Electrolysis device with gap communication structure for separating cathode and anode groove areas and electrolysis method thereof

Abstract

The invention discloses an electrolysis device for separating cathode and anode tank areas by a gap communication structure, which comprises an electrolysis tank, an electrolysis anode, an electrolysis cathode and an electrolysis power supply, and is characterized in that the gap communication structure is arranged in the electrolysis tank and divides the electrolysis tank into an anode tank area and a cathode tank area; at least one liquid discharge pipe with a flow control valve is arranged in at least one tank area and is used for controlling the real-time flow condition of the electrolyte in each tank area according to the flow; the electrolytic anode is arranged in the anode tank area and is connected with the positive electrode of the electrolytic power supply; and the electrolytic cathode is arranged in the cathode tank area and is connected with the negative electrode of the electrolytic power supply. According to the electrolysis device, functional division of the anode tank area and the cathode tank area of the electrolysis tank is effectively achieved, meanwhile, use of an electrolysis tank separator is avoided, the electrolysis reaction is facilitated, and the use cost of electrolysis equipment can be reduced. The invention further discloses an electrolysis method implemented by using the electrolysis device.

Description

An electrolysis device and electrolysis method using a gap communication structure to separate anode and cathode slots Technical Field

[0001] The present invention belongs to the field of electrolytic cells and electrolysis technology, and particularly relates to an electrolytic device having a gap communication structure separating anode and cathode cell areas and an electrolytic method thereof. Background Art

[0002] Electrolysis technology is widely used in the chemical and environmental protection industries, including chlor-alkali production, hydrogen production as a new energy source, metal industry processing and purification, production of metal salt solutions, environmental waste liquid COD degradation, and ammonia nitrogen removal waste liquid treatment. The electrolytic cells used in existing electrolysis technology are structurally divided into two types: an electrolytic cell without a partition, and an electrolytic cell with an electrolytic cell partition to divide it into an anode cell area and a cathode cell area (hereinafter referred to as an electrolytic cell with a partition); the electrolytic cell partition includes an anion exchange membrane, a cation exchange membrane, a non-ion-selective partition membrane, a bipolar membrane, a reverse osmosis membrane, etc. Among them,

[0003] (1) In an unpartitioned electrolytic cell, the anode and cathode are placed in the same electrolyte for electrolysis. Since the unpartitioned electrolytic cell does not separate the electrolyte near the anode and the electrolyte near the cathode, both oxidation and reduction reactions occur in the electrolyte. In other words, oxidizing substances in the electrolyte of the unpartitioned electrolytic cell are easily reduced by contact with the cathode, and reducing substances in the electrolyte are easily oxidized by contact with the anode, making it difficult to achieve the reaction purpose in a short period of time.

[0004] (2) Electrolytic cells with separators: The separators in these cells not only effectively separate the anolyte and catholyte during electrolysis, but also allow the electrolysis reaction to proceed smoothly. The separators allow the anolyte to undergo oxidation reactions relatively independently, and the catholyte to undergo reduction reactions relatively independently. Therefore, electrolytic cells with separators have the advantage of significantly higher reaction efficiency than electrolytic cells without separators.

[0005] However, the electrolytic cell separator needs to be replaced after a period of use, is a consumable item, and is relatively expensive. Therefore, the electrolytic cell with a separator has the following disadvantages:

[0006] (1) Replacing the electrolytic cell separator increases the cost of using the electrolytic equipment.

[0007] (2) When an electrolytic cell with a separator is used to treat organic waste liquid in an environmentally friendly manner, some of the organic waste liquid undergoes chemical reactions due to some of its components to generate foamed slurry and / or viscous oil droplets that adhere to the electrolytic cell separator, hindering the ion exchange of the electrolyte between the anode and cathode cell areas, and affecting the normal operation of the electrolytic cell.

[0008] (3) When an electrolytic cell with a separator is used to electrolyze a solid-liquid mixture, the solid matter in the electrolyte will adhere to the separator of the electrolytic cell, hindering the ion exchange of the electrolyte between the anode and cathode cell areas, and affecting the normal operation of the electrolytic cell.

[0009] (4) When using an electrolytic cell with a separator for copper extraction in the metal industry, such as copper chloride electrolysis, when the copper content in the cathode electrolyte is less than 40g / L, loose and brittle metallic copper is typically electrolyzed at the cathode. Fine copper particles float with the electrolyte and adhere to the cell separator. These copper particles become bipolar electrodes, causing current to concentrate. As electrolysis continues, they gradually grow into punctures, eventually piercing and damaging the separator.

[0010] Summary of the Invention

[0011] The first object of the present invention is to provide an electrolysis device with a gap structure separating the anode and cathode tank areas, which effectively realizes the functional division of the anode tank area and the cathode tank area of ​​the electrolysis cell while avoiding the use of electrolysis cell separators, which is beneficial to the progress of the electrolysis reaction and reduces the use cost of the electrolysis equipment.

[0012] A second object of the present invention is to provide a method for performing electrolysis using the above-mentioned device.

[0013] The first object of the present invention is achieved through the following technical solutions.

[0014] An electrolysis device with a gap communication structure separating the anode and cathode tank areas, comprising an electrolysis tank, an electrolysis anode, an electrolysis cathode and an electrolysis power supply, characterized in that:

[0015] The electrolytic cell is provided with a gap communication structure, which divides the electrolytic cell into an anode cell area and a cathode cell area, and at least one discharge pipe with a flow control valve is installed in at least one cell area to control the real-time flow status of the electrolyte in each cell area according to the flow rate;

[0016] The electrolytic anode is placed in the anode tank area and connected to the positive electrode of the electrolytic power supply, and the electrolytic cathode is placed in the cathode tank area and connected to the negative electrode of the electrolytic power supply.

[0017] The working principle of the present invention is to replace expensive, consumable electrolytic cell separators with a combination of a gap connection structure and a flow control valve on the drain pipe to functionally separate the anode and cathode compartments of the electrolytic cell. The present invention connects the anode and cathode compartments of the electrolytic cell only through the gap structure, that is, only a small area of ​​communication is provided between the cathode and anode compartments. This effectively separates the anolyte and catholyte without hindering desired ion migration. The flow control valve on the drain pipe can also be opened, closed, or adjusted to control the flow direction and velocity of the electrolyte in the anode and cathode compartments, or to create a liquid flow trend to prevent undesirable ion migration and solution mixing. That is, in the electrolysis device of the present invention, a flow and / or solution flow trend that is different from the migration direction of the ions or molecules to be blocked can be generated by controlling the flow control valve on the discharge pipe, thereby effectively preventing the electrolyte in one cell zone from entering another cell zone, or effectively preventing the ions in one cell zone from migrating to another cell zone due to the attraction of the electric field, thereby avoiding the phenomenon of large-scale oxidation and reduction reactions occurring simultaneously in the electrolyte of an undivided electrolytic cell. Therefore, during electrolysis, the present invention can orderly and controllably allow the anolyte and catholyte to undergo electrochemical reactions and other chemical reactions that may occur in their respective cell zones under temporary liquid flow separation, thereby achieving an electrolysis function similar to that of an electrolytic cell with a separator without using an electrolytic cell separator. Therefore, the present invention can solve the production difficulties encountered in the use of electrolytic production equipment in existing electrolytic cells with separators, such as electrolyte gelation and slurrying, floating metal powder in the electrolyte, and solid-liquid mixture electrolyte.

[0018] The gap communication structure is an ion exchange channel between the electrolyte in the anode tank area and the electrolyte in the cathode tank area, specifically at least one communication gap and / or communication pipe provided between the anode tank area and the cathode tank area to connect the electrolytes in the two tank areas. The electrolytic cell adopts at least one of the following gap communication structures:

[0019] ① At least a portion of at least one side of the anode tank area and the cathode tank area are joined together, and at least one connecting gap is provided at the joining position, so that the two tank areas are connected to a separately provided pipeline through the connecting gap or simultaneously through the connecting gap.

[0020] The connecting gap can be a straight gap, a curved gap, a polygonal or irregular shape; it can be composed of one or more long gaps, several short gaps, or a combination of long gaps and short gaps; it can form any angle with the bottom surface of the electrolytic cell.

[0021] ②The anode tank area and the cathode tank area are two independent tank areas connected by pipelines.

[0022] The drain pipe is arranged in the anode tank area and / or the cathode tank area, and the flow control valve on the drain pipe is specifically a valve that can be opened and closed and / or has an adjustable opening.

[0023] As a recommended embodiment of the present invention, the electrolytic cell employs a combined high- and low-level cell structure. Specifically, the anode and cathode cell sections of the electrolytic cell are structurally divided into a high-level cell section and a low-level cell section. The bottom of the high-level cell section is higher than the bottom of the low-level cell section, thereby creating a potential energy difference between the solutions in the two cells. The high-level cell section can be either the anode or cathode cell section; correspondingly, the low-level cell section can be either the cathode or anode cell section.

[0024] As another recommended embodiment of the present invention, the electrolytic cell adopts a U-tube combination structure, that is, the anode tank area and the cathode tank area of ​​the electrolytic cell have no structural difference in height, and their bottoms are located on the same horizontal line.

[0025] In the above two recommended implementations, the gap communication structure between the anode tank area and the cathode tank area can adopt either the above structure ① or the above structure ②.

[0026] The flow control valve on the discharge pipe of the present invention is specifically a valve that can be opened and closed and / or has an adjustable opening, and is used to control the outflow of electrolyte from the electrolytic cell. The use of the flow control valve assists in controlling the chemical reaction process of the reaction liquid in each tank zone of the electrolytic cell. Preferably, in an electrolytic cell with a high- and low-level tank zone combination structure, at least one discharge pipe with a flow control valve is installed in the low-level tank zone.

[0027] During the electrolysis process, the electrolytic cell of the present invention is equipped with an electrolytic anode and an electrolytic cathode in the anode and cathode compartments, respectively, and connected to the electrolytic power supply as positive and negative conductive wires. The volumes of the anode and cathode compartments can be equal or unequal, and the volumes of the corresponding compartments are adjusted according to the conditions of the reaction solution (i.e., electrolyte) to achieve more efficient reaction of the reaction solution.

[0028] When a high- and low-level tank area combination structure is adopted, the electrolyte in the high-level tank area and the electrolyte in the low-level tank area respectively form the solution gravity center on different horizontal lines, and the gravity exerted on the solution makes the solution in the high-level tank area have a tendency to flow to the low-level tank area. When the low-level tank area is provided with a discharge pipe with a flow control valve, the flow rate of the solution in the high-level tank area entering the low-level tank area can also be controlled by controlling the opening of the flow control valve on the discharge pipe of the low-level tank area. At the same time, combined with the gap communication structure, it can effectively reduce the situation where the electrolyte in the low-level tank area overflows back into the high-level tank area. According to the specific gravity value of the electrolyte and / or the process requirements for gas evolution, the high-level tank area or the low-level tank area is selected as the anode tank area, and the other tank area opposite is selected as the cathode tank area. Figures 8 and 19 are schematic diagrams of the basic structure of an electrolytic cell adopting a high- and low-level tank area combination structure.

