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WO2024160212A1 - Appareil d'électrolyse ayant une structure de communication à fentes séparant des compartiments d'anode et de cathode, et procédé d'électrolyse associé - Google Patents

Appareil d'électrolyse ayant une structure de communication à fentes séparant des compartiments d'anode et de cathode, et procédé d'électrolyse associé Download PDF

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Publication number
WO2024160212A1
WO2024160212A1 PCT/CN2024/074790 CN2024074790W WO2024160212A1 WO 2024160212 A1 WO2024160212 A1 WO 2024160212A1 CN 2024074790 W CN2024074790 W CN 2024074790W WO 2024160212 A1 WO2024160212 A1 WO 2024160212A1
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Prior art keywords
tank area
electrolysis
cathode
anode
area
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PCT/CN2024/074790
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English (en)
Chinese (zh)
Inventor
叶涛
叶旖婷
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Individual
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Individual
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Priority to CN202480008907.4A priority Critical patent/CN120603987A/zh
Publication of WO2024160212A1 publication Critical patent/WO2024160212A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/46—Regeneration of etching compositions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper

Definitions

  • the invention belongs to the field of electrolytic cells and electrolysis technology, and particularly relates to an electrolytic device and an electrolytic method thereof in which a gap communication structure separates anode and cathode cell areas.
  • Electrolysis technology is widely used in the chemical industry and environmental protection industry, including chlor-alkali production, hydrogen production and new energy, metal industry processing and purification, production of metal salt solutions, environmental waste liquid COD degradation and ammonia nitrogen removal waste liquid treatment, etc. Electrolysis technology is used in existing electrolysis technology.
  • the electrolytic cells used are structurally divided into the following 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 separator membrane, a bipolar membrane, a reverse osmosis membrane, etc.
  • the electrolytic anode and the electrolytic cathode are placed in the same electrolyte for electrolysis. Since the electrolytic cell without a partition does not separate the electrolyte near the anode and the electrolyte near the cathode, both oxidation and reduction reactions occur in the electrolyte. That is, the oxidizing substances in the electrolyte of the electrolytic cell without a partition are easily reduced by contacting the electrolytic cathode, and the reducing substances in the electrolyte are easily oxidized by contacting the electrolytic anode, so it is difficult to achieve the reaction purpose in a short time.
  • Electrolyzer with separators The separators in the electrolyzer can effectively separate the anolyte and the catholyte during electrolysis and make the electrolysis reaction proceed smoothly.
  • the anolyte can undergo oxidation reaction relatively independently and the catholyte can undergo reduction reaction relatively independently. Therefore, the electrolyzer with separators has the advantage of significantly higher reaction efficiency than the electrolyzer without separators.
  • 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 separator has the following disadvantages:
  • the first object of the present invention is to provide an electrolytic device with a gap structure separating the anode and cathode cell areas, which effectively realizes the functional division of the anode cell area and the cathode cell area of the electrolytic cell while avoiding the use of electrolytic cell separators, which is beneficial to the electrolytic reaction and reduces the use cost of the electrolytic equipment.
  • a second object of the present invention is to provide a method for performing electrolysis using the above-mentioned device.
  • the first object of the present invention is achieved through the following technical solutions.
  • An electrolysis device with a gap communication structure separating anode and cathode slots comprising an electrolysis cell, an electrolysis anode, an electrolysis cathode and an electrolysis power supply, characterized in that:
  • a gap communication structure is provided in the electrolytic cell, and the gap communication structure 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, which is used 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.
  • the working principle of the present invention is to use a combination method of a gap communication structure and a flow control valve on a discharge pipe to replace the expensive consumable electrolytic cell separator to functionally separate the positive and negative electrode tank areas of the electrolytic cell.
  • the present invention connects the anode tank area and the cathode tank area of the electrolytic cell only with a gap structure, that is, the negative and anode tank areas are only connected in a small area, so that the anolyte and the cathode electrolyte are effectively separated, but the desired ion migration is not hindered, and the flow direction and flow velocity of the electrolyte in the positive and negative electrode tank areas can be controlled by opening or closing or adjusting the opening of the flow control valve on the discharge pipe, or a liquid flow trend is formed to prevent undesired ion migration and solution mixing.
