride etching solution contains Fe 2+ When the electrolysis is positive, the following reactions will also occur on the components that are positively charged during electrolysis: Fe 2+ -e - →Fe 3+

[0075] During the above electrochemical reaction, the electrolyte also undergoes the following chemical reaction: 2HCl+CuO→CuCl2+H2O

[0076] When the etching working solution is an alkaline copper chloride ammonia etching solution, taking oxygen as the oxidizing gas as an example, the electrochemical reaction formula is as follows:

[0077] Components that have negative charge during electrolysis: 2Cu 2+ +O2+4e - →2CuO

[0078] Components that are positively charged during electrolysis: [Cu(NH3)2] + +2NH3-e - →[Cu(NH3)4] 2+

[0079] During the above electrochemical reaction, the electrolyte also undergoes the following chemical reaction: CuO+4NH3+H2O+2NH4Cl→Cu[(NH3)4]Cl2+2NH4OH

[0080] As can be seen from the above, the negatively charged components in the gas-liquid hybrid electrolytic cell achieve electrocatalytic function through electrochemical reaction with the oxidizing gas, thereby increasing the reaction speed of the oxidative regeneration copper etching agent in the etching solution.

[0081] The present invention can be improved as follows: a cathode filter device is used in a gas-liquid hybrid electrolytic cell to surround the electrolytic cathode and / or insoluble cathode conductor, which has two functions: the first is to prevent copper particles electrolytically deposited when operating at an excessive electrolyte decomposition voltage value from entering the etching machine; the second is to pump the gas-liquid mixture in the gas-liquid hybrid electrolytic cell into the negatively charged electrode space wrapped by the cathode filter device. Since the electrolyte here contains a higher concentration of oxidizing gas, the positively charged components can better exert an oxidizing effect under the electrocatalysis of the negatively charged components.

[0082] The present invention can also be improved as follows: to increase the oxidation regeneration reaction rate of the acidic etching solution, an auxiliary electrolytic cell is used in combination with a gas-liquid hybrid electrolytic cell, and the auxiliary electrolytic cell is divided into an anode cell area and a cathode cell area by an electrolytic cell separator. Specifically, the anode of the auxiliary electrolytic cell is used to directly electrochemically oxidize the acidic etching working solution at a voltage higher than the electrolyte decomposition voltage. In addition, since the cathode electrolyte of the auxiliary electrolytic cell produces a large amount of reducing agent due to the electrochemical reduction reaction, a gas-liquid hybrid electrolytic cell is used to oxidize the discharged cathode electrolyte. Preferably, the electrolytic cell separator of the auxiliary electrolytic cell uses an anion exchange membrane, and its cathode electrolyte uses acidic copper chloride etching waste liquid to better play the role of the auxiliary electrolytic cell.

[0083] The present invention can also be improved as follows: in order to increase the spray oxidation rate in the etching machine, the oxidizing gas escaping from the gas-liquid mixed electrolytic cell reaction is drained into the spray space inside the etching machine for utilization, so that the etching working fluid reacts with the oxidizing gas during spray atomization to accelerate the regeneration rate of the copper etching agent.

[0084] The present invention can also be improved as follows: a variable frequency pump or a variable flow valve is used to control the amount of regenerated etching sub-liquid added to the etching machine according to process requirements, so that the etching working liquid maintains stable etching performance.

[0085] Compared with the prior art, the present invention has the following beneficial effects:

[0086] 1. The present invention uses a gas-liquid hybrid electrochemical reaction device to oxidize and regenerate the copper etching agent in the etching working solution and / or the etching waste liquid through electrocatalysis;

[0087] The device of the present invention oxidizes and regenerates the acid-chloride copper etching solution with an oxidizing gas as an oxidant, so that the copper etching agent concentration of the acid etching solution is less diluted by the liquid oxidant, thereby increasing the copper ion concentration of the etching working solution to improve the etching performance, thereby enhancing production efficiency and etching quality, solving the existing quality problems of acid etching, and reducing or even eliminating the use of liquid oxidants.

[0088] For alkaline copper chloride ammonium etching solution, an electrochemical oxidation regeneration process is added as an auxiliary on the basis of absorbing oxygen in the air during the original etching machine spray to cause the etching working solution to undergo an oxidation regeneration reaction. This can quickly regenerate the copper etching agent, increase the concentration of the copper etching agent in the etching working solution, and thereby improve production efficiency and etching speed, thereby improving etching quality and increasing production efficiency.

[0089] 2. The present invention uses a gas-liquid hybrid electrochemical reaction device, and there is no new pollution source in the process, which fully meets the requirements of environmentally friendly production.

[0090] 3. The process of the present invention is simple, safe and reliable, with a simple equipment structure, small investment and high economic benefits, thus overcoming the equipment investment problem of the electrolytic cell in the prior art.

[0091] 4. The present invention uses a gas-liquid hybrid electrochemical reaction device to oxidize the etching solution, which can increase the copper ion concentration of the etching solution and reduce the discharge of etching waste liquid. It also provides a solution for using the oxalic acid method to recover copper salts and 100% recycling of the acidic etching waste liquid, enabling the implementation of the oxalic acid method and significantly reducing etching production costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0092] The present invention will be further described below with reference to the accompanying drawings.

[0093] FIG1 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 6 of the present invention.

[0094] FIG2 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 7 of the present invention.

[0095] FIG3 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 8 of the present invention.

[0096] FIG4 is a schematic diagram showing a bipolar electrode of the gas-liquid hybrid electrochemical reaction device of the present invention, wherein the surface of the middle portion of the conductor is partially wrapped with an insulating material.

[0097] FIG5 is a schematic diagram of a portion of the outer shape of the insoluble conductor of the gas-liquid mixing electrochemical reaction device of the present invention.

[0098] FIG6 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 9 of the present invention.

[0099] FIG7 is a schematic structural diagram of an electrolyte ion current interrupter of a gas-liquid hybrid electrochemical reaction device according to the present invention.

[0100] FIG8 is a schematic structural diagram of the gas-liquid hybrid electrochemical reaction device of the present invention using two ion current interrupter temporary storage tanks as electrolyte ion current interrupters.

[0101] FIG9 is a schematic diagram of the bipolar electrode cage structure of the gas-liquid hybrid electrochemical reaction device of the present invention.

[0102] FIG10 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 1 of the present invention.

[0103] FIG11 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 2 of the present invention.

[0104] FIG12 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 3 of the present invention.

[0105] Figure 13 is a schematic diagram of the gas-liquid hybrid electrochemical reaction device of Example 4 of the present invention; Figures 13-1 and 13-2 are partial enlarged views of Figure 13, and the two are combined to form a complete schematic diagram of the device of Example 4.

[0106] Figure 14 is a schematic diagram of a gas-liquid mixed electrochemical reaction device according to Example 5 of the present invention; Figures 13-1 and 14-2 are partial enlarged views of Figure 14, and the two are combined to form a complete schematic diagram of the device according to Example 5.