[0029] When a U-tube structure is used, the U-tube principle is utilized to maintain the same level of solution in the anode and cathode compartments. Flow control valves on the compartment drain pipes are then used to adjust the level of the solution in each compartment. Figure 15 illustrates the basic structure of an electrolytic cell using a U-tube structure.

[0030] As a preferred embodiment of the present invention: when a high-low tank area combination structure is adopted, the electrolyte with a larger specific gravity or the electrolyte mixed with solid matter is placed in the low tank area to give full play to the characteristic function of the present invention of temporarily separating the anolyte and the cathode electrolyte.

[0031] The present invention can be improved as follows: a valve and / or gate with adjustable size is installed at the gap communication structure.

[0032] The present invention can be improved as follows: an inlet and / or an outlet are added to the anode tank area and / or cathode tank area. Specifically, when the electrolytic cell adopts a high-low tank area combination structure and is provided with an inlet and / or an outlet (as shown in FIG9 ), if the amount of liquid entering the low tank area through the inlet and the amount of liquid discharged from the drain pipe are substantially balanced, a liquid flow can be formed within the low tank area to effectively prevent the electrolyte in the high tank area from entering the low tank area, allowing the electrolyte in the high tank area to undergo electrochemical oxidation or electrochemical reduction reactions independently.

[0033] The present invention can be improved as follows: during electrolysis operation, the gases produced in the electrolytic cell are collected separately for separate treatment, specifically by adding a gas collecting tank cover and an exhaust pipe on the top of the anode tank area and / or cathode tank area.

[0034] When an exhaust duct is added to the lower tank section of the high-low tank section combination structure, the exhaust duct of the lower tank section forms a U-shaped tube structure with the higher tank section. This allows the outlet of the exhaust duct of the lower tank section to be higher than the electrolyte level in the higher tank section, thus preventing electrolyte overflow from the exhaust duct outlet of the lower tank section due to the U-shaped tube structure. Figure 10 is a schematic diagram of the electrolytic cell structure with a high-low tank section combination structure, an improvement over the structure in Figure 8.

[0035] Preferably, when the exhaust pipe is used to discharge hydrogen at a high altitude, the length of the exhaust pipe for discharging hydrogen is increased according to the surrounding environment to make it a hydrogen high-altitude discharge pipe, so as to discharge the electro-deposited hydrogen safely at a high altitude.

[0036] Preferably, a release chamber is connected to the exhaust duct or its outlet end. The release chamber is a container with an inner diameter larger than the inner diameter of the exhaust duct. When the electrolyte in the tank is a solid-liquid mixture or has a high viscosity, the gas generated during electrolysis often has difficulty precipitating from the electrolyte, resulting in foam that forces the electrolyte into the exhaust duct. The release chamber provides a larger space than the exhaust duct for the foam or solid-liquid mixture that overflows into the exhaust duct, effectively preventing foam overflow and splashing caused by foam collapse during electrolysis.

[0037] The present invention can be improved by adding a stirring device within the anode tank and / or cathode tank. Specifically, the stirring device can be a liquid flow stirrer or a mechanical stirrer. The stirring device can ensure uniformity in the concentration and temperature of the electrolyte during the electrochemical reaction. Either a mechanical stirrer or a liquid flow stirrer can achieve this goal. The liquid flow stirrer creates a liquid flow within the electrolyte through a pump and pipes to achieve the stirring effect.

[0038] The present invention can be further improved by adding a stirring device to the anode and / or cathode tanks, installing a gas collecting tank cover and an exhaust pipe on the top of the tank, and connecting a gas-liquid separator to the exhaust pipe. Using a liquid flow stirrer as the stirring device can more effectively direct the reaction gas to the gas-liquid separator, thereby accelerating the escape and separation of gas from the solution.

[0039] The present invention can be further improved by connecting a gas-liquid separator to the exhaust pipe. The gas-liquid separator is a tubular cavity or container with at least one gas-liquid mixture inlet, at least one gas outlet, and at least one liquid outlet. Specifically, a tubular cavity or tank with three or more passages, such as a tee or cross-tube, can be used as the gas-liquid separator. Figure 12 is a schematic diagram of the electrolytic cell structure after the above structure has been improved.

[0040] The present invention can be improved as follows: when the electrolyte in the lower tank of the high-low tank combination structure is a solid-liquid mixture, the bottom plate of the high tank is designed to be an inclined plate structure inclined toward the lower tank. This helps solid matter that overflows from the lower tank into the high tank due to gassing surge during electrolysis to return to the lower tank along the inclined plate under the action of gravity, allowing the electrolysis to operate normally. Figure 11 is a schematic diagram of the electrolytic cell structure after the bottom plate of the high tank is replaced with an inclined plate inclined toward the lower tank in the structure of Figure 10.

[0041] The present invention can be improved by installing a bubble barrier, specifically a filter cloth and / or screen, within at least one of the gap communication structures to prevent bubbles generated during the reaction in one tank zone from crossing over to another tank zone and causing undesirable chemical reactions. Figure 13 is a schematic diagram of the improved electrolytic cell structure.

[0042] The present invention can be improved as follows: a bipolar electrode is placed in at least one of the connecting pipes in the gap communication structure to enhance electrolysis efficiency. The bipolar electrode is made of an insoluble conductive material. After the bipolar electrode is placed, the internal space of the connecting pipe at both ends of the bipolar electrode becomes the electrolyte reaction chamber for the bipolar electrode. In the high- and low-level tank zone combination structure, the bipolar electrolysis electrolyte reaction chamber near the high-level tank zone is referred to as the high-level tank zone electrolyte reaction chamber, and the bipolar electrolysis electrolyte reaction chamber near the low-level tank zone is referred to as the low-level tank zone electrolyte reaction chamber.

[0043] Preferably, when the bipolar electrodes are in the connecting pipes, gaps are left between them and the pipe walls. This allows the solution in the electrolyte reaction chamber of the upper tank to flow slowly through the gaps into the electrolyte reaction chamber of the lower tank, or allows the solution to flow between the anode and cathode tanks. The solutions in the electrolyte reaction chambers at both ends undergo redox reactions in the connecting pipes, preventing the solution in the electrolyte reaction chambers from affecting the primary chemical reactions in the anode and cathode tanks. Figure 14 shows a schematic diagram of the electrolytic cell structure after adding bipolar electrodes, taking the high and low tank combination structure as an example.

[0044] The present invention can be improved as follows: in order to better perform the electrolytic gas evolution reaction of the electrolyte, at least one of the following structural improvements is adopted:

[0045] (1) The bottom ends of the electrolytic anode and the electrolytic cathode are higher than the position of the gap communication structure to reduce the crosstalk between the electrolytic gas on the electrolytic anode and the electrolytic cathode and / or the gas produced by the reaction in the electrolyte, which may cause adverse chemical reactions. The improved structure is shown in Figure 15;

[0046] (2) Installing a switch valve and / or gate on the gap communication structure, opening the valve or gate as a passage during electrolysis and closing it after the electrolysis reaction is completed, so that the solution in each tank area can be processed independently after the electrolysis reaction; the structure is improved as shown in Figure 16 or Figure 17.

[0047] The electrolytic anode of the present invention can be selected from at least one of an electrode having a surface coating of gold, platinum, nickel, and / or alloys thereof, a titanium-based coating, and conductive graphite. The electrolytic anode is selected based on the properties of the electrolyte. The electrolytic cathode can be made of a material having a surface coating of gold, platinum, silver, titanium, copper, tin, iron, nickel, and / or alloys thereof, stainless steel, or conductive graphite.

[0048] The present invention can also be improved as follows: an electrolyte circulation flow tank is added, and the electrolyte circulation flow tank is connected to the anode tank area or the cathode tank area through at least two pipes to form a liquid flow circulation, wherein at least one connecting pipe is provided with a pump to solve the production problem of a small volume of the electrolytic cell area and a large volume of reaction liquid to be processed.

[0049] Preferably, when the electrolytic cell adopts a U-tube combination structure, an automatic level control and compensation system for the circulating electrolyte is added. Specifically, a pressure sensor and / or a level gauge is installed in the electrolyte circulating flow cell and / or the cell area connected thereto, and at least one pump on the connecting pipe is a variable frequency pump. The operating state of the variable frequency pump is controlled and adjusted according to the data measured by the pressure sensor and / or the level gauge. The variable frequency pump is used to control the circulating flow rate so that the center of gravity of the electrolyte in the anode cell area and the cathode cell area remains in a stable state of mutual balance during the flow, thereby reducing the impact on production due to uncontrolled electrolyte flow during electrolysis operation.

[0050] The present invention can be improved as follows: a hydrogenation device is added (the structure of the hydrogenation device is described in Chinese Patent Application No. 202310394209.X, "A Method and Apparatus for Utilizing Hydrogen to Participate in Organic Reactions at Normal Pressure," and in Chinese Patent No. ZL202220949622.9, "An Apparatus for Safely Processing Hydrogen by Electrochemical Processes," for promoting the electrolyzed hydrogen to participate in other chemical reactions or to eliminate it. The hydrogenation device is connected to at least one of the exhaust pipes, or the hydrogenation device and the cathode tank are integrated into a single unit (see Examples 7 and 8), for promoting the electrolyzed hydrogen to participate in other chemical reactions in the electrolyte.

[0051] The present invention can also be improved as follows: additional detection sensors and automatic detection and feeding controllers are provided so that during the electrolysis process, the electrolyte in the anode tank area and / or cathode tank area and / or electrolyte circulation flow tank is detected and the working current output by the electrolysis power supply is controlled and / or started and shut down, so as to implement safe and efficient automatic process control. The detection sensor is placed in the electrolytic cell and / or in a container connected to the electrolytic cell for liquid flow and / or on a connecting pipe. The detection sensor is selected from at least one of a pH meter, a hydrometer, an oxidation-reduction potentiometer (ORP meter), a pH meter, a thermometer, a liquid level meter, a photoelectric colorimeter, a viscometer, a hydrogen detector, a chlorine detector and a COD detector. The detection signal input end of the automatic detection and feeding controller is connected to the detection signal output section of the detection sensor, and the control signal output end of the automatic detection and feeding controller is connected to the control signal input end of at least one of the electrolysis power supply, a valve and a gate.

[0052] The present invention can also be improved as follows: a temporary storage tank is added to temporarily store materials and used as a process chemical reaction tank. The temporary storage tank is connected to the electrolytic tank and / or the electrolyte circulation flow tank through a pipeline.