  • the flow control valve on the discharge pipe can be controlled to generate a liquid flow and/or solution flow trend that is different from the migration direction of the ions or molecules to be blocked, so as to effectively prevent the electrolyte in one tank area from entering another tank area, or effectively prevent the ions in one tank area from migrating to another tank area due to the attraction of the electric field, thereby avoiding the phenomenon of large-scale oxidation and reduction reactions occurring simultaneously as in the electrolyte in an undivided electrolytic cell.
  • the present invention can orderly and controllably allow the anolyte and the catholyte to undergo electrochemical reactions and other chemical reactions that may occur relatively independently in their respective tank areas under temporary liquid flow separation, thereby achieving an electrolysis function similar to that of an electrolytic cell with a separator membrane without using an electrolytic cell separator membrane.
  • the present invention can therefore solve the production difficulties encountered when using electrolytic production equipment, such as gelation and slurrying of electrolyte, floating metal powder in the electrolyte, and solid-liquid mixture electrolyte in the existing electrolytic cells with separators.
  • 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 arranged 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:
  • At least a portion of at least one side of the anode tank area and the cathode tank area are bonded together, and at least one connecting gap is provided at the bonding position, so that the two tank areas are connected to another pipeline through the connecting gap or simultaneously through the connecting gap.
  • 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.
  • the 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 can be adjusted in opening degree.
  • the electrolytic cell adopts a high-low tank area combination structure, that is, the anode tank area and the 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, so as to form a potential energy difference between the solutions in the two tanks.
  • the high tank area can be either the anode tank area or the cathode tank area; correspondingly, the low tank area can be either the cathode tank area or the anode tank area.
  • the electrolytic cell adopts a U-tube combination structure, that is, the anode cell area and the cathode cell area of the electrolytic cell have no height difference in structure, and their bottoms are located on the same horizontal line.
  • the gap communication structure between the anode slot area and the cathode slot area can adopt either the above structure 1 or the above structure 2.
  • the flow control valve on the discharge pipe of the present invention is specifically a valve that can be opened and closed, and/or can be adjusted in opening, and is used to control the outflow of the electrolyte in the electrolytic cell, and the flow control valve is used to assist in controlling the chemical reaction process of the reaction liquid in each tank area of the electrolytic cell.
  • the flow control valve is used to assist in controlling the chemical reaction process of the reaction liquid in each tank area of the electrolytic cell.
  • at least one discharge pipe with a flow control valve is installed in the low tank area.
  • the electrolytic cell of the present invention is equipped with an electrolytic anode and an electrolytic cathode in the anode tank area and the cathode tank area respectively and connected to the electrolytic power source as positive and negative conductive wires accordingly.
  • the volumes of the anode tank area and the cathode tank area can be equal or unequal, and the volumes of the corresponding tank areas are adjusted according to the conditions of the reaction solution (i.e., the electrolyte) to better enable the reaction solution to react efficiently.
  • the electrolyte in the high tank area and the electrolyte in the low tank area are respectively formed into The gravity center of the solution on different horizontal lines is formed, and the gravity exerted on the solution is used to make the solution in the high-level tank area have a tendency to flow to the low-level tank area.
  • 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.
  • the gap communication structure can effectively reduce the situation where the electrolyte in the low-level tank area overflows back to the high-level tank area.
  • 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 used as the cathode tank area.
  • Figures 8 and 19 are schematic diagrams of the basic structure of an electrolytic cell using a high-low tank area combination structure.
  • the electrolytic cell in Figure 15 is a schematic diagram of the basic structure of an electrolytic cell using a U-tube combination structure.
  • an electrolyte with a larger specific gravity or an electrolyte mixed with solid matter is arranged in the low tank area to give full play to the characteristic function of the present invention of temporarily separating the anode electrolyte and the cathode electrolyte.
  • the present invention can be improved as follows: a valve and/or gate with adjustable size is installed at the gap communication structure.
  • the present invention can be improved as follows: an inlet and/or an outlet are added to the anode tank area and/or the cathode tank area.
  • an inlet and/or an outlet are added to the anode tank area and/or the cathode tank area.
  • the electrolytic cell adopts a high and low tank area combination structure and an inlet and/or an outlet are added (as shown in FIG9 )
  • a liquid flow inside the low tank area can be formed to effectively prevent the electrolyte in the high tank area from entering the low tank area, so that the electrolyte in the high tank area can be subjected to electrochemical oxidation or electrochemical reduction reaction alone.