[0107] Figure 1: 1-electrolytic cell, 2-electrolyte (i.e., treated solution), 3-electrolytic anode, 4-electrolytic cathode, 5-electrolytic power supply, 6-bipolar electrode, 7-vacuum jet electrolytic cell gas-liquid mixer, 8-bubbling electrolytic cell gas-liquid mixer, 9-vacuum jet and bubbling combination electrolytic cell gas-liquid mixer, 10-bipolar electrode insulating mesh box, 11-insulating through-hole support baffle, 12-gas scrubber, 13-conventional bubbling gas-liquid mixer, 14-conventional vacuum jet gas-liquid mixer, 15-conventional spray tower gas-liquid mixer, 16-hot and cold temperature controller Degree exchanger, 17-liquid flow pump tube agitator, 18-temporary storage tank, 19-insoluble anode conductor, 20-insoluble cathode conductor, 21-cathode filter, 22-electrolytic cell exhaust gas discharge pipe, 23-electrolytic cell reaction escape gas hole sealing tank cover, 24-air, 25-oxygen, 26-ozone, 27-chlorine, 28-external oxidizing gas participating in the reaction, 29-clean water, 30-etching working solution, 31- Oxidizing gas escaping from the reaction liquid, 32- Valve, 33- Pump, 34- Gas booster pump, 35- Electrical insulator, 36- Conductor, 37- Conductive connecting line, 38- Automatic detection and feeding controller, 39- Sensor, 40- Waste gas environmental protection treatment tank, 41- Insulating partition plate in the electrolytic cell, 42- Electrolyte ion flow cut-off trough (device), 43- Air pressure balance connecting pipe, 44- Hydrochloric acid, 45- Ferric chloride, 46- Ammonium chloride, 47- Sulfuric acid, 48- Sodium hydroxide, 49- Etching liquid mixing exchange tank, 50- Overflow buffer tank, 51- Solid-liquid separator, 52- Bubble-containing reaction liquid guide cover, 53- Etching machine, 54- Regenerated etching sub-liquid, 55- Etching circuit board, 56- Ammonia water, 57- Ammonium carbonate, 58- Etching sub-liquid, 59- Etching waste liquid, 60- Chemical reaction tank, 61- Auxiliary electrolytic cell, 62- Electrolytic cell partition.

[0108] In the drawings and the following embodiments, multiple components of the same component type in a device are represented by "reference numerals." For example, electrolytic cell body 1-1 refers to one electrolytic cell body, and electrolytic cell body 1-2 refers to another electrolytic cell body. When there are three or more components of the same component type, "~" is used for abbreviation. For example, electrolytic cell bodies 1-1, 1-2, and 1-3 are referred to as electrolytic cell bodies 1-1 to 1-3, or 1-1 to 3. DETAILED DESCRIPTION

[0109] The present invention will be further described below through specific embodiments.

[0110] The electrolytic cell, electrolytic anode, electrolytic cathode, bipolar electrode, bipolar electrode electrical insulation cage, electrolytic cell gas-liquid mixer, liquid flow pump and agitator, temporary storage tank, insoluble anode conductor, insoluble cathode conductor, electrolyte ion current interrupter, cathode filter, and exhaust gas environmental treatment tank used in the gas-liquid mixing electrochemical reaction device described in the embodiments of the present invention are all manufactured by Yegao Environmental Protection Equipment Manufacturing Co., Ltd. in Foshan, Guangdong Province, China. The PLC program logic controller, sensors, solid-liquid separator, etching machine, automatic detection and feeding controller, valves, pumps, and chemical raw materials are all commercially available products.

[0111] In addition to the above-mentioned products, those skilled in the art may also select other products with similar properties to the above-mentioned products listed in the present invention according to routine selection, and all of them can achieve the purpose of the present invention.

[0112] Example 1

[0113] The gas-liquid mixed electrochemical reaction device shown in FIG10 is Example 1 of the present invention. The device includes a gas-liquid mixed electrolytic cell.

[0114] The gas-liquid hybrid electrolytic cell adopts the electrolytic cell structure of Figure 1 and is connected to the etching machine 53 via a circulating liquid flow pipeline. The gas-liquid hybrid electrolytic cell comprises an electrolytic cell body 1, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, and a combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. The electrolytic cell body 1 is equipped with an insoluble anode conductor 19 directly electrically connected to the electrolytic anode, an insoluble cathode conductor 20 directly electrically connected to the electrolytic cathode, a bipolar electrode 6, a bipolar electrode insulating mesh box 10, and an electrically insulating mesh through-hole multi-shaped support baffle 11. The bipolar electrode 6, insoluble anode conductor 19, and insoluble cathode conductor 20 are electrocatalytic components.

[0115] The electrolytic cell gas-liquid mixer 9 is connected to the electrolytic cell body 1 through the overflow buffer tank 50-2, the pump 33-2, the etcher 53, the overflow buffer tank 50-1, and the pump 33-1 as a liquid flow pipeline, and its outlet is directed toward the electrolytic cathode 4, the insoluble cathode conductor 20 and the bipolar electrode 6; the outlet of the electrolytic cell gas-liquid mixer 9 is directed toward the electrolytic cathode 4 and the insoluble cathode conductor 20.

[0116] The electrolytic anode, electrolytic cathode, insoluble anode conductor, insoluble cathode conductor metal fragments and metal wire are all conductors with platinum-plated surfaces. The electrolytic tank gas-liquid mixer 9 is a conductor with platinum-plated surface and is conductively connected to the negative electrode of the electrolytic power supply 5, so that the gas-liquid mixer 9 becomes part of the insoluble cathode conductor electrocatalytic component.

[0117] The treated solution 2 is an acidic copper chloride etching solution, the acidity of the etching working solution is 2.5M / L, the copper ion concentration is 130g / L, the electrolyte decomposition voltage value is 0.4V, and the ORP is 505mv.

[0118] The external gas input to participate in the chemical reaction is ozone 26.

[0119] The etching machine is an etching machine for acidic copper chloride etching solution, which is connected to the gas-liquid mixing electrochemical reaction device through an overflow buffer tank.

[0120] The steps of the method for oxidizing the etching solution using a gas-liquid mixed electrochemical reaction device are as follows:

[0121] 1. Add acidic copper chloride etching working solution to the etcher and the gas-liquid mixed electrolytic tank, use the acidic copper chloride etching working solution as the electrolyte, start the electrolysis power supply 5 and adjust the voltage between the electrolysis anode and the electrolysis cathode to 1V.