[0053] The present invention can also be improved by adding an overflow buffer tank to solve the problem of solution flow between the various tanks in the device. The overflow buffer tank is connected to at least one of the electrolytic tank, electrolyte circulation tank, and temporary storage tank via a pipeline, or is installed on the connecting pipeline between any two tanks.

[0054] The present invention can also be improved by adding a gas-liquid mixer to collect the escaping gas from the reaction for reuse in a gas-liquid reaction or to pump it into an exhaust gas treatment tank for environmentally friendly treatment. The gas-liquid mixer is connected to at least one of the electrolytic cell, electrolyte circulation tank, temporary storage tank, and overflow buffer tank via a gas pipeline. Preferably, the gas-liquid mixer is a vacuum jet gas-liquid mixer and / or a spray tower gas-liquid mixer.

[0055] The present invention can also be improved as follows: a solid-liquid separator is added, and the solid-liquid separator is connected to at least one of the electrolytic cell, electrolyte circulation flow tank, temporary storage tank, and overflow buffer tank through a pipeline, or is arranged on the connecting pipe between any two of the above tanks, for filtering and removing solid impurities in the reaction liquid.

[0056] The present invention can also be improved as follows: a hot and cold temperature exchanger is added to adjust and control the temperature of the reaction solution according to the process. The hot and cold temperature exchanger is arranged in at least one of the electrolytic cell, the electrolyte circulation flow tank, the temporary storage tank, and the overflow buffer tank.

[0057] The present invention can also be improved by adding an electrolyte solution current isolator for production safety, which electrically isolates the electrolyte in the electrolytic cell from the outside world. This electrolyte solution current isolator is installed on the electrolytic cell's feed inlet and / or discharge pipes, and / or drain pipe. It utilizes a solution spraying device to transform the electrolyte solution into droplets during the spraying process, thereby interrupting conductivity. The specific structure of the current isolator is shown in Figure 18.

[0058] The second object of the present invention is achieved through the following technical solutions.

[0059] An electrolysis method implemented using the electrolysis device comprises the following steps:

[0060] (1) Select an electrolytic cell with a suitable gap communication structure according to the process requirements, add the solution or solid-liquid mixture to be electrochemically treated into the anode tank area and / or cathode tank area respectively, and turn on the electrolysis power supply to start the electrolysis operation;

[0061] (2) During the electrolysis operation, the flow control valve on the discharge pipe is opened or closed or the opening is adjusted to control the flow of the solution in the anode and cathode tank areas or the outflow of the solution on the discharge pipe, so that the electrolyte in the anode tank area and the cathode tank area can undergo electrochemical reactions and other possible chemical reactions in an orderly and controllable manner.

[0062] During the electrolysis operation, the present invention uses the electrolyte flow rate and / or reaction time length of the anode tank area and the cathode tank area as the control basis for the reaction under the set electrolysis current conditions. In addition, it is also necessary to consider the change in the specific gravity parameter of the electrolyte before and after the reaction during the reaction process.

[0063] The present invention can be improved as follows: due to the gap communication structure of the present invention, the distance between the electrolytic anode and the electrolytic cathode is relatively far, resulting in an increase in the resistance between the two electrodes of the present invention under the condition of electrolyte with the same electrolyte concentration compared with the existing electrolytic cell with a separator; in order to improve the production efficiency of the electrolytic cell, the electrolyte concentration in the electrolyte can be increased for adjustment and / or an electrolytic power supply with a higher output voltage can be selected to meet the requirements of safe electricity use.

[0064] The present invention can also be improved as follows: Because the aforementioned electrolytic power supply can use a higher output voltage to improve the production efficiency of the electrolytic cell, the operating voltage output by the power supply of the present invention may be greater than the human body's safe voltage of 36 volts. To ensure safe production, it is necessary to add a safe operating area space, use a photoelectric sensor to establish a safe operating area space, and add an electrolyte solution current isolator. The photoelectric sensor uses an optical path to demarcate a control space. When a person's limb enters the controlled area, the light is blocked and a signal is generated to shut down the electrolytic power supply. The electrolyte solution current isolator uses a solution spraying device to transform the electrolyte solution into droplets during the spraying process to achieve the function of conductive interruption.

[0065] Compared with the prior art, the present invention has the following beneficial effects:

[0066] 1. The present invention adopts a gap communication structure to functionally separate the anode and cathode cell areas of the electrolytic cell and a flow control valve on the discharge pipe. This solves the production process problems of existing electrolytic cells with separators, such as slurrying and gelling of the electrolyte during the electrolysis process, solid-liquid mixture electrolyte, and floating metal particles in the electrolyte, which damage the electrolytic cell.

[0067] 2. The present invention can control the reaction process of the electrolyte in the anode and cathode tank areas separately during the electrolysis process, so that the anode and cathode tank areas can still carry out their own electrochemical reactions on the solutions in each tank area and separately collect and process the gases produced in each electrolyte without installing an electrolytic cell separator, so that the chemical reaction can achieve the process purpose.

[0068] 3. The gap communication structure of the present invention separates the anode and cathode areas of the electrolytic cell. It has a simple structure, no consumable separators, and eliminates the need to replace separators. Therefore, it can significantly reduce the operating costs of electrolytic production.

[0069] 4. The process and device of the present invention are simple, safe and reliable to operate and have wide market applicability. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] The present invention will be further described below with reference to the accompanying drawings.

[0071] FIG1 is a flow chart of an electrolysis device and a process for separating anode and cathode tank regions using a gap communication structure according to Example 1 of the present invention;

[0072] FIG2 is a flow chart of an electrolysis device and a process according to Embodiment 2 of the present invention, in which a gap-connected structure is used to separate the anode and cathode tank areas;

[0073] FIG3 is a flow chart of an electrolysis device and a process for separating anode and cathode tank regions using a gap communication structure according to Example 3 of the present invention;

[0074] FIG4 is a flow chart of an electrolysis device and a process for separating anode and cathode tank regions using a gap communication structure according to Example 4 of the present invention;

[0075] FIG5 is a flow chart of an electrolysis device and a process for separating anode and cathode tank regions using a gap communication structure according to Example 5 of the present invention;

[0076] FIG6 is a flow chart of an electrolysis device and a process in which a gap-connected structure is used to separate the anode and cathode tank areas according to Example 6 of the present invention.

[0077] FIG7 is a flow chart of an electrolysis device and a process in which a gap-connected structure is used to separate the anode and cathode tank areas according to a seventh embodiment of the present invention.

[0078] FIG8 is a schematic diagram of the basic structure of the high and low tank areas of the electrolytic cell in which the anode and cathode tank areas are separated by a gap communication structure;

[0079] FIG9 is a schematic diagram of a high-low tank area combination structure of an electrolytic cell having a gap-connected structure separating the anode and cathode tank areas, and having a low tank area inlet and a high tank area outlet;

[0080] FIG10 is a schematic diagram of the combined structure of high and low tank areas of an electrolytic cell having a gap-connected structure separating the anode and cathode tank areas, and having a feed inlet and a low tank area exhaust duct;

[0081] FIG11 is a schematic structural diagram of an electrolytic cell having an exhaust pipe and a release chamber in which the anode and cathode tank areas are separated by a gap communication structure;

[0082] FIG12 is a schematic structural diagram of an electrolytic cell having an exhaust pipe and a gas-liquid separator in which the anode and cathode tank areas are separated by a gap communication structure;

[0083] FIG13 is a schematic structural diagram of an electrolytic cell having a gap-connected structure separating the anode and cathode tank areas and provided with a bubble barrier, an exhaust pipe, and a gas-liquid separator;

[0084] FIG14 is a schematic diagram showing the structure of bipolar electrodes placed in the communicating pipe of an electrolytic cell with a gap communicating structure separating the anode and cathode cell areas;

[0085] FIG15 is a schematic diagram of a U-shaped tube assembly structure of an electrolytic cell with a gap connecting structure separating the anode and cathode tank areas and connected to a temporary storage tank;

[0086] FIG16 is a schematic diagram showing the structure of an on-off valve installed on a gap communication structure of an electrolytic cell in which a gap communication structure separates the anode and cathode tank areas;

[0087] FIG17 is a schematic diagram showing the structure of a gate installed on a gap communication structure of an electrolytic cell in which a gap communication structure separates the anode and cathode tank areas;

[0088] FIG18 is a schematic structural diagram of a current-breaking isolator;

[0089] FIG19 is a schematic diagram of the basic structure of the high and low tank areas of the electrolytic cell where the anode and cathode tank areas are separated by a gap communication structure.

[0090] Figure numerals: 1-electrolytic cell with a gap structure separating the anode and cathode zones, 2-high-level tank zone, 3-low-level tank zone, 4-electrolysis power supply, 5-electrolysis anode, 6-electrolysis cathode, 7-flow control valve, 8-gas collecting tank cover, 9-exhaust pipe, 10-solution communication gap between tanks, 11-small pipe for solution communication between tanks, 12-bipolar electrode, 13-drain pipe, 14-feed port of high-level tank zone, 15-feed port of high-level tank zone, 16-feed port of low-level tank zone, 17-impeller stirring device, 18-liquid circulation stirring device, 19-gas-liquid separator, 20-cold and hot temperature exchanger, 21-vacuum ejector, 22-spray tower, 23-temporary storage tank, 24-solid-liquid separator, 25-overflow buffer tank, 26-detection sensor, 27-automatic detection and feeding control Controller, 28-solution to be treated, 29-solution treated by electrolysis, 30-valve, 31-pump, 32-copper metal electrolyzed on the cathode, 33-water-oil separator, 34-anodic electrolysis reaction solution, 35-cathode electrolysis reaction solution, 36-bipolar electrode electrolyte reaction chamber, 37-bubble barrier (filter cloth or filter screen), 38-sodium hydroxide, 39-sulphuric acid, 40-fastening screws, 41-hydrogenation device components, 42-tap water, 43-electrolyte solution, 44-safety area space photoelectric sensor, 45-electrolyte solution current cut-off isolator, 46-hydrogen high-altitude safety discharge pipe, 47-gate, 48-U-shaped anode tank area, 49-U-shaped cathode tank area, 50-electrical insulator particles, 51-U-shaped tube structure tank area inlet. DETAILED DESCRIPTION

[0091] The present invention is further described below with reference to specific examples.

[0092] In the following embodiments, the cell body of the electrolytic cell with a gap structure separating the anode and cathode, the electrolytic anode, the electrolytic cathode, the vacuum ejector, the spray tower, the temporary storage tank, the overflow buffer tank, the stirring device, the hydrogen high-altitude safety discharge pipe, and the gas-liquid separator used are all products manufactured by Yegao Environmental Protection Equipment Manufacturing Co., Ltd. in Foshan City, Guangdong Province, China. The detection sensors, automatic detection and feeding controller, solid-liquid separator, electrolytic power supply, valves, pumps, and chemical raw materials are all commercially available products. In addition to the above-mentioned products, those skilled in the art can also select other products with similar performance to the above-mentioned products according to routine selection, and all of them can achieve the purpose of the present invention.