  • 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.
  • FIG. 10 is a schematic diagram of the electrolytic cell structure of the high-low tank area combination structure after improvement on the structure of Figure 8.
  • 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.
  • a release chamber is connected to the exhaust pipe or its outlet end, and the release chamber is a container whose inner diameter is larger than the inner diameter of the exhaust pipe.
  • the electrolyte in the tank area is a solid-liquid mixture or the electrolyte has a high viscosity, the gas generated during the electrolysis process is often difficult to precipitate from the electrolyte, and thus foam is generated to squeeze the electrolyte.
  • the release chamber provides a larger space than the exhaust pipe for the foam or solid-liquid mixture overflowing into the exhaust pipe, which can effectively solve the problem of foam overflow and liquid splashing caused by foam bursting during the electrolysis process.
  • the present invention can be improved as follows: a stirring device is added to the anode tank area and/or cathode tank area, and the stirring device is specifically divided into a liquid flow stirrer or a mechanical stirrer.
  • the stirring device can solve the problem of uniformity of the concentration and temperature of the electrolyte during the electrochemical reaction, and the mechanical stirrer or the liquid flow stirrer can achieve the above purpose.
  • the liquid flow stirrer is to create a liquid flow in the electrolyte through a pump and a pipeline to achieve a stirring effect.
  • the present invention can be further improved: 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 arranged on the top of the tank area, and a gas-liquid separator is connected to the exhaust pipe.
  • a stirring device adopts a liquid flow stirrer, the gas produced by the reaction can be more effectively discharged into the gas-liquid separator to accelerate the escape and separation of gas in the solution.
  • a gas-liquid separator is connected to the exhaust pipe, and 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.
  • a tube cavity or tank with three or more passages such as a three-way pipe or a four-way pipe can be used as the gas-liquid separator.
  • Figure 12 is a schematic diagram of the electrolytic cell structure after the above structure is improved.
  • the present invention can be improved as follows: 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 surging 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 run normally.
  • Figure 11 is a schematic diagram of the electrolytic cell structure after the bottom plate of the high-level tank area is changed to an inclined plate inclined toward the low-level tank area in the structure of Figure 10.
  • the present invention can be improved as follows: a bubble barrier is installed in at least one gap communication structure, specifically a filter cloth and/or a filter screen, to overcome the problem that the electrolyte in one tank area is generated by bubbles during the reaction process and then crosses over to another tank area to cause an undesirable chemical reaction.
  • FIG13 is a schematic diagram of the electrolytic cell structure after the structure is improved.
  • the present invention can be improved as follows: a bipolar electrode is placed in at least one of the connecting pipes in the gap connecting structure to improve the electrolysis efficiency.
  • the bipolar electrode is an insoluble conductive material. After the bipolar electrode is placed, the internal space of the connecting pipes at both ends of the bipolar electrode becomes the electrolyte reaction chamber of the bipolar electrode.
  • the bipolar electrolysis electrolyte reaction chamber close to the high tank area is called the high tank area electrolyte reaction chamber
  • the bipolar electrolysis electrolyte reaction chamber close to the low tank area is called the low tank area electrolyte reaction chamber.
  • FIG. 14 is a schematic diagram of the electrolytic cell structure after adding bipolar electrodes, taking the high and low tank area combination structure as an example.
  • 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:
  • the electrolytic anode of the present invention can be selected from at least one of electrodes with gold and/or platinum and/or nickel and/or their alloy materials, titanium-based coatings, and conductive graphite.
  • a suitable material is selected as the electrolytic anode according to the properties of the electrolyte.
  • the material of the electrolytic cathode can be selected from at least one of gold and/or platinum and/or silver and/or titanium and/or copper and/or tin and/or iron and/or nickel and/or at least one of the above metal alloy materials, or stainless steel, or conductive graphite.
  • the present invention can also be improved as follows: an electrolyte circulation flow trough is added, and the electrolyte circulation flow trough is connected to the anode tank area or the cathode tank area through at least two pipelines to form a liquid flow circulation, wherein at least one of the connecting pipelines is provided with a pump to solve the production problem of a small volume of the electrolytic cell area and a large volume of the reaction liquid to be processed.