[0122] 2. Start the pump in the device to deliver the acid copper chloride etching working solution to the gas-liquid mixer of the electrolytic cell, and input ozone 26, mix the ozone with the acid copper chloride etching working solution as a gas-liquid mixture, and then spray it onto the electrolytic cathode and electrocatalytic component;

[0123] The etching working liquid flows into the gas-liquid hybrid electrolytic tank and undergoes electrochemical oxidation reaction, so that its ORP value rises to 518mv to generate regenerated etching sub-liquid 54, which is pumped back to the etcher to participate in the etching reaction and maintain the etching performance of the etching liquid.

[0124] 3. Put the etching circuit board 55 into the etching machine for etching, and put hydrochloric acid into the etching machine through manual detection and control and adjust the electrolytic cell to continuously pump the regenerated etching sub-liquid back into the etching machine for continuous etching production.

[0125] Example 2

[0126] The gas-liquid hybrid electrochemical reaction device shown in Figure 11 is Example 2 of the present invention. The device comprises a gas-liquid hybrid electrolytic cell, an environmentally friendly waste gas treatment tank 40, an etching solution mixing exchange tank 49, and two overflow buffer tanks 50-1 and 50-2. The etching solution mixing exchange tank 49 is connected to the etching machine via a circulating liquid flow conduit and is also connected to the gas-liquid hybrid electrolytic cell via a liquid circulation conduit.

[0127] The gas-liquid mixing electrolytic cell adopts the electrolytic cell structure of Figure 2, including an electrolytic cell body 1, two electrolytic anodes 3-1 and 3-2, an electrolytic cathode 4, an electrolytic power supply 5, and two vacuum jet electrolytic cell gas-liquid mixers 7-1 and 7-2. The electrolytic anodes 3-1 and 3-2 are respectively connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5.

[0128] The electrolytic cell 1 is equipped with insoluble anode conductors 19-1 and 19-2, which are directly conductively connected to the electrolytic anode; an insoluble cathode conductor 20, which is directly conductively connected to the electrolytic cathode; and a cathode filter 21. The cathode filter 21 is a filter bag that surrounds the electrolytic cathode 4 and the insoluble cathode conductor 20 and is used to intercept floating copper particles generated by cathode electrolysis. The insoluble cathode conductor 20 is an electrocatalytic component. The vacuum jet electrolytic cell gas-liquid mixers 7-1 and 7-2 are connected to the electrolytic cell 1 via pumps 33-4 and 33-5, respectively, via liquid flow conduits. Their outlets face the electrolytic cathode 4 and the insoluble cathode conductor 20 within the cathode filter 21.

[0129] The electrolytic anode is an insoluble anode with a titanium-based coating, the electrolytic cathode is stainless steel, the insoluble anode conductor is a gold-plated metal wire, the insoluble cathode conductor is stainless steel fragments and stainless steel wire, and the material of the electrolytic tank gas-liquid mixer is a polymer resin.

[0130] The etching liquid mixing exchange tank 49 is provided with sensors 39-3 and 39-4, and the etching machine 53 is provided with sensors 39-1 and 39-2. The sensor 39-1 is a pH meter, 39-2 and 39-4 are ORP meters, and 39-3 is a liquid level meter.

[0131] The treated solution 2 is an alkaline cuprammonium chloride etching solution with a pH value of 8.6, a copper ion concentration of 140 g / L, an ORP value of 5 mv, and an electrolyte decomposition voltage of 1.1 V.

[0132] The external gas input to participate in the chemical reaction is air 24.

[0133] The etching machine adopts alkaline cuprammonium chloride etching solution and uses a specific gravity meter to control the addition of etching liquid. It is indirectly connected to the gas-liquid mixing electrolytic tank through an overflow buffer tank and an etching liquid mixing exchange tank as a liquid flow pipeline.

[0134] The waste gas environmental protection treatment tank 40 is connected to each tank that discharges tail gas through a gas pipeline, so as to treat the escaped tail gas in an environmentally friendly manner.

[0135] The etching liquid is a mixture of ammonia water, ammonium chloride, ammonium carbonate and ammonium bicarbonate.

[0136] The steps of the method for oxidizing the etching solution using a gas-liquid mixed electrochemical reaction device are as follows:

[0137] 1. Add alkaline copper chloride ammonium working solution to the etcher, etching solution mixed exchange tank and gas-liquid mixed electrolytic cell, use alkaline copper chloride ammonium working solution as electrolyte, start the electrolysis power supply 5 and adjust it to 1.1V between the electrolysis anode and the electrolysis cathode.

[0138] 2. Start the pumps in the device to deliver electrolyte to the gas-liquid mixers of the two electrolytic cells respectively, and input air 24 to mix the electrolyte and air into a gas-liquid mixture and then spray it onto the electrolytic cathode and electrocatalytic component;

[0139] The alkaline etching working solution flows into the electrolytic tank and undergoes an electrochemical oxidation reaction, causing its ORP value to rise to 50mv to generate regenerated etching sub-liquid 54, which is pumped to the etching solution mixing exchange tank through pump 33-6, so that the ORP value of the mixed solution in the tank reaches 30mv; the ORP meter in the etching machine controls the frequency conversion pump 33-2 to add the mixed solution to the etching machine to participate in the etching reaction and maintain the etching performance of the etching solution. The pH meter in the etching machine controls the addition of etching sub-liquid 58.

[0140] 3. Put the etching circuit board 55 into the etcher for etching, control the liquid level of the mixed liquid by the liquid level gauge in the etching liquid mixing exchange tank and discharge it in time, and its ORP meter controls the shutdown of the electrolytic power supply 5 according to the process set value; under process control, the gas-liquid mixed electrolytic cell continuously pumps the regenerated etching sub-liquid indirectly back to the etcher for continuous etching production.

[0141] 4. The waste gas environmental treatment tank absorbs the waste gas escaping from each tank for environmental treatment.

[0142] Example 3

[0143] The gas-liquid hybrid electrochemical reaction device shown in FIG12 is Example 3 of the present invention. The device includes a gas-liquid hybrid electrolytic cell, a temporary storage tank 18, an electrolyte ion flow channel 42, an overflow buffer tank 50, a solid-liquid separator 51, an etching machine 53, and a chemical reaction tank 60.

[0144] The gas-liquid mixing electrolytic cell adopts the electrolytic cell with the circular electrode distribution structure shown in Figure 3, including an electrolytic cell body 1, an electrolytic anode 3, eight electrolytic cathodes 4-1 to 4-8, eight electrolytic power supplies 5-1 to 5-8, a vacuum jet electrolytic cell gas-liquid mixer 7, and eight bubbling electrolytic cell gas-liquid mixers 8. The electrolytic anode 3 is connected to the positive pole of the electrolytic power supplies 5-1 to 5-8, and the electrolytic cathodes 4-1 to 4-8 are respectively connected to the negative poles of their corresponding electrolytic power supplies 5-1 to 5-8.