[0093] Example 1

[0094] As shown in FIG1 , this embodiment uses the gap communication structure of FIG8 to separate the anode and cathode tank areas of the electrolytic cell, which is a basic embodiment of the electrolytic device and electrolytic method of the present invention in which a gap structure separates the anode and cathode tank areas.

[0095] The electrolytic cell 1 comprises a high- and low-level cell structure. The bottoms of the high- and low-level cell sections 2 and 3 are on the same horizontal plane. One side of the high- and low-level cell sections partially overlaps, forming an inter-cell solution communication gap 10. The high- and low-level cell sections serve as cathodes, while the high- and low-level cell sections serve as anodes. The volume of each of the cathode and anode cell sections is 100 liters. The low-level cell section 3 is equipped with a drain pipe 13. A flow control valve 7 is installed on the drain pipe 13. The low-level cell section 3 also features a gas collecting tank cover and an exhaust pipe 9, which are connected to a solid-liquid separator 24 for circulation.

[0096] The insoluble anode is a titanium-based coating anode, the electrolytic cathode is a titanium plate, and the output voltage of the electrolytic power supply can reach 9V.

[0097] The solution 28 to be treated in this embodiment is the iron-containing acidic copper chloride etching waste liquid of the circuit board, with an acidity of 2M, a copper ion concentration of 40g / L, a divalent iron ion concentration of 50g / L, and a volume of 500L of the solution to be treated.

[0098] The operation steps of this embodiment are as follows:

[0099] (1) With the flow control valve 7 closed, the solution 28 to be treated is injected into the high-level tank area 2 until the liquid level of the solution in the high-level tank area reaches the process requirement.

[0100] (2) The electrolysis power supply 4 is turned on to allow the electrolytic cell of the high and low tank area combination structure to perform electrolysis operation. On the insoluble anode, an electrochemical reaction occurs in which divalent iron ions are oxidized to trivalent iron ions, a small amount of monovalent copper ions are oxidized to divalent copper ions, and chlorine is electrolyzed. The main electrochemical reaction at the electrolytic cathode is the electrolysis of metallic copper on the cathode. During the process, some ions in the electrolyte migrate between the positive and negative tank areas.

[0101] (3) The flow control valve 7 is fine-tuned and opened to continuously flow out the electrolytically treated solution 29. The collected solution is ferric chloride and cupric chloride solution. At the same time, the liquid level in the high-level tank area is continuously replenished to ensure normal electrolysis.

[0102] This embodiment demonstrates that the electrolysis apparatus and method of the present invention can effectively temporarily separate the electrolytes in the anode and cathode cell zones, electrolyze the solution containing a lower copper ion concentration to extract copper, and electrolytically oxidize the iron-containing acidic etching waste liquid to regenerate the copper-etching agent, ferric chloride. During the electrolysis process, the electrolytic cell of the present invention, with its high-low cell zone structure, discharges an appropriate amount of anolyte by regulating the opening and closing of flow control valve 7, allowing the electrolyte in the high-level cell zone to flow in a controlled manner to the low-level cell zone, thereby reducing the migration of trivalent iron ions generated in the anode cell zone into the cathode cell zone and preventing the metallic copper electrolyzed at the cathode from being reversely etched and dissolved.

[0103] Therefore, this embodiment effectively solves the problem of inefficient reactions caused by both oxidation and reduction reactions occurring in the electrolyte when using an unpartitioned electrolytic cell. Furthermore, the low concentration of copper ions in the cathode electrolyte allows for the electrolysis of sponge copper, which floats in the cathode electrolyte. Because the electrolytic cell structure of the present invention lacks partitions, the process problem of sponge copper powder damaging the electrolytic cell equipment is eliminated.

[0104] Through the above operation, the circuit board iron-containing acidic etching waste liquid 28 is electrolytically treated to extract copper. The copper ion concentration in the waste liquid is reduced from the original 40g / L to 22g / L after electrolytic copper extraction, and an acidic ferric chloride copper etching agent is prepared for recycling.

[0105] Example 2

[0106] As shown in Figure 2, this embodiment uses the electrolytic cell with a high-low tank area combination structure of Figure 10, with the cathode and anode tank areas each having a volume of 100 liters, and a liquid level gauge 26 installed in the cathode tank area. Two temporary storage tanks are also added.

[0107] The electrolytic cell 1 is a combination structure of high and low level tank areas, and the bottom of the high level tank area 2 is higher than the bottom of the low level tank area 3. One side of the high level tank area is partially connected to one side of the low level tank area, and a gap 10 for connecting the solutions between the tanks is provided at the bonding position. In this embodiment, the high level tank area 2 is used as the cathode tank area, and the low level tank area 3 is used as the anode tank area. The high level tank area 2 is equipped with a detection sensor 26 and a control pump 31 for adding the solution 28-2 that needs to be treated, and the high level tank area 2 is provided with an exhaust pipe 9-2. The low level tank area 3 is provided with an exhaust pipe 9-1. The low level tank area 3 is provided with a drain pipe 13, on which a flow control valve 7 is installed and connected to the temporary storage tank 23-1. The high level tank area 2 is also connected to the temporary storage tank 23-2 for adding the solution that needs to be treated thereto.

[0108] The insoluble anode of the electrolytic cell is a platinum plate anode, the electrolytic cathode is a titanium plate, and the output voltage of the electrolytic power supply can reach 36 V. The detection sensor 26 is a liquid level meter.

[0109] In this embodiment, solution 28-1 to be treated is wastewater from ammonia-alkaline copper chloride etching of circuit boards, containing 1700 mg / L of ammonia nitrogen and 3 g / L of copper ions. Sodium hydroxide is added to the 500 liters of wastewater in temporary storage tank 23-2 to adjust the pH of the solution to 11, yielding solution 28-2 to be treated.

[0110] The operation steps of this embodiment are as follows:

[0111] (1) With the flow control valve 7 closed, the solution 28 - 2 to be treated is injected into the high-level tank 2 until the liquid level in the high-level tank reaches the position controlled by the liquid level gauge 26 , and the pump 31 is shut down.

[0112] (2) The electrolysis power supply 4 is turned on to allow the electrolytic cell with the high and low cell area combination structure to perform electrolysis operation; at this time, the electrolyte in the anode and cathode cell areas is temporarily and effectively separated, chlorine is electrolytically deposited on the insoluble anode to generate sodium hypochlorite, and hydrogen and sponge copper particles are electrolytically deposited on the electrolytic cathode; during the electrolysis process, some ammonium and copper ions in the anode cell area migrate to the cathode cell area, and some chloride ions in the cathode cell area migrate to the anode cell area, and the sodium hypochlorite in the anode cell area reacts with ammonia to produce nitrogen.

[0113] (3) The solution in the temporary storage tank 23-1 was sampled and tested for its ammonia nitrogen concentration. The test result was 340 mg / L, and the treatment result met the process standard.

[0114] This embodiment demonstrates that the electrolysis method and apparatus of the present invention can be used to treat ammonia-nitrogen-containing wastewater. The chemical reaction is as follows: 3NaClO+2NH3→3NaCl+3H2O+N2↑

[0115] During electrolysis, the electrolytic cell of the present invention, with its high-low tank structure, utilizes gravity to force the solution in the high tank to flow toward the low tank, thereby reducing the migration of chlorine and sodium hypochlorite generated in the anode tank into the cathode tank where they are consumed. Therefore, this embodiment effectively addresses the problem of low reaction efficiency associated with undivided electrolytic cells. Furthermore, since the electrolytic cell structure of the present invention lacks a separator, the process problem of sponge copper particles in the electrolyte adhering to the cell separator and damaging the electrolytic cell equipment is eliminated.

[0116] After the above operation, the ammonia alkaline copper chloride ammonia etching and washing plate waste liquid is prepared and then electrolytically precipitated to remove chlorine and generate sodium hypochlorite to react with NH3. After treatment, the ammonia nitrogen impurity of the treated solution 29 is 340 mg / L.

[0117] Example 3

[0118] As shown in FIG3 , this embodiment uses the electrolytic cell with a high-low tank area combination structure of FIG11 , wherein the volume of the cathode and anode tank areas is 100 liters each.

[0119] The electrolytic cell 1 is a combination of high and low-level tank sections. The bottom of the high-level tank section 2 is higher than the bottom of the low-level tank section 3, and the bottom plate of the high-level tank section 2 is inclined toward the low-level tank section 3. One side of the high-level tank section is partially joined to one side of the low-level tank section, and a connecting gap is provided at the joint. The high-level tank section 2 is provided with an exhaust pipe 9-2. The low-level tank section 3 is provided with an exhaust pipe 9-1, which is connected to a release chamber; it is also provided with a drain pipe 13 with a flow control valve 7. Detection sensors 26-1 and 26-2, a hot and cold temperature exchanger 20, and a liquid circulation and stirring device 18 are installed in the low-level tank section 3.

[0120] The upper tank area 2 is used as the cathode tank area, the lower tank area is used as the anode tank area, the insoluble anode and the electrolytic cathode are both made of nickel plates, and the output voltage of the electrolytic power supply can reach 60 V. The detection sensor 26-1 is a photoelectric colorimeter sensor, and the detection sensor 26-2 is a thermometer.

[0121] The hot and cold temperature exchanger is used to control the temperature of the anolyte at 10°C.

[0122] The solution 28 to be treated is a solid-liquid mixture of manganese dioxide solid, sodium hydroxide, and sodium manganate, wherein the concentration of sodium manganate is 7.47 g / L. The sodium manganate solution is produced by electrolysis. The chemical reaction formula is as follows:

[0123] Electrolysis reaction: 2Na2MnO4+2H2O→2NaMnO4+2NaOH+H2↑

[0124] Reduction reaction: 2NaMnO4+MnO2+4NaOH→3Na2MnO4+2H2O

[0125] The operation steps of this embodiment are as follows:

[0126] (1) With the flow control valve 7 closed, the solution 28 to be treated is injected into the high-level tank area until the liquid level meets the process requirements.

[0127] (2) The electrolysis power supply 4 is turned on to carry out the electrolysis operation and the hot and cold temperature exchanger 20 and the liquid circulation stirring device 18 are started. At this time, the solutions in the anode and cathode tank areas are temporarily and effectively separated. Part of the sodium manganate in the anode tank area undergoes electrochemical oxidation reaction to produce sodium permanganate, which then undergoes a neutralization reaction with manganese dioxide and sodium hydroxide to produce more sodium manganate. The main reaction in the cathode tank area is the electrolysis of hydrogen accompanied by the reduction of a small amount of sodium manganate to manganese dioxide. The manganese dioxide solid in the cathode tank area falls back to the anode tank area due to gravity.