  • an automatic control and compensation system for the liquid level of the circulating electrolyte is added.
  • a pressure sensor and/or a liquid level meter is installed in the electrolyte circulating flow tank and/or the tank area connected thereto, and at least one pump on the connecting pipeline adopts a variable frequency pump, and the working state of the variable frequency pump is controlled and adjusted according to the data measured by the pressure sensor and/or the liquid level meter.
  • variable frequency pump is used to control the circulating flow so that the gravity center of the electrolyte in the anode tank area and the cathode tank area maintains a stable state of mutual balance during the flow, thereby reducing the impact on production due to the uncontrolled flow of the electrolyte during the electrolysis operation.
  • the present invention can be improved as follows: a hydrogenation device is added (the structure of the hydrogenation device refers to the device for participating in organic reactions using hydrogen at normal pressure in Chinese patent application 202310394209.X "A method and device for participating in organic reactions using hydrogen at normal pressure” and the device for safely treating hydrogen through an electro-oxidation process in Chinese patent number ZL202220949622.9 "A device for safely treating hydrogen through an electrochemical process”), which is used to promote the electroprecipitated 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 (see Example 7 and Example 8), which is used to promote the electrolyzed hydrogen to participate in other chemical reactions in the electrolyte.
  • 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 of the electrolysis power supply is controlled and/or the start and stop is started, 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 an acidity 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 an electrolysis power supply, a valve and a gate.
  • 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 tank through a pipeline.
  • the present invention can also be improved as follows: an overflow buffer tank is added to solve the problem of solution flow between 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 through a pipeline, or is arranged on a connecting pipeline between any two tanks.
  • the present invention can also be improved as follows: a gas-liquid mixer is added to collect the gas escaped from the reaction and then reuse it for gas-liquid reaction or pump it to the tail gas treatment tank for environmental protection 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 through a gas pipeline.
  • the gas-liquid mixer is a vacuum jet gas-liquid mixer and/or a spray tower gas-liquid mixer.
  • the present invention can also be improved as follows: a solid-liquid separator is added, 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 a connecting pipeline between any two of the above tanks, and is used to filter and remove solid impurities in the reaction liquid.
  • the present invention can also be improved as follows: a cold and hot temperature exchanger is added to adjust and control the temperature of the reaction solution according to the process.
  • the cold and hot temperature exchanger is arranged at at least one of the electrolytic tank, electrolyte circulation tank, temporary storage tank, and overflow buffer tank.
  • the present invention can also be improved as follows: for production safety, an electrolyte solution current cutoff isolator is added to electrically insulate the electrolyte in the electrolytic cell from the outside world.
  • the electrolyte solution current cutoff isolator is arranged on the feed inlet connecting pipe and/or the discharge port connecting pipe and/or the drain pipe of the electrolytic cell, and uses a solution spraying device to change the electrolyte solution into droplets during the spraying flow process to achieve the function of conductivity cutoff.
  • the specific structure of the current cutoff isolator is shown in Figure 18.
  • the second object of the present invention is achieved through the following technical solutions.
  • An electrolysis method implemented by the electrolysis device comprises the following steps:
  • an electrolytic cell with a suitable gap communication structure is selected, the solution or solid-liquid mixture to be electrochemically treated is added to the anode tank area and/or the cathode tank area respectively, and the electrolysis power supply is turned on to start 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 solution in the anode and cathode tanks or the outflow of solution from the discharge pipe, so that the electrolyte in the anode tank and cathode tank can undergo electrochemical reactions and other possible chemical reactions in an orderly and controllable manner.
  • 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.
  • the specific gravity parameter change of the electrolyte before and after the reaction also needs to be considered during the reaction process.
  • the present invention can be improved as follows: due to the gap connection structure of the present invention, the distance between the electrolytic anode and the electrolytic cathode is farther, 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 while meeting the requirements for safe electricity use.
  • the present invention can also be improved as follows: because the electrolytic power supply with a higher output voltage can be used to improve the production efficiency of the electrolytic cell, the working voltage output by the power supply voltage of the present invention may be greater than the safe voltage of 36 volts for the human body.
  • a photoelectric sensor In order to ensure safe production, it is necessary to add a safe operation area space, use a photoelectric sensor to establish a safe operation area space and add an electrolyte solution current cut-off isolator.