[0145] The electrolytic cathodes 4-1 to 4-8 in the electrolytic cell body 1 are arranged around the electrolytic anode 3. Insulating partitions 41 separate the electrolytic cathodes 4-1 to 4-8. The electrocatalytic performance of the electrolytic anodes and cathodes has been improved: the electrolytic anodes 3 and cathodes 4-1 to 4-8 are connected in parallel and constructed as electrocatalytic components. The angle formed by the electrodes with the gas-liquid mixture ejection line of the electrolytic cell gas-liquid mixer is greater than 0° and less than 90°. The electrolytic cell body 1 also includes an insoluble anode conductor 19 directly conductively connected to the electrolytic anodes, eight insoluble cathode conductors 20-1 to 20-8 directly conductively connected to the electrolytic cathodes, and an insulating through-hole support plate 11.

[0146] The vacuum jet electrolytic cell gas-liquid mixer 7 is connected to the electrolytic cell body 1 as a liquid circulation pipeline through eight bubbling electrolytic cell gas-liquid mixers 8-1 to 8 and a pump 33-5, wherein the outlets of the eight bubbling electrolytic cell gas-liquid mixers 8-1 to 8 are directed toward the eight electrolytic cathodes 4-1 to 4-8 and the insoluble cathode conductors 20-1 to 20-8.

[0147] The electrolytic anode material is conductive graphite, the electrolytic cathode is a conductor with a gold-plated surface, the insoluble anode conductor is consistent with the anode material, and the insoluble cathode conductor is metallic copper.

[0148] The etching machine 53 is an alkaline etching solution etching machine that controls the feeding of the etching solution by pH value, and is equipped with a hot and cold temperature exchanger 16-1, sensors 39-2, 39-2 and 39-3. The tail gas outlet of the electrolytic cell body 1 and the tail gas outlet of the electrolyte ion flow channel 42 are connected to the etching machine 53 through a gas pressure pump 34.

[0149] The electrolyte ion flow cutoff slot 42 is used to prevent the short circuit of the electrolyte ion flow in the electrolytic cell of the gas-liquid mixed electrochemical reaction device, and is provided with a sensor 39-9.

[0150] The temporary storage tank is filled with regenerated etching sub-liquid 54, and a hot and cold temperature exchanger 16-2 and sensors 39-6, 39-7, and 39-8 are installed in the tank.

[0151] The chemical reaction tank 60 is used to add etching sub-liquid to mix the treated liquid so that the treated liquid can accelerate the electrochemical oxidation reaction under appropriate conditions. It is equipped with sensors 39-4 and 39-5.

[0152] The adjustable valve opening control flow valve 32 - 2 is used to control the amount of the regenerated etching sub-liquid 54 fed into the etching machine 53 to participate in the reaction.

[0153] The sensors 39-1 and 39-6 are thermometers, 39-2 and 39-4 are pH meters, 39-3 and 39-7 are ORP meters, and 39-5, 39-8, 39-9, and 39-10 are liquid level meters. The ORP meter controls the opening and closing of eight electrolysis power supplies.

[0154] The etching liquid is a mixture of ammonia water, ammonium chloride and ammonium carbonate.

[0155] The alkaline cuprammonium chloride etching working solution mainly comprises ammonia water, ammonium chloride, ammonium carbonate and cuprammonium chloride, wherein the pH value is pH7.3, the copper ion concentration is 100g / L, the ORP value is 40mv, and the electrolyte decomposition voltage value is 1.1V.

[0156] The process features of this embodiment are as follows: first, the oxidizing gas 31 escaping from the reaction liquid of the gas-liquid mixed electrolytic cell is drained into the spray space of the etching machine for utilization; second, the electrolyte of the gas-liquid mixed electrolytic cell is first prepared in the chemical reaction tank 60 so that the balance of the oxidation reaction is in the direction of regenerating the copper etching agent.

[0157] The steps of the method for oxidizing the etching solution using a gas-liquid mixed electrochemical reaction device are as follows:

[0158] 1. Add 30% alkaline etching working solution to the etcher, chemical reaction tank, gas-liquid mixed electrolytic tank, and electrolyte ion flow tank, use alkaline copper chloride ammonium working solution as the electrolyte, turn on eight electrolytic power supplies and adjust the voltage between the electrolytic anode and the electrolytic cathode to 1.4V.

[0159] 2. Start the pumps in the device to deliver electrolyte and oxygen to the vacuum jet electrolyzer gas-liquid mixer 7. After the electrolyte and oxygen are mixed as a gas-liquid mixture, they are sprayed onto the electrolytic cathode and electrocatalytic component through the eight bubbling electrolyzer gas-liquid mixers;

[0160] The alkaline etching working liquid undergoes an electrochemical oxidation reaction in the gas-liquid mixed electrolytic tank, making its ORP value reach 90mv, thereby obtaining a regenerated etching sub-liquid 54, which is then sent to the etching machine through the temporary storage tank 18.

[0161] 3. Continuously add etching circuit boards 55 into the etcher, wherein the sensor controls the valve opening of valve 32-2 to control the amount of regenerated etching sub-liquid 54 added to the etcher, sensor 39-2 controls the etching sub-liquid 58 to be added to the etcher, sensor 39-4 controls the etching sub-liquid to be added to the chemical reaction tank 60, and sensor 39-7 controls the opening and closing of eight electrolytic power supplies. The oxidizing gas escaping from the electrolytic tank reaction liquid is drained to the spray space of the etcher for reuse, so that the etcher can operate normally.

[0162] Example 4

[0163] The gas-liquid hybrid electrochemical reaction device shown in FIG13 is Example 4 of the present invention. The device includes a gas-liquid hybrid electrolytic cell, four temporary storage tanks 18-1 to 18-4, an automatic detection and feeding machine 38, an exhaust gas environmental treatment tank 40, two electrolyte ion flow cells 42-1 and 42-2, three overflow buffer tanks 50-1 to 50-3, an etching machine 53, a chemical reaction tank 60, and an auxiliary electrolytic cell 61.

[0164] The gas-liquid mixing electrolytic cell comprises an electrolytic cell body 1, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, and a combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. The electrolytic cell body 1 is equipped with an insulating through-hole support baffle 11, a liquid flow pump agitator 17, an insoluble anode conductor 19 directly conductively connected to the electrolytic anode, an insoluble cathode conductor 20 directly conductively connected to the electrolytic cathode, a sensor 39-13, and a bubble-containing reaction liquid deflector 52. The insoluble anode conductor 19 and the insoluble cathode conductor 20 serve as electrocatalytic components.

[0165] The vacuum jet electrolytic cell gas-liquid mixer 9 is connected to the electrolytic cell body 1 by a liquid flow pipeline, and its outlet faces the electrolytic cathode 4 and the insoluble cathode conductor 20. It is also provided with an ultrasonic generator (not shown).

[0166] The gas-liquid hybrid electrolytic cell has a platinum-plated anode 3, titanium-plated cathode 4, a titanium-based insoluble coating on the insoluble anode conductor 19, and a gold-plated insoluble cathode conductor 20. The gas-liquid hybrid electrolytic cell is used to oxidize the cathode electrolyte of the auxiliary electrolytic cell.