[0128] (3) During the electrolysis process, after the anolyte 34 reaches the process setting value of the photoelectric colorimeter, the electrolysis power supply 4, the hot and cold temperature exchanger 20, and the liquid circulation stirring device 18 are turned off, and the flow control valve 7 is opened to extract part of the electrolyte in the anode tank area to obtain the prepared sodium manganate solution product.

[0129] During electrolysis, the electrolytic cell of the present invention, with its high-low tank structure, utilizes gravity to force the solution in the high tank to flow toward the low tank, thereby reducing the migration of sodium manganate and sodium permanganate generated in the anode tank into the cathode tank where they are consumed by electrochemical reduction. Therefore, this embodiment effectively addresses the problem of low reaction efficiency associated with undivided electrolytic cells. Furthermore, since the electrolytic cell structure of the present invention lacks a separator, solid matter in the solid-liquid mixture electrolyte does not adhere to the cell separator, hindering the electrolysis reaction and damaging the electrolytic cell equipment.

[0130] The above operation can solve the process problem of electrochemical oxidation reaction of solid-liquid mixture electrolyte alone. In this embodiment, the solution 28 to be processed originally contained 7.47 g / L of sodium manganate, and after processing, a product solution with a sodium manganate concentration of 18 g / L was obtained.

[0131] Example 4

[0132] As shown in FIG4 , this embodiment adopts an electrolytic cell with a high and low tank area combination structure as shown in FIG14 .

[0133] The bottom of the upper tank section 2 of the electrolytic cell is higher than the bottom of the lower tank section 3. The upper tank section 2 serves as the anode section, while the lower tank section 3 serves as the cathode section. One side of the upper tank section is partially joined to another side of the lower tank section, with a gap 10 providing intertank solution communication at the joint. The bottom of the upper tank section 2 is also connected to the lower tank section 3 via a small intertank solution communication pipe 11. A bipolar electrode 12 is placed within this intertank solution communication pipe 11.

[0134] The high-level tank area 2 is provided with a high-level tank area discharge port 15, and the low-level tank area is provided with a drainage pipe. Flow control valves 7-1 and 7-2 are respectively provided on the pipeline of the high-level tank area discharge port 15 and the drainage pipe. The two tank areas each have a volume of 100 liters, and a stirring device, a hot and cold temperature exchanger, and multiple detection sensors are added to the two tank areas. The high-level tank area 2 and the low-level tank area 3 are also provided with feed ports. The discharge port of the high-level tank area 2 is connected to the temporary storage tank 23-3 through the electrolyte solution current-breaking isolator 45-2, and the temporary storage tank 23-3 is then connected to the feed port of the low-level tank area 3. The drainage pipe of the low-level tank area 3 is connected to the temporary storage tank 23-2 through the electrolyte solution current-breaking isolator 45-1, and then to the temporary storage tank 23-1 equipped with a vacuum ejector 21. The device of this embodiment also includes a set of safe area space photoelectric sensors. Detection sensors 26 - 1 and 26 - 2 are installed in the low-level tank area 3 , and detection sensors 26 - 3 , 26 - 4 , 26 - 5 and 26 - 6 are installed in the high-level tank area 2 .

[0135] The electrolytic cell uses an insoluble anode coated with gold, a platinum cathode, and an electrolytic power supply with an output voltage of up to 80 V. Sensors 26-1 and 26-3 are thermometers, sensors 26-2 and 26-4 are ORP meters, and sensors 26-5 and 26-6 are liquid level gauges.

[0136] In this embodiment, the temporary storage tank 23-3 collects solution 29-3, which has undergone oxidation treatment in the upper tank area, and transfers it to the lower tank area for reduction treatment. The combined treatment of the temporary storage tank 23-1 and the vacuum ejector 21 collects oxygen escaping from the upper tank area for recycling. Solution 29-2, which has undergone electrolytic reduction treatment, undergoes an oxidation reaction with oxygen to produce solution 29-1. This process flow allows for the separate electrochemical treatment of each electrolyte in a combined upper and lower tank electrolytic cell.

[0137] The solution 28 to be treated in this embodiment is alkaline degreasing waste liquid produced when electroplating parts are cleaned. The COD value of the solution is 31000 mg / L, and the volume of the solution is 400 L.

[0138] This embodiment illustrates that the electrolysis method and apparatus of the present invention can effectively degrade COD in organic wastewater using an "oxidation-reduction-oxidation" treatment process.

[0139] The steps of this embodiment are as follows:

[0140] (1) Close all valves and add the solution 28 to be treated into the high-level tank area 2 until the liquid level reaches the set value of the liquid level gauge 26-5.

[0141] (2) Stirring devices 17 and 18 are turned on, and hot and cold temperature exchangers 20-1 and 20-2 are activated to control the electrolyte at 70°C. The electrolysis power supply 4 is activated to perform electrolysis. The two hot and cold temperature exchangers are controlled to perform heat exchange based on the detection results of detection sensors 26-1 and 26-3. The adjustable opening of flow control valve 7-1 and the output current of electrolysis power supply 4 are controlled or shut down based on the detection results of detection sensor 26-2. During the electrolysis process, oxygen is electrolytically deposited on the insoluble anode, and hydrogen is obtained on the electrolysis cathode.

[0142] When the measured value of detection sensor 26-4 rises to the set value, flow control valve 7-2 is opened according to process requirements, and pump 31-4 is activated to divert part of the solution in the high-level tank area through the current-breaking isolator 45-2 into the temporary storage tank 23-3. When the liquid level drops to the set value of liquid level gauge 26-6, flow control valve 7-2 and pump 31-4 are closed. The solution 28 to be treated is then added to the high-level tank area until the liquid level reaches the set value of detection sensor 26-5. When detection sensor 26-2 drops to the process set value, electrolysis power supply 4 and stirring devices 17 and 18 are shut down according to process control, and flow control valve 7-1 is opened. Pump 31-3 is activated to pump part of the solution in the low-level tank area through the current-breaking isolator 45-1 to the temporary storage tank 23-2 for temporary storage. When the liquid level in the high-level tank area drops to the liquid level setting value of detection sensor 26-6, flow control valve 7-1 is closed and pump 31-5 is started to add the electrolytically treated solution 29-3 to the low-level tank area until the liquid level in the high-level tank area returns to the original high-level setting value of detection sensor 26-5. Then, electrolysis power supply 4 is restarted and stirring devices 17 and 18 are activated to continue operation until the treatment of solution 28 is completed. Pump 31-2 is started to pump the electrolytically treated solution 29-2 from temporary storage tank 23-2 into temporary storage tank 23-1. The vacuum ejector 21 is used to absorb oxygen escaping from the anode tank area of ​​the electrolytic cell for oxidation reaction.

[0143] During the electrolysis process, the electrolytic cell of the present invention, with its high-low tank zone combination structure, utilizes the gravity acting on the solution to cause the solution in the high-level tank zone to flow toward the low-level tank zone. Furthermore, the flow control valves controlling the drain pipes of the two tank zones reduce the amount of electrolyte in the cathode zone from entering the anode zone, thereby effectively and temporarily separating the electrolyte in the anode and cathode zones. Therefore, this embodiment effectively solves the problem of low reaction efficiency when using an electrolytic cell without a partition. Furthermore, because the electrolytic cell structure of the present invention lacks a partition, there is no process problem of viscous oil droplets in the electrolyte adhering to the electrolytic cell partitions during electrochemical environmental treatment of organic wastewater, hindering the electrolysis reaction and damaging the electrolytic cell equipment.

[0144] After the above operations, the alkaline degreasing waste liquid produced when the electroplated parts are cleaned is electrochemically treated under the added production safety facilities. The sample of the treated solution 29-1 from the temporary storage tank 23-1 is tested and it is found that the COD value in the waste liquid is reduced from the original 31000 mg / L to 13500 mg / L, thereby achieving the purpose of degrading the organic waste liquid.

[0145] Example 5

[0146] As shown in FIG5 , this embodiment is based on an electrolytic cell having a U-shaped tube combination structure as shown in FIG16 .

[0147] The bottoms of the anode tank 48 and cathode tank 49 of the electrolytic cell 1 are located on the same horizontal plane and connected by a small intertank solution communication pipe 11. This pipe is equipped with a valve 30-1 and bubble barriers at both ends. The volume of the 200-liter cathode tank 49 is approximately twice that of the anode tank 48. Both the anode tank 48 and cathode tank 49 are equipped with drain pipes with flow control valves.

[0148] Detection sensors 26-1 and 26-2, and 26-3 and 26-4 are installed in the anode and cathode tanks, respectively. Anode tank 48 and cathode tank 49 are connected to large, tank-like temporary storage tanks 23-1 and 23-2, respectively, via overflow buffer tanks. Temporary storage tank 23-3 is a pH adjustment tank, equipped with detection sensors 26-5 and 26-6. These sensors are connected to the inlets of cathode tank 49 and anode tank 48, respectively, via solid-liquid separators 24-1 and 24-2. The two solid-liquid separators perform solid-liquid separation on solution 28-2 to remove solid impurities from the organic wastewater.

[0149] Sensors 26-1, 26-3, 26-5, 26-7, and 26-8 are level gauges, sensors 26-2 and 26-4 are thermometers, and 26-6 is a pH meter. Pumps 31-1 and 31-4 are variable-frequency pumps, controlling the circulation flow and balancing and stabilizing the electrolyte levels in the anode and cathode tanks during solution flow. The electrolytic power supply 4 has an output voltage of up to 120V.

[0150] The solution 28-1 to be treated is an organic waste liquid containing a relatively high chloride ion concentration, wherein the chloride ion concentration is 4.3 g / L and the COD is 18000 mg / L. Therefore, it is necessary to remove some of the chloride ions so that the chloride ion concentration in the solution is reduced to below 2 g / L before it can enter the biochemical pool for further biochemical treatment according to the process requirements.

[0151] In this embodiment, the solution 28-1 to be treated is a raw organic waste liquid containing a relatively high chloride ion concentration.

[0152] The operation steps of this embodiment are as follows:

[0153] (1) Under the control of the liquid level meter 26-5 and the pH meter 26-6, sulfuric acid 39 is added to the temporary storage tank 23-3 to adjust the pH value of the solution 28-1 to be treated with a high chloride ion concentration to a pH value not higher than 1. After mixing, the solution 28-2 to be treated is obtained.