  • the photoelectric sensor uses an optical path to demarcate the control space, and when a person's limb enters the controlled area and blocks the light, a signal is given to shut down the electrolytic power supply.
  • the electrolyte solution current cut-off isolator uses a solution spraying device to change the electrolyte solution into droplets during the spraying flow process to achieve the function of conductivity cut-off.
  • the present invention has the following beneficial effects:
  • the present invention adopts a gap communication structure to functionally separate the positive and negative electrode tank areas of the electrolytic cell and a combination method of a flow control valve on the discharge pipe, thereby solving the production process problems of the existing electrolytic cells with separators, such as slurrying, solid-liquid mixture electrolyte, and floating metal particles in the electrolyte, which damage the electrolytic cell during the electrolysis process.
  • the present invention can control the reaction process of the electrolyte in the anode and cathode tank areas respectively 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 collect and process the gases produced in each electrolyte separately without installing an electrolytic cell separator, so that the chemical reaction can achieve the process purpose.
  • the gap communication structure of the present invention separates the anode and cathode slot areas of the electrolytic cell, which has a simple structure and no separator consumables. The operation of replacing the separator is eliminated, thus significantly reducing the operating cost of electrolytic production.
  • the process and device of the present invention are easy to operate, safe and reliable, and have wide market applicability.
  • FIG1 is a flow chart of an electrolysis device and a process flow chart of a gap-connected structure separating anode and cathode slot areas according to Embodiment 1 of the present invention
  • FIG2 is a flow chart of an electrolysis device and a process flow chart of a gap-connected structure for separating anode and cathode slot areas according to Embodiment 2 of the present invention
  • FIG. 3 is a flow chart of an electrolysis device and a process flow chart of a gap-connected structure for separating anode and cathode slots according to Embodiment 3 of the present invention
  • FIG4 is a flow chart of an electrolysis device and a process for separating anode and cathode slots using a gap communication structure according to Embodiment 4 of the present invention
  • FIG. 5 is a flow chart of an electrolysis device and a process flow chart of a gap-connected structure for separating anode and cathode slots according to Embodiment 5 of the present invention
  • FIG6 is a diagram of an electrolysis device and a process flow chart of a gap-connected structure for separating anode and cathode slot areas according to Example 6 of the present invention.
  • FIG. 7 is a diagram of an electrolysis device and a process flow chart of a gap-connected structure for separating anode and cathode slot areas according to Embodiment 7 of the present invention.
  • FIG8 is a schematic diagram of the combined basic structure of the high and low tank areas of the electrolytic cell in which the gap communication structure separates the anode and cathode tank areas;
  • FIG. 9 is a schematic diagram of a high-low tank area combination structure of an electrolytic cell having a gap communication structure separating the anode and cathode tank areas and having a low tank area inlet and a high tank area outlet;
  • FIG. 10 is a schematic diagram of a combined structure of high and low tank areas of an electrolytic cell having a gap communication structure separating the anode and cathode tank areas and provided with a feed inlet and a low tank area exhaust pipe;
  • FIG11 is a schematic diagram of the structure of an electrolytic cell having an exhaust pipe and a release chamber, wherein the gap communication structure separates the anode and cathode tank areas;
  • FIG12 is a schematic diagram of the structure 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;
  • FIG13 is a schematic diagram of the structure of an electrolytic cell having a gap communication structure separating the anode and cathode tank areas and provided with a bubble barrier, an exhaust pipe and a gas-liquid separator;
  • FIG14 is a schematic diagram of the structure of placing bipolar electrodes in the connecting pipe of the electrolytic cell where the gap connecting structure separates the anode and cathode cell areas;
  • 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 cell areas and connected to a temporary storage tank;
  • FIG16 is a schematic diagram of the structure of a switch valve installed on the gap communication structure of the electrolytic cell in which the gap communication structure separates the anode and cathode tank areas;
  • 17 is a schematic diagram of 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 cell areas;
  • FIG18 is a schematic diagram of the structure of a current-breaking isolator
  • Figure 19 is a schematic diagram of the combined 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 connection structure.
  • the slot structure used to separate the cathode and anode of the electrolytic cell, 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 are all products manufactured by Foshan Yegao Environmental Protection Equipment Manufacturing Co., Ltd