[0167] The auxiliary electrolytic cell 61 includes an electrolytic anode, an electrolytic cathode, an electrolytic power supply, and an electrolytic cell separator anion exchange membrane. The anode and cathode electrolytes are acidic copper chloride etching working fluid, which is used to electrochemically oxidize the etching working fluid and regenerate the copper etching agent.

[0168] The two electrolyte ion-isolating flow channels are used to electrically isolate the etching system from the electrolytic oxidation system.

[0169] The temporary storage tank 18-1 is used for temporarily storing hydrochloric acid and is equipped with a sensor 39-1, the tank 18-2 is used for temporarily storing the etching working liquid and for distribution and is equipped with sensors 39-6 and 39-7, the tank 18-3 is used for temporarily storing the regenerated etching sub-liquid and is equipped with sensors 39-8, 39-9 and 39-10, and the tank 18-4 is used for temporarily storing the etching waste liquid 59.

[0170] The etching machine is an etching machine for acidic copper chloride etching liquid. Sensor 39-3, i.e., the acidity meter, controls the addition of hydrochloric acid, sensor 39-4, i.e., the hydrometer, controls the addition of water, and sensor 39-5, i.e., the ORP meter, controls the variable frequency pump 33-6 to add the regenerated etching liquid in tank 18-3.

[0171] The chemical reaction tank 60 is equipped with a common vacuum jet gas-liquid mixer 14 and is provided with sensors 39-14 and 39-15, which are used to absorb and utilize the chlorine tail gas escaping from the auxiliary electrolytic cell and oxidize the electrolyte solution flowing out of the electrolytic cell of the gas-liquid mixing electrochemical reaction device.

[0172] Sensors 39-1, 39-6, 39-8, and 39-14 are liquid level gauges; 39-2 and 39-9 are thermometers; 39-3 and 39-11 are acidity meters; 39-4 is a hydrometer; 39-5, 39-7, 39-10, 39-12, 39-13, and 39-15 are ORP meters; and 39-16 is a chlorine concentration detector. Sensor 39-11 controls pump 33-4 to add etching solution to replenish the hydrochloric acid in the auxiliary electrolytic cell's cathode electrolyte. Sensor 39-10 controls the auxiliary electrolytic cell's electrolytic power supply and turns on and off the electrolytic power supply 5 for the gas-liquid hybrid electrolytic cell.

[0173] The gas of the gas-liquid mixed electrochemical reaction device is externally input oxygen 25.

[0174] The main component of the cathode electrolyte of the auxiliary electrolytic cell is an acidic copper chloride etching working solution, in which the copper ion concentration is 120g / L, the acidity is 1.5M / L, the ORP is 400mv, and the electrolyte decomposition voltage value is 0.4V; the electrolyte of the gas-liquid mixed electrolytic cell is the cathode electrolyte of the auxiliary electrolytic cell.

[0175] The steps of the method for oxidizing the etching solution using a gas-liquid mixed electrochemical reaction device are as follows:

[0176] 1. Add acidic copper chloride etching working solution to the etching machine, temporary storage tank 18-2, auxiliary electrolytic tank anode tank area and cathode tank area, and gas-liquid mixed electrolytic tank, add regenerated etching sub-liquid to the temporary storage tank 18-3 and electrolyte ion flow tank 42-1, and add sodium hydroxide solution 48 to the waste liquid environmental protection treatment tank.

[0177] 2. Connect the power supply of the device to start the automatic detection and feeding controller 38, process the on-site sampling data, control the start of the etching machine and the corresponding pumps, open the auxiliary electrolytic cell and the gas-liquid hybrid electrolytic cell, and start the vacuum ejector 14 of the chemical reaction tank 60 to perform the oxidation operation;

[0178] The cathode electrolyte of the auxiliary electrolytic cell and the input air 24 are delivered to the electrolytic cell gas-liquid mixer 9, and the gas and liquid are mixed and sprayed onto the electrolytic cathode and electrocatalytic components in the gas-liquid mixing electrolytic cell;

[0179] The electrolytic power supply 5-1 applies a voltage of 2.3V between the electrolytic anode and the electrolytic cathode to carry out an electrochemical oxidation reaction. The electrolyte 2 is detected by the sensor 39-13 and the result is 430mv. The detection result of the sensor 39-15 is 440mv. The bubble-containing reaction liquid continuously circulates through the liquid flow pump tube agitator 17 for reaction.

[0180] 3. The etching circuit board is put into the etcher for etching production. The auxiliary electrolytic cell anode electrolyte, that is, the regenerated etching liquid of the etcher, is continuously fed back into the etcher to participate in the etching reaction, and the divalent copper ions and trivalent iron ions in the cathode electrolyte of the auxiliary electrolytic cell participate in the electrochemical reduction reaction of the electrolytic cathode to reduce its valence. During the working process, the cathode electrolyte continuously circulates in the gas-liquid mixed electrolytic cell and between the chemical reaction tank and undergoes an oxidation reaction, so that the electrolytic cathode and the insoluble cathode conductor in the gas-liquid mixed electrolytic cell do not electrolytically deposit copper metal, so that the etched circuit board 55 can be continuously etched and produced.

[0181] 4. The waste liquid escaping from each tank in the device is drained into the waste gas environmental protection treatment tank for environmental protection treatment.

[0182] Example 5

[0183] The gas-liquid hybrid electrochemical reaction device shown in FIG14 is Example 5 of the present invention. The device includes two gas-liquid hybrid electrolytic cells, three electrolyte ion flow cells 42, an etching solution mixing exchange cell 49, an overflow buffer cell 50, a solid-liquid separator 51, and an etching machine 53.

[0184] One of the gas-liquid hybrid electrolytic cells described above includes an electrolytic cell body 1-1, an electrolytic anode 3-1, an electrolytic cathode 4-1, an electrolytic power supply 5-1, and a combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9-1. The electrolytic anode 3-1 is connected to the positive electrode of the electrolytic power supply 5-1, and the electrolytic cathode 4-1 is connected to the negative electrode of the electrolytic power supply 5-1. The electrolytic cell body 1-1 is provided with an insoluble anode conductor 19-1 directly electrically connected to the electrolytic anode, an insoluble cathode conductor 20-1 directly electrically connected to the electrolytic cathode, a bipolar electrode 6, a bipolar electrode insulating mesh box 10, and an electrically insulating mesh with multi-shaped through-hole support baffle 11-1. The bipolar electrode 6, insoluble anode conductor 19-1, and insoluble cathode conductor 20-1 serve as electrocatalytic components. The electrolytic cell gas-liquid mixer 9 - 1 is connected to the electrolytic cell body 1 - 1 via a liquid flow pipeline, with its outlet facing the electrolytic cathode 4 - 1 , the insoluble cathode conductor 20 - 1 and the bipolar electrode 6 .