[0154] (2) Pumps 31-5 and 31-6 are turned on to respectively add the solution 28-2 to be treated into the anode and cathode tank areas of the electrolytic cell, and at the same time, the solution 28-2 to be treated is added to the temporary storage tanks 23-1 and 23-2 by circulating the electrolyte with the anode tank area and the cathode tank area respectively; after reaching the set liquid level, pumps 31-5 and 31-6 are turned off, and the circulating flow pumps 31-1 and 31-4 are started, valve 30-1 is opened and the electrolysis power supply 4 is turned on to perform the electrolysis operation; during the electrolysis process, the anode tank area 48 is enriched with chloride ions and chlorine gas is electrolyzed, and the chloride ions in the cathode tank area 49 are migrated to the anode tank area 48 under the action of the electric field force, so that the chloride ions in the cathode electrolyte are reduced and hydrogen gas is electrolyzed at the cathode. During the electrolysis process, pumps 31-1 and 31-4 are controlled by the results of detection sensors 26-7 and 26-8 respectively, and the rotation speeds of pumps 31-1 and 31-4 are controlled to deliver the solution to maintain a dynamic balance between the positive and negative electrolytes during flow, so that the bubble-containing solution can quickly precipitate the bubbles through the liquid flow.

[0155] (3) Sampling and checking the cathode electrolyte in the cathode tank area 49. When the chloride ion concentration drops to less than 2 g / L, close the valve 30-1 and turn off the electrolysis power supply 4. Open the flow control valve 7-2 and collect the solution in the cathode tank area 49 and the temporary storage tank 23-2 as the electrolytically treated solution 29-2.

[0156] (4) Pump 31-5 is started to extract the solution from temporary storage tank 23-3 and add it to cathode tank area 49 and temporary storage tank 23-2. After the set liquid level is reached, pump 31-5 is shut down and circulating flow pumps 31-1 and 31-4 and electrolysis power supply 4 are restarted to continue electrolysis for dechlorination treatment.

[0157] During the electrolysis process, the electrolytic cell of the U-shaped tube combination structure of the present invention utilizes the anode and cathode tank areas, respectively, and the connected temporary storage tanks to generate the electrolyte circulation flow, effectively preventing the electrolytes in the anode and cathode tank areas from mixing, thereby temporarily and effectively separating the electrolytes in the anode and cathode tank areas, and preventing the chlorine gas generated at the anode from entering the cathode tank area and being electrochemically reduced to chloride ions. Therefore, this embodiment can effectively solve the problem of low reaction efficiency when using an electrolytic cell without a partition. Moreover, because the electrolytic cell structure of the present invention does not have a partition, there is no process problem of generating foaming slurry and / or viscous oil droplets during environmentally friendly treatment of organic waste liquid, which adhere to the electrolytic cell partitions, hindering the electrolytic reaction and damaging the electrolytic cell equipment.

[0158] The above operation can be used to remove chlorine from organic wastewater containing high concentrations of chloride ions. The chloride ion concentration of solution 29-2 after electrolysis was detected to be 1.93 g / L, and it can be sent to the biochemical treatment tank for further treatment according to the process requirements.

[0159] Example 6

[0160] As shown in FIG6 , it is a flow chart of the device and process of Example 6.

[0161] This embodiment uses an electrolytic cell with a combined structure of two high and low tank sections, i.e., the bottom of the high tank section is higher than the bottom of the low tank section, and the high tank section serves as the cathode tank section. The apparatus of this embodiment specifically includes electrolytic cell 1-1, electrolytic cell 1-2, electrolytic cell section sealing tank covers 8-1 to 8-4, bipolar electrodes 12, impeller stirring device 17, liquid circulation stirring device 18, gas-liquid separator 19, vacuum ejector 24, spray tower 22, three temporary storage tanks, multiple sensors 26, automatic detection and feeding controller 27, and two hydrogen high-altitude safety discharge pipes 46. The output voltage of electrolytic power supply 4-1 can reach 160V, and the output voltage of electrolytic power supply 4-2 can reach 180V.

[0162] Electrolytic cell 1-1 has the structure shown in Figure 12, and electrolytic cell 1-2 has the structure shown in Figure 14. One side of the upper tank sections 2-1 and 2-2 of both are partially joined to one side of the lower tank sections 3-1 and 3-2, respectively. Intertank solution communication gaps 10-1 and 10-2 are provided at these joints, respectively. In electrolytic cell 1-1, a bubble barrier 37-1, a filter cloth, is provided at the joint between the two tank sections. The bottom of the upper tank section 2 of electrolytic cell 1-2 is also connected to the lower tank section 3 via a small intertank solution communication pipe 11. A bipolar electrode 12 is placed within this intertank solution communication pipe 11, with a gap between it and the pipe wall.

[0163] The top of the high-level tank section 2-1 is equipped with a gas collecting tank cover 8-1 and an exhaust pipe 9-3. The top of the low-level tank section 3-1 is sealed as a gas collecting tank cover and is equipped with exhaust pipes 9-1 and 9-2. Exhaust pipes 9-1 and 9-2 are both equipped with a release chamber and connected to a gas-liquid separator 19, which is specifically a tee pipe. The top of the high-level tank section 2-2 is equipped with a gas collecting tank cover 8-4 and an exhaust pipe 9-5. The top of the low-level tank section 3-2 is equipped with a gas collecting tank cover 8-3 and an exhaust pipe 9-4.

[0164] The low-level tank area 3-1 is equipped with a drain pipe connected to the flow control valve 7-1. The liquid outlet of the gas-liquid separator 19 is connected to this drain pipe and leads to the temporary storage tank 23-2. The temporary storage tank 23-2 is equipped with a vacuum ejector 21. The temporary storage tank 23-2 is connected to the temporary storage tank 23-1 via a liquid pipeline and to the spray tower 22 located in the temporary storage tank 23-1 via a gas pipeline. The vacuum ejector 21 is used to draw oxygen escaping from the electrolytic tank 1-2 and the gas-liquid separator 19 into the temporary storage tank 23-2 for oxidation reaction with the electrolytically treated solution 29-2. The spray tower 22 is used to absorb oxygen escaping from the temporary storage tank 23-2 and introduce it into the temporary storage tank 23-1 for the secondary oxygen oxidation reaction.

[0165] The low-level tank section 3-2 is equipped with a drain pipe with a flow control valve 7-2, which is connected to the feed port of the high-level tank section 2-1. The feed port of the high-level tank section 2-2 is connected to the temporary storage tank 23-3 via a solid-liquid separator 24. The solid-liquid separator 24 filter is used to filter solid impurities from the solution 28 to be treated. Detection sensors 26-3 (an ORP meter), 26-4 (an ORP meter), and 26-5 (a liquid level gauge) are installed in the low-level tank section 3-1 and the high-level tank section 2-1 of the electrolytic cell 1-1. The insoluble anode 5-1 is a conductive graphite plate, and the electrolytic cathode 6-1 is stainless steel.

[0166] Detection sensors 26-6, which are ORP meters, 26-7, which are ORP meters, and 26-8, which are liquid level meters, are installed in the low-level tank area 3-2 and the high-level tank area 2-2 of the special structure electrolytic cell 1-2. The insoluble anode 5-2 is a titanium-based coated electrode, and the electrolysis cathode 6-2 is a nickel plate. The bipolar electrode particles in the connecting pipe are conductive graphite.

[0167] The automatic detection and feeding controller 27 is used for operating program control of the entire equipment.

[0168] The temporary storage tank 23-1 and the temporary storage tank 23-2 are oxidation reaction tanks, and detection sensors 26-1 and 26-2 are installed in both tanks, which are ORP meters.

[0169] The solution 28 to be treated in this embodiment is an organic waste liquid containing acrylic acid, and its COD is 120,000 mg / L.

[0170] This embodiment uses the device of the present invention to perform a multi-step treatment process of reduction → oxidation → reduction → oxidation → oxidation on the organic waste liquid to degrade the acrylic acid organic waste liquid and solve the process problem of cross-linking of reactants in the process.

[0171] The operation steps of this embodiment are as follows:

[0172] (1) Close the flow control valves 7-1 and 7-2, turn on the automatic detection and feeding controller 27 to control the pump 31-6 to filter the solution 28 to be treated in the temporary storage tank 23-3 and then feed it into the high-level tank area 2-2. When the liquid level reaches the liquid level setting value of the detection sensor 26-8, turn off the pump 31-6.

[0173] (2) Impeller agitator 17-2 and liquid circulation agitator 18-2 are started, and electrolysis power supply 4-2 is activated to conduct electrolysis. Oxygen is electrolytically deposited on insoluble anode 5-2 and directed to vacuum ejector 21. Hydrogen is electrolytically deposited on electrolytic cathode 6-2 and directed to a higher location for safe discharge. Because bipolar electrodes 12 are placed in the small pipes 11 connecting the solutions between the cells, oxidation and reduction reactions continuously occur in the electrolyte within the connecting pipes.

[0174] (3) When the value measured by the detection sensor 26-7 drops to the process set value, the automatic detection feeding controller 27 controls the opening of the flow control valve 7-2, and slowly pumps the electrolytically oxidized solution 29-3 into the high-level tank area 2-1 by starting pumps 31-5 and 31-4 to undergo reduction reaction again; in this process, under the constant value control of the detection sensor 26-7, the pump 31-6 is started to continuously feed a small amount of solution 28 to be treated into the high-level tank area 2-2 for replenishment, and the solution is converged to the low-level tank area through the connecting pipe 11, and an electrochemical redox reaction is carried out with the bipolar electrode.

[0175] (4) When the liquid level in the high-level tank area 2-1 reaches the set value of the detection sensor 26-5, the impeller stirrer 17-1 and the liquid circulation stirrer 18-1 are started, and the electrolysis power supply 4-1 is started to perform the electrolysis operation; during the electrolysis process, oxygen is precipitated on the insoluble anode 5-1, and hydrogen is electrolytically precipitated on the electrolytic cathode 6-1 and discharged into the air. During the process, the oxygen electrolyzed by the anode 5-1 is separated and escaped through the gas-liquid separator 19; when the value measured by the detection sensor 26-3 reaches the process set value, the automatic detection feeding controller 27 controls the opening of the flow control valve 7-1 and the valve 30-2 according to the time, so that the electrolytically treated solution 29-2 (which has undergone two major electrochemical oxidations) flows out and is pumped into the temporary storage tank 23-2, and at the same time, the pump 31-4 is started to replenish the electrolytically treated solution 29-3 in the overflow buffer tank 25 into the high-level tank area 2-1 for the reduction reaction again.

[0176] (5) After the electrolytically treated solution 29-2 is stored in the temporary storage tanks 23-1 and 23-2, pumps 31-1 and 31-3 are started to operate, causing the vacuum ejector 21 and spray tower 22 to absorb oxygen escaping from the electrolytic tank and gas-liquid separator, thereby performing a two-stage oxidation reaction on the electrolytically treated solution 29-2. When the values ​​measured by the detection sensors 26-1 and 26-2 reach the process set values, the automatic detection and feeding controller 27 controls the opening of valve 30-1 to discharge part or all of the treated solution 29-1. The COD concentration of the solution 29-1 is 45,000 mg / L, indicating the final treated solution.

[0177] During the electrolysis process, the electrolytic cell of the present invention, with its high-low tank zone combination structure, utilizes the gravity acting on the solution to cause the solution in the high tank zone to flow toward the low tank zone, and controls the flow of electrolyte from the high tank zone toward the low tank zone, thereby reducing the amount of electrolyte in the cathode tank zone entering the anode tank zone. This effectively separates the electrolyte in the anode and cathode tank zones. Therefore, this embodiment effectively solves the problem of low reaction efficiency when using an electrolytic cell without a partition. Furthermore, because the electrolytic cell structure of the present invention lacks a partition, the process problem of foamed slurry in the electrolyte adhering to the electrolytic cell partition during electrochemical environmental treatment of organic wastewater, hindering the electrolysis reaction and damaging the electrolytic cell equipment, is eliminated.

[0178] According to the above-mentioned operating method, after the acrylic acid-containing waste liquid is treated through the process of reduction → oxidation → reduction → oxidation → oxidation, the process problem of electrolyte cross-linking foaming is solved during the electrochemical reaction process and the COD value of the original liquid can be degraded from as high as 120,000 mg / L to 45,000 mg / L.

[0179] Example 7

[0180] As shown in Figure 7, which is a flow chart of the apparatus and process of Example 7, this example uses the electrolytic cell with the U-shaped tube partition structure of Figure 17. Furthermore, this example combines the electrolysis apparatus of the present invention with the hydrogenation apparatus described in Chinese Patent Application No. 202310394209.X, "A Method and Apparatus for Involving Hydrogen in Organic Reactions at Atmospheric Pressure," to produce a new, highly efficient hydrogen-enriched water generator.

[0181] This embodiment mainly includes an electrolytic cell having a U-shaped tube partition structure as shown in Figure 17, and a hydrogenation device. The electrodes of the electrolytic cell and the hydrogenation device are required to use electrodes with platinum surfaces to ensure that the hydrogen-rich water produced contains no or minimal heavy metal ions.

[0182] The bottoms of the anode tank section 48 and the cathode tank section 49 of the electrolytic cell 1 are located on the same horizontal line, joined together. A connecting gap 10 is provided only below the spacer where the two meet. A gate 47 is installed in this connecting gap, along with a bubble barrier 37. Both the anode tank section 48 and the cathode tank section 49 are equipped with drain pipes, each equipped with a flow control valve 7-2 and 7-1, respectively.

[0183] The cathode tank area 49 of the electrolytic cell 1 is equipped with a hydrogenation device and a detection sensor 26-1; the detection sensor 26-1 is an ORP meter, which is used to safely monitor the reduction value of the hydrogen-rich water. The anode tank area is equipped with detection sensors 26-2 and 26-3, which are an ORP meter and a liquid level gauge, respectively. During the electrolysis process, the detection and control of each detection sensor are used to ensure that the hydrogen-rich water produced meets the drinking water standard. The electrolytic cell adopts the structure of Figure 17. During the electrolysis of tap water, the anode electrolysis gas and the cathode electrolysis gas can be separately utilized and processed, so that the anode electrolyte produces a chlorine-containing disinfectant and washing liquid, and the cathode electrolyte produces hydrogen-rich water that meets the drinking water standard. For electrical safety, the operating voltage of the electrolysis power supply used in this embodiment is 24V.

[0184] The cathode tank area 49 of the electrolytic cell 1 and the hydrogenation device component 41 are combined to form the hydrogenation device. The hydrogenation device adopts the device for safely treating hydrogen through an electro-oxidation process described in Chinese Patent No. ZL202220949622.9, "Apparatus for Safely Treating Hydrogen by an Electrochemical Process," specifically a hydrogen oxidation electrolytic cell. It comprises a hydrogen oxidation electrolytic cell body, a hydrogen oxidation electrolytic anode, an oxygen-consuming electrolytic cathode, and a hydrogen introduction device. The hydrogen oxidation electrolytic anode and the oxygen-consuming electrolytic cathode are connected by a bridge to form an electrochemical reaction electrode pair and are disposed within the hydrogen oxidation electrolytic cell body. The hydrogen introduction device is a hydrogen source electrolytic cell integrated with the hydrogen oxidation electrolytic cell. The hydrogen oxidation electrolyzer is directly installed in the hydrogen source electrolyzer. The hydrogen oxidation electrolysis anode and the oxygen-consuming electrolysis cathode are installed in the hydrogen source electrolyzer body near the hydrogen source electrolysis cathode. The hydrogen oxidation electrolysis anode and the oxygen-consuming electrolysis cathode are connected by the bridge. In this embodiment, the electrolyzer 1 of the present invention is used as the hydrogen source electrolyzer.

[0185] The operation steps of this embodiment are as follows:

[0186] (1) Close the flow control valves 7-1 and 7-2, open the gate 47, inject tap water 42 into the electrolytic cell 1, and shut down after the detection sensor 26-3 reaches the set position.

[0187] (2) Turn on the liquid circulation agitators 18-1 and 18-2 in the anode and cathode tank areas, and turn on the electrolysis power supply to carry out the electrolysis operation. During the electrolysis process, the electrolysis anode is enriched with chloride ions and an electrochemical reaction occurs to electrolyze a trace amount of chlorine gas and react to generate hypochlorous acid products, causing the value of the detection sensor 26-2 to rise. A trace amount of hydrogen gas is electrolyzed in the cathode tank area and undergoes a hydrogenation reaction with the cathode electrolyte, causing the value of the detection sensor 26-1 to decrease. The hydrogenation device in the cathode tank area then exerts further electrochemical catalysis on the hydrogen to remove oxidizing substances in the tap water, making full use of the trace amount of hydrogen raw materials to produce hydrogen-rich water. When the value of the detection sensor 26-1 drops to a preset value, the electrolysis power supply 4 is turned off and the gate 47 is closed.

[0188] (3) Open the flow control valves 7-1 and 7-2 to take out the cathode electrolyte (hydrogen-rich water) and the anode electrolyte (chlorine-containing disinfectant water) respectively.

[0189] During the electrolysis process, the electrolytic cell of the U-tube combination structure of the present invention effectively prevents the electrolytes in the cathode and anode tank areas from mixing by installing a gate and a bubble barrier at the connecting gap and a flow control valve on the drain pipe, thereby temporarily and effectively separating the electrolytes in the cathode and anode tank areas. This prevents the chlorine generated on the anode from entering the cathode tank area and being electrochemically reduced to chloride ions, and prevents the hydrogen generated on the cathode from entering the anode tank area. Therefore, this embodiment can effectively solve the problem of low reaction efficiency when using an electrolytic cell without a partition. Moreover, since there is no partition in the electrolytic cell structure of the present invention, the cost of using and replacing the electrolytic cell partition can be saved.

[0190] By combining the above electrolysis and hydrogenation processes, the device can be used as a hydrogen-rich water machine to produce hydrogen-rich water (ORP value 130mv) and chlorine-containing disinfectant washing water (ORP value 150mv) that are beneficial to people's health.

[0191] Note: The ORP values ​​of the produced hydrogen-rich water and chlorine-containing disinfectant water depend on the local tap water quality and drinking water standards.

[0192] Example 8

[0193] As shown in FIG7 , the apparatus diagram of Example 7 is adopted.

[0194] The difference between this embodiment and embodiment 7 is that:

[0195] The detection sensor 26-1 is a liquid level gauge;

[0196] The solution to be treated is injected into the electrolytic cell 1, specifically nickel precipitation wastewater containing chloride ions, which contains organic acids and other organic matter;

[0197] The exhaust pipe 9-1 is connected to the device (not shown) for safely treating hydrogen by an electro-oxidation process in Chinese Patent No. ZL202220949622.9 "Device for safely treating hydrogen by an electrochemical process" to treat the hydrogen tail gas; the hydrogen introduction device used is a gas-liquid mixing device;

[0198] The hydrogenation device adopts the device for utilizing hydrogen to participate in organic reactions at normal pressure in Chinese patent application 202310394209.X "A method and device for utilizing hydrogen to participate in organic reactions at normal pressure", which includes an anaerobic reactor, a hydrogen activation conductor and a hydrogen introducer; the anaerobic reactor is a normal pressure closed container provided with an exhaust gas outlet or provided with both a hydrogen inlet and an exhaust gas outlet; the hydrogen activation conductor is arranged in the anaerobic reactor, and is a conductor, one end of which is close to the hydrogen enrichment area is a hydrogen activation anode, and the other end is a reaction cathode; or it is a conductive device formed by two independent conductors connected by a conductive bridge, the conductor of which is close to the hydrogen enrichment area is a hydrogen activation anode, and the other conductor is a reaction cathode; the hydrogen introducer is connected to the anaerobic reactor to create a hydrogen enrichment area in the anaerobic reactor, and the hydrogen production electrolysis device.

[0199] The hydrogen production electrolysis device described in this patent application is equipped with an electrolytic cell divider to separate the electrolytic cell into an anode cell area and a cathode cell area. The electrolytic anode is placed in the anode cell area and connected to the positive electrode of the electrolytic power supply, while the electrolytic cathode is placed in the cathode cell area and connected to the negative electrode of the electrolytic power supply. The cathode cell area and the space in the anaerobic reactor where the hydrogen activation anode is located are combined into a single, integrated space. In this embodiment, the electrolytic cell 1 of the present invention replaces the electrolytic cell equipped with the electrolytic cell divider and serves as the hydrogen production electrolytic device in the hydrogenation device.

[0200] The operation steps of this embodiment are as follows:

[0201] (4) Close the flow control valves 7-1 and 7-2, open the gate 47, inject the solution to be treated into the electrolytic cell 1, and shut down after the detection sensors 26-1 and 26-3 reach the set positions.

[0202] (5) The liquid circulation agitators 18-1 and 18-2 in the anode and cathode tank areas are turned on, and the electrolysis power supply is turned on to carry out the electrolysis operation. During the electrolysis process, the electrolysis anode is enriched with chloride ions and an electrochemical reaction occurs to electrolyze chlorine gas and generate hypochlorous acid products, causing the value of the detection sensor 26-2 to rise. Hydrogen gas is electrolyzed in the cathode tank area, and the hydrogenation device in the cathode tank area electrochemically catalyzes the hydrogen gas to remove organic matter in the electrolyte. When the preset reaction time is reached, the electrolysis power supply 4 is turned off and the gate 47 is closed.

[0203] (6) Open the flow control valves 7-1 and 7-2 to take out the cathode electrolyte and the anode electrolyte respectively.