[0185] The second gas-liquid mixing electrolytic cell comprises an electrolytic cell body 1-2, an electrolytic anode 3-2, an electrolytic cathode 4-2, an electrolytic power supply 5-2, and a combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9-2. The electrolytic anode 3-2 is connected to the positive electrode of the electrolytic power supply 5-2, and the electrolytic cathode 4-2 is connected to the negative electrode of the electrolytic power supply 5-2. The electrolytic cell body 1-2 is provided with an insoluble anode conductor 19-2 directly electrically connected to the electrolytic anode, an insoluble cathode conductor 20-2 directly electrically connected to the electrolytic cathode, an electrically insulating mesh with multi-shaped through-hole baffle 11-2, and a cathode filter device 21. The insoluble anode conductor 19-2 and the insoluble cathode conductor 20-2 are electrocatalytic components. The electrolytic cell gas-liquid mixer 9-2 is connected to the electrolytic cell body 1-2 via a liquid flow conduit, with its outlet facing the electrolytic cathode 4-2 and the insoluble cathode conductor 20-2.

[0186] The electrolytic anodes 3-1 and 3-2 are both insoluble anodes with titanium-based coatings, the electrolytic cathodes 4-1 and 4-2 are both made of titanium, the insoluble anode conductor 19-1 is graphite, 19-2 is an insoluble anode with titanium-based coatings, the insoluble cathode conductor 20-1 is copper metal fragments and copper metal wire, 20-1 is a conductor with a platinum-plated surface, and the material of the two electrolytic cell gas-liquid mixers 9 is titanium metal.

[0187] One of the gas-liquid mixed electrolytic cells uses chlorine as a reaction gas, and the second gas-liquid mixed electrolytic cell uses the reaction exhaust gas of cell 1-1 and externally input oxygen as reaction gases.

[0188] The etching liquid mixing exchange tank 49 is connected to the etching machine through a liquid flow pipeline circulation, and is also connected to the electrolytic cell body 1-1 and the electrolytic cell body 1-2 through the electrolyte ion flow channel through a liquid flow pipeline circulation.

[0189] The solid-liquid separator 51 is used to filter out solid impurities in the etching working solution 30 .

[0190] The two hot and cold temperature exchangers 16 allow the etching working fluid to meet the temperature required by the process.

[0191] The sensors 39-1 and 39-5 are thermometers, 39-2 is a pH meter, 39-3 is a hydrometer, 39-4, 39-6, 39-8, and 39-9 are ORP meters, and 39-7 is a liquid level meter.

[0192] The solution to be processed in this embodiment is an acidic copper chloride and ferric chloride mixed etching solution, with an acidity of 2.2M / L, a copper ion concentration of 130g / L, an ORP value of 580mv and an electrolyte decomposition voltage of 0.4V.

[0193] The pressure-balancing connecting pipe 43-1 connects the electrolytic cell 1-1 and the electrolytic cell 1-2 to form an intra-cell airway. The pressure-balancing connecting pipe 43-2 connects the two cell areas within the electrolytic cell 1-2, which are separated by filter cloth. The cathode filter device 21 uses filter cloth to intercept copper particles generated during cathode electrolysis from drifting into the etching machine.

[0194] The etching machine is an etching machine for acidic copper chloride etching solution, which is connected to the etching solution mixing exchange tank via an overflow buffer tank as a liquid circulation pipeline.

[0195] The temporary storage tank 18-1 is used to store etching waste liquid, and the temporary storage tank 18-2 is used to temporarily store acidic ferric chloride.

[0196] The steps of the method for oxidizing the etching solution using a gas-liquid mixed electrochemical reaction device are as follows:

[0197] 1. Add acidic copper chloride and ferric chloride mixed etching working solution to the etching machine, two gas-liquid mixed electrolytic cells and etching solution mixed exchange tank.

[0198] 2. Start the pump and electrolysis power supplies 5-1 and 5-2, input chlorine gas 27 into the electrolytic cell gas-liquid mixer 9-1, and input external oxygen and gas 31-1 escaped from the electrolyte of the electrolytic cell body 1-1 into the electrolytic cell gas-liquid mixer 9-2; wherein the electrolytic cell gas-liquid mixer 9-1 mixes the gas with the acidic copper chloride and ferric chloride mixed etching working solution from the etching solution mixing exchange tank and sprays the mixture onto the electrolytic cathode and electrocatalytic component in the electrolytic cell body 1-1, and the electrolytic cell gas-liquid mixer 9-2 mixes the gas with the electrolyte from the electrolytic cell body 1-2 and sprays the mixture onto the electrolytic cathode and electrocatalytic component in the electrolytic cell body 1-2;

[0199] The solutions in the etching solution mixing exchange tank flow into the electrolytic tanks 1-1 and 1-2 respectively, undergo electrochemical oxidation reaction, and generate regenerated etching sub-liquid 54, which is pumped into the electrolyte ion flow tank 42-1 for conductive isolation. The regenerated etching sub-liquid 54 is then added to the etching solution mixing exchange tank 49 for mixing, so that the ORP value of the solution therein reaches 630mv.

[0200] Finally, the solution is pumped back to the etching machine from the etching solution mixing exchange tank 49 through the variable frequency pump 33-4 to participate in the etching reaction and maintain the etching performance of the etching solution. The reading of sensor 39-8 is 680mv and the reading of sensor 39-9 is 650mv.

[0201] 3. Put the etching circuit board 55 into the etching machine for etching, and adopt manual control to put the acidic ferric chloride solution into the etching machine according to the data of the acidity meter so that the etching production can be carried out continuously.

[0202] Example 6

[0203] The gas-liquid hybrid electrochemical reaction device shown in FIG1 is Example 6 of the present invention and comprises an electrolytic cell 1, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, an electrolytic cell gas-liquid mixer, and an insulating through-hole support baffle 11. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. An electrocatalytic component, namely a bipolar electrode 6, an insoluble anode conductor 19, and an insoluble cathode conductor 20, is arranged in the electrolytic cell body 1; a sealing slot cover 23 for leaving holes for escaped gas from the electrolytic cell reaction covers the electrolytic cell body; the electrolytic cell gas-liquid mixer adopts an electrolytic cell gas-liquid mixer 9 that combines a vacuum jet type and a bubbling type, which is electrically connected to the electrolysis power supply and has an air inlet, a liquid inlet, and an outlet. The liquid inlet is connected to the electrolytic cell body. That is, this embodiment uses external input gas from outside the electrolytic cell to mix with the electrolyte in the electrolytic cell body, and the gas and liquid are ejected through an outlet extending below the electrolytic cathode 4 and the electrocatalytic component, namely the insoluble cathode conductor 20; an insulating through-hole support baffle 11 is arranged between the electrolytic cathode 4 and the outlet of the electrolytic cell gas-liquid mixer.

[0204] Example 7

[0205] The gas-liquid mixing electrochemical reaction device shown in Figure 2 is Example 7 of the present invention. It is a single gas-liquid mixing electrolytic cell, comprising an electrolytic cell body 1, electrolytic anodes 3-1 and 3-2, an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, and an electrolytic cell gas-liquid mixer. Electrolytic anodes 3-1 and 3-2 are connected to the positive electrode of the electrolytic power supply 5, and electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. The electrolytic cell gas-liquid mixers are vacuum jet electrolytic cell gas-liquid mixers 7-1 and 7-2. Electrolytic cell body 1 is provided with insoluble anode conductors 19-1 and 19-2, which are directly electrically connected to the electrolytic anodes, and an insoluble cathode conductor 20, which is directly electrically connected to the electrolytic cathode. Insoluble anode conductors 19-1 and 19-2 and insoluble cathode conductor 20 serve as electrocatalytic components. A sealed cell cover 23 is provided at the top of electrolytic cell body 1 to provide a hole for escaped gas from the electrolytic cell reaction. The vacuum jet electrolytic cell gas-liquid mixers 7-1 and 7-2 are connected to the electrolytic cell body as liquid flow pipes through pumps 33-1 and 33-2 respectively, and their outlets are directed toward the electrolytic anodes 3-1 and 3-2 and the insoluble anode conductors 19-1 and 19-2.

[0206] Example 8

[0207] The gas-liquid mixing electrochemical reaction device shown in Figure 3 is Example 8 of the present invention. It is a gas-liquid mixing electrolytic cell with a circular electrode distribution structure, comprising an electrolytic cell body 1, an electrolytic anode 3, electrolytic cathodes 4-1 to 4-8, electrolytic power supplies 5-1 to 5-8, an electrocatalytic component, an electrolytic cell gas-liquid mixer, and a sealed cell cover 23 for retaining holes for escaped gas from the electrolytic cell reaction. Within the electrolytic cell body 1, the electrolytic anode is positioned at the center of the cell body as the central electrode, with multiple electrolytic cathodes positioned around it. Alternatively, the electrolytic anode 3 is connected to the positive electrode of each electrolytic power supply 5-1 to 5-8, and the electrolytic cathodes 4-1 to 4-8 are connected to the negative electrode of the corresponding electrolytic power supply 5-1 to 5-8. The electrolytic cell gas-liquid mixer is a combination of vacuum jet and bubbling type electrolytic cell gas-liquid mixers 9-1 to 9-8. The electrolytic cell 1 is provided with an insoluble anode conductor 19, which is directly electrically connected to the electrolytic anode, and insoluble cathode conductors 20-1 to 20-8, which are directly electrically connected to the electrolytic cathode. Electrolytic cell gas-liquid mixers 9-1 to 9-8, which combine vacuum jet and bubbling methods, are connected to the electrolytic cell body via liquid flow conduits through pumps 33 and valves 32-1 to 32-8. Their outlets flow toward the electrolytic cathodes 4-1 to 4-8 and insoluble cathode conductors 20-1 to 20-8, respectively.

[0208] Example 9

[0209] The gas-liquid hybrid electrochemical reaction device shown in FIG6 is Example 9 of the present invention and comprises an electrolytic cell 1, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, an electrolytic cell gas-liquid mixer, and a cathode filter 21. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. The cathode filter 21-1 surrounds the electrolytic cathode and / or insoluble cathode conductor, and the cathode filter 21-2 is disposed between the electrolytic anode 3 and the electrolytic cathode 4. An electrocatalytic component, namely an insoluble anode conductor 19 and an insoluble cathode conductor 20, is arranged in the electrolytic cell body 1; a sealed slot cover 23 for leaving holes for escaped gas from the electrolytic cell reaction covers the electrolytic cell body, and is connected to a pressure balance connecting pipe at the top near the electrolytic anode and the top near the electrolytic cathode; the electrolytic cell gas-liquid mixer adopts an electrolytic cell gas-liquid mixer 9 that combines a vacuum jet type and a bubbling type, which has an air inlet, a liquid inlet and an outlet, and the liquid inlet is connected to the electrolytic cell body. That is, this embodiment uses external input gas from outside the electrolytic cell to mix with the electrolyte in the electrolytic cell body, and the gas and liquid are sprayed out through the outlet extending below the electrolytic cathode 4 and the electrocatalytic component, namely the insoluble cathode conductor 20.

[0210] Comparative Example 1

[0211] This comparative example uses the method of Example 1, except that a conventional electrolytic cell is used to oxidize the acidic copper chloride etching solution instead of the gas-liquid hybrid electrolytic cell of the present invention. The conventional electrolytic cell lacks an electrolytic cell gas-liquid mixer and does not employ any electrocatalytic components. The ORP value of the acidic copper chloride etching solution measured in the conventional electrolytic cell did not change significantly.

[0212] Comparative Example 2

[0213] This comparative example adopts the method of Example 1, except that only a common electrolytic anode and a common electrolytic cathode are used without any electrocatalytic component. As a result, it is found that the ORP value of the acidic copper chloride etching solution in the electrolytic cell is difficult to increase to 518mv.

[0214] Comparative Example 3

[0215] This comparative example adopts the method of Example 1, except that there is no electrolytic cell gas-liquid mixer. As a result, it is found that the ORP value of the acidic copper chloride etching solution in the electrolytic cell is difficult to increase to 518mv.

[0216] By comparing the result data of Example 1 and Comparative Examples 1-3, it can be seen that the combination of the gas-liquid mixture of the electrolyzer and the electrocatalytic structure can achieve a significant electrocatalytic effect of the electrochemical reaction.

[0217] The embodiments of the present invention can achieve production with lower energy consumption when the electrochemical reaction is performed at a voltage less than or equal to the electrolyte decomposition voltage, or when the electrochemical reaction is performed at a voltage slightly higher than the electrolyte decomposition voltage when there is sufficient gas participating in the reaction so that it is difficult for electrical components to electrolyze gas.