[0204] During the electrolysis process, the electrolytic cell of the U-tube combination structure of the present invention effectively prevents the electrolytes in the cathode and anode tank areas from mixing by installing a gate and a bubble barrier at the connecting gap and a flow control valve on the drain pipe, thereby temporarily and effectively separating the electrolytes in the cathode and anode tank areas. This prevents the chlorine generated on the anode from entering the cathode tank area and being electrochemically reduced to chloride ions, and prevents the hydrogen generated on the cathode from entering the anode tank area. Therefore, this embodiment can effectively solve the problem of low reaction efficiency when using an electrolytic cell without a partition. Moreover, since there is no partition in the electrolytic cell structure of the present invention, the cost of using and replacing the electrolytic cell partition can be saved.

[0205] After 20 hours of reaction using the combined electrolysis and hydrogenation process, the chloride ion concentration of the solution in the cathode tank area was measured to be reduced from 15g / L to 2g / L. Then, after reacting it with conventional waste liquid treatment oxidants, its COD value dropped from 30,000mg / L to 1,500mg / L, allowing it to enter the biochemical pool for conventional treatment.

[0206] Comparative Example 1

[0207] The solution to be treated in Example 1 was electrolyzed using an electrolytic cell without partitions. The electrolytic anode was an insoluble anode, specifically a titanium-based coating anode; and the electrolytic cathode was a titanium plate.

[0208] The solution to be treated is the iron-containing acidic copper chloride etching waste liquid of the circuit board, with an acidity of 2M, a copper ion concentration of 40g / L, a divalent iron ion concentration of 50g / L, and a volume of 500L of the solution to be treated.

[0209] During the electrolysis process, electrochemical reactions occur at the insoluble anode: ferrous ions are oxidized to ferric ions, a small amount of monovalent copper ions are oxidized to cupric ions, and chlorine is electrolyzed. The primary electrochemical reaction at the cathode is the electrochemical deposition of metallic copper. However, because the electrolyte near the anode and the electrolyte near the cathode are not separated, some of the ferric ions generated at the anode come into contact with the cathode and are electrochemically reduced. Other ferric ions corrode and dissolve the metallic copper deposited at the cathode, resulting in low reaction efficiency.

[0210] Through the above operation, after the same electrolysis operation time as in Example 1, the copper ion concentration in the iron-containing acidic etching waste liquid of the circuit board was reduced from the original 40 g / L to 35 g / L.

[0211] Comparative Example 2

[0212] The solution to be treated in Example 1 was electrolyzed using an electrolytic cell with an electrolytic cell separator. The electrolytic cell separator was an anion exchange membrane. The electrolytic anode was an insoluble anode, specifically a titanium-based coated anode; the electrolytic cathode was a titanium plate.

[0213] The solution to be treated is the iron-containing acidic copper chloride etching waste liquid of the circuit board, with an acidity of 2M, a copper ion concentration of 40g / L, a divalent iron ion concentration of 50g / L, and a volume of 500L of the solution to be treated.

[0214] During the electrolysis process, electrochemical reactions occur at the insoluble anode: ferrous iron ions are oxidized to ferric iron, a small amount of monovalent copper ions are oxidized to cupric copper, and chlorine gas is electrolyzed. The primary electrochemical reaction at the cathode is the electrochemical deposition of metallic copper. However, due to the low concentration of copper ions in the catholyte, sponge copper is deposited. Finely divided copper particles float with the electrolyte and adhere to the electrolytic cell separator. As electrolysis proceeds, they act as bipolar electrodes, growing into needle-like structures due to the concentrated current flow, piercing and damaging the separator.

[0215] Through the above operation, after the same electrolysis operation time as in Example 1, the copper ion concentration in the iron-containing acidic etching waste liquid of the circuit board was reduced from the original 40g / L to 21g / L. Puncture damage was found on the electrolytic cell separator.

Claims

1. An electrolysis device with a gap communication structure separating the anode and cathode tank areas, comprising an electrolytic tank, an electrolytic anode, an electrolytic cathode and an electrolytic power supply, characterized in that: The electrolytic cell is provided with a gap communication structure, which divides the electrolytic cell into an anode cell area and a cathode cell area, and at least one discharge pipe with a flow control valve is installed in at least one cell area to control the real-time flow status of the electrolyte in each cell area according to the flow rate; The electrolytic anode is placed in the anode tank area and connected to the positive electrode of the electrolytic power supply, and the electrolytic cathode is placed in the cathode tank area and connected to the negative electrode of the electrolytic power supply.

2. The electrolysis device according to claim 1, characterized in that The electrolytic cell adopts at least one of the following gap communication structures: ① The anode tank area and the cathode tank area are bonded together on at least a portion of at least one side, and at least one connecting gap is provided at the bonding position, so that the two tank areas are connected to a separately provided pipeline through the connecting gap or simultaneously through the connecting gap; ②The anode tank area and the cathode tank area are two independent tank areas connected by pipelines; The drain pipe is arranged in the anode tank area and / or the cathode tank area, and the flow control valve on the drain pipe is specifically a valve that can be opened and closed and / or has an adjustable opening.

3. The electrolysis device according to claim 2, characterized in that The electrolytic cell adopts a high-low tank area combination structure, that is, the anode tank area and cathode tank area of ​​the electrolytic cell are structurally divided into a high tank area and a low tank area, and the bottom of the high tank area is higher than the bottom of the low tank area to form a potential energy difference between the solutions in the two tanks.

4. The electrolysis device according to claim 3, characterized in that In an electrolytic cell with a combined structure of high and low level tank areas, at least one liquid discharge pipe with a flow control valve is installed in the low level tank area.

5. The electrolysis device according to claim 2, characterized in that The electrolytic cell adopts a U-shaped tube combination structure, that is, the anode tank area and the cathode tank area of ​​the electrolytic cell have no difference in height in structure, and their bottoms are located on the same horizontal line.

6. The electrolysis device according to claim 4, characterized in that When a high-low tank area combination structure is adopted, the electrolyte with a larger specific gravity or the electrolyte mixed with solid matter is placed in the low tank area to give full play to the characteristic function of the present invention of temporarily separating the anolyte and the cathode electrolyte.

7. The electrolysis device according to claim 4 or 5, characterized in that Install valves and / or gates with adjustable sizes at the gap communication structure.

8. The electrolysis device according to claim 7, characterized in that An inlet and / or an outlet are additionally provided in the anode tank area and / or cathode tank area.

9. The electrolysis device according to claim 8, characterized in that During electrolysis operation, the gases produced in the electrolytic cell are collected separately for separate treatment, specifically by adding a gas collecting tank cover and an exhaust pipe on the top of the anode tank area and / or cathode tank area; When an exhaust pipe is added to the low-level tank area in the high-low tank area combination structure, the outlet of the exhaust pipe of the low-level tank area is made higher than the liquid level of the electrolyte in the high-level tank area.

10. The electrolysis device according to claim 9, characterized in that The exhaust pipe or its outlet end is connected to a release chamber, and the release chamber is a container whose inner diameter is larger than the inner diameter of the exhaust pipe.

11. The electrolysis device according to claim 10, characterized in that A stirring device is added in the anode tank area and / or cathode tank area.

12. The electrolysis device according to claim 11, characterized in that A stirring device is added to the anode tank area and / or cathode tank area, and a gas collecting tank cover and an exhaust pipe are set on the top of the tank area, and a gas-liquid separator is connected to the exhaust pipe; the gas-liquid separator is a tube cavity or container with at least one gas-liquid mixture inlet, at least one gas outlet, and at least one liquid outlet.

13. The electrolysis device according to claim 12, characterized in that When the electrolyte in the low-level tank area in the high-low tank area combination structure is a solid-liquid mixture, the bottom plate of the high-level tank area is designed as an inclined plate structure inclined toward the low-level tank area, so as to help the solid matter overflowing from the low-level tank area into the high-level tank area due to gas evolution during the electrolysis operation to return to the low-level tank area along the inclined plate under the action of gravity, so that the electrolysis operation can operate normally.

14. The electrolysis device according to claim 13, characterized in that A bubble barrier, specifically a filter cloth and / or filter screen, is installed in at least one gap communication structure to prevent the electrolyte in one tank area from flowing into another tank area due to bubbles generated during the reaction process, causing adverse chemical reactions.

15. The electrolysis device according to claim 14, characterized in that A bipolar electrode is placed in at least one communication pipe in the gap communication structure to improve electrolysis efficiency.

16. The electrolysis device according to claim 15, characterized in that In order to better perform the electrolytic gas evolution reaction of the electrolyte, at least one of the following structural improvements is adopted: (1) The bottom ends of the electrolytic anode and the electrolytic cathode are higher than the position of the gap communication structure to reduce the crosstalk between the electrolytic gas on the electrolytic anode and the electrolytic cathode and / or the gas produced by the reaction in the electrolyte, which may cause adverse chemical reactions; (2) Installing a switch valve and / or gate on the gap communication structure, opening the valve or gate as a passage during electrolysis and closing it after the electrolysis reaction is completed, so that the solution in each tank area can be processed independently after the electrolysis reaction.

17. The electrolysis device according to claim 16, characterized in that An electrolyte circulation flow tank is added, and the electrolyte circulation flow tank is connected to the anode tank area or the cathode tank area through at least two pipes to form a liquid flow circulation, at least one of which is equipped with a pump to solve the production problem of a small volume of the electrolytic tank area and a large volume of reaction liquid to be processed.

18. The electrolysis device according to claim 17, characterized in that When the electrolytic cell adopts a U-tube combined structure, an automatic liquid level control and compensation system for circulating electrolyte is added.

19. The electrolysis device according to claim 17, characterized in that A hydrogenation device is added to promote the electrolyzed hydrogen to participate in other chemical reactions or to eliminate it; the hydrogenation device is connected to at least one of the exhaust pipes, or the hydrogenation device and the cathode tank area are combined into a whole.

20. An electrolysis method implemented using the electrolysis device according to claim 1, characterized in that: The following steps are involved: (1) Select an electrolytic cell with a suitable gap communication structure according to the process requirements, add the solution or solid-liquid mixture to be electrochemically treated into the anode tank area and / or cathode tank area respectively, and turn on the electrolysis power supply to start the electrolysis operation; (2) During the electrolysis operation, the flow control valve on the discharge pipe is opened or closed or the opening is adjusted to control the flow of the solution in the anode and cathode tank areas or the outflow of the solution on the discharge pipe, so that the electrolyte in the anode tank area and the cathode tank area can undergo electrochemical reactions and other possible chemical reactions in an orderly and controllable manner.

21. The electrolysis method according to claim 20, characterized in that Under the set electrolysis current conditions, the electrolyte flow rate and / or reaction time length in the anode tank area and the cathode tank area are used as the control basis for the reaction.

22. The electrolysis method according to claim 21, characterized in that Adjustments can be made by increasing the electrolyte concentration in the electrolyte and / or selecting an electrolytic power supply with a higher output voltage while meeting the requirements for safe electricity use.

23. The electrolysis method according to claim 22, characterized in that Add safe operating area space, use photoelectric sensors to establish safe operating area space and add electrolyte solution current-breaking isolators.

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