Claims

1. A gas-liquid mixed electrochemical reaction device for oxidation treatment of etching solution, comprising an electrolytic cell mainly composed of an electrolytic cell body, an electrolytic anode, an electrolytic cathode, and an electrolytic power supply, wherein: The electrolysis anode is connected to the positive electrode of the electrolysis power supply, and the electrolysis cathode is connected to the negative electrode of the electrolysis power supply. The electrolytic cell is characterized in that it includes at least one electrolytic cell gas-liquid mixer and an electrocatalytic component, forming a gas-liquid mixing electrolytic cell; the outlet of the electrolytic cell gas-liquid mixer is oriented toward or located in the electrolytic cell body, and is used to bring the gas-liquid mixture obtained by mixing the electrolyte in the electrolytic cell with the reaction gas into contact with the electrocatalytic component; the electrocatalytic component adopts any one or more of the following methods: Electrocatalytic method (1): at least one electrocatalytic component is provided in the electrolytic cell body, and the outlet of the electrolytic cell gas-liquid mixer faces the electrocatalytic component and / or the electrolytic cathode; Electrocatalytic method (2): Improve the electrocatalytic performance structure of the electrolytic cathode, or improve the electrocatalytic performance structure of both the electrolytic anode and the electrolytic cathode; that is, the electrolytic cathode or the electrolytic anode and the electrolytic cathode are two or more parallel-connected electrodes, and the outlet of the electrolytic tank gas-liquid mixer faces the electrolytic cathode with improved electrocatalytic performance structure or the electrolytic anode and the electrolytic cathode with improved electrocatalytic performance structure; Electrocatalytic method (3): The electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode is improved, and the angle ɑ formed by a part or the whole of at least one of the electrolytic anode and the electrolytic cathode and the straight line of the gas-liquid mixture ejected from the outlet of the electrolytic tank gas-liquid mixer is greater than 0° and less than 90°, and the outlet of the electrolytic tank gas-liquid mixer is oriented toward the electrolytic cathode with improved electrocatalytic performance structure or toward the electrolytic anode and electrolytic cathode with improved electrocatalytic performance structure.

2. The gas-liquid hybrid electrochemical reaction device according to claim 1, characterized in that: The electrolytic cell gas-liquid mixer has an inlet and at least two outlets, or has a structure with a liquid inlet, an air inlet and an outlet. When the electrolytic cell gas-liquid mixer has an inlet and at least two outlets, the outlet extends into the electrolytic cell body and is used to disperse the reaction gas or gas-liquid mixture into the electrolyte in the electrolytic cell for gas-liquid mixing; when the electrolytic cell gas-liquid mixer has a liquid inlet, an air inlet and an outlet, the liquid inlet is connected to the electrolytic cell body by a pipeline, and the outlet is directed toward or extends into the electrolytic cell body, and is used to input the electrolyte in the electrolytic cell into the gas-liquid mixer so that it is mixed with the reaction gas entering the gas-liquid mixer and then returned to the electrolytic cell.

3. The gas-liquid hybrid electrochemical reaction device according to claim 2, characterized in that: The electrocatalytic component in the electrocatalytic method (1) is arranged in the electrolytic cell body and below the electrolyte level, and is used to realize the electrochemical catalytic reaction capability under the action of the electric field force.

4. The gas-liquid hybrid electrochemical reaction device according to claim 3, characterized in that: The electrocatalytic component is a bipolar electrode and / or an insoluble conductor; The bipolar electrode is an insoluble conductor that is placed between the electrolytic anode and the electrolytic cathode and is not connected to an external power source and is immersed in the electrolyte; the insoluble conductor is directly connected to the electrolytic anode or the electrolytic cathode to make The electrolytic anode or the electrolytic cathode becomes an irregularly shaped electrode, wherein the insoluble conductor connected to the electrolytic anode is called an insoluble anode conductor, and the insoluble conductor connected to the electrolytic cathode is called an insoluble cathode conductor.

5. The gas-liquid hybrid electrochemical reaction device according to claim 4, characterized in that: The material of the contact part between the electrolytic cell body and the electrolyte is selected from polymer resin material, or other materials coated with insulating anti-corrosion coating or lined with insulating anti-corrosion material.

6. The gas-liquid hybrid electrochemical reaction device according to claim 5, characterized in that: The surface of the electrolytic anode is selected from at least one material selected from gold, platinum, gold-platinum alloy, titanium-based coated insoluble anode, and graphite; the surface of the electrolytic cathode is selected from at least one material selected from gold, platinum, titanium, copper, alloys containing at least one of the above metals, and graphite; The surface material of the bipolar electrode is at least one of gold, platinum, gold-platinum alloy, and conductive graphite; When the insoluble conductor contacts the electrolytic anode, the surface of the insoluble anode conductor is made of at least one material selected from the group consisting of gold, platinum, gold-platinum alloy, titanium-based coated insoluble anode, and graphite; the surface of the insoluble cathode conductor is made of at least one material selected from the group consisting of gold, platinum, titanium, copper, alloys of the above metals, and graphite.

7. The gas-liquid hybrid electrochemical reaction device according to claim 6, characterized in that: A sealing tank cover with at least one gas outlet is added to the gas-liquid mixing electrolytic tank to seal the electrolytic tank with a hole; the gas outlet of the sealing tank cover is connected to the gas inlet of at least one electrolytic tank gas-liquid mixer and / or other common gas-liquid mixer, or is connected to the atmosphere.

8. The gas-liquid hybrid electrochemical reaction device according to claim 6, characterized in that: Two or more gas-liquid mixed electrolyzers are set up and connected to form a combination of two-stage or multi-stage gas-liquid mixed electrolyzers connected in series with gas pipelines. That is, the gas-liquid mixed electrochemical reaction devices of the front and rear stages are connected through gas pipelines, and the reaction gas escaping from the reaction process of the front-stage gas-liquid mixed electrolyzer is collected and drained to the rear-stage gas-liquid mixed electrolyzer for use as reaction gas raw material.

9. A method for oxidizing an etching solution using the gas-liquid hybrid electrochemical reaction device according to claim 1, characterized in that: The following steps are involved: (1) using the gas-liquid mixed electrochemical reaction device in combination with an etching machine during an etching production process to oxidize an etching liquid, wherein the etching liquid is an etching working liquid and / or etching waste liquid; using the etching working liquid and / or etching waste liquid as the electrolyte of a gas-liquid mixed electrolytic cell in the gas-liquid mixed electrochemical reaction device, connecting an electrolysis power supply, and performing an electrochemical oxidation reaction; (2) starting at least one electrolytic cell gas-liquid mixer in the gas-liquid mixing electrochemical reaction device, mixing the oxidizing gas with the electrolyte to form a gas-liquid mixture, and contacting the mixture with at least one of the electrolytic cathode and the electrocatalytic component, and utilizing the electrolytic electrode and / or the electrocatalytic component with an improved electrocatalytic structure to exert an electrocatalytic effect on the substances to be treated in the etching working solution and / or the etching waste liquid to regenerate the copper etching agent.

10. The method for oxidation treatment of etching solution according to claim 9, characterized in that: When electricity is applied for electrolysis, the gas-liquid mixture containing the oxidizing gas is brought into contact with the negatively charged electrode in the gas-liquid hybrid electrolytic cell, causing the oxidizing gas to undergo an electrochemical reaction. The etching working liquid and / or etching waste liquid are brought into contact with the positively charged electrode in the gas-liquid hybrid electrolytic cell to undergo an electrochemical oxidation reaction, while effectively preventing the electrolytic deposition of metallic copper on the electrolytic cathode, the cathode end of the bipolar electrode, and the insoluble cathode conductor.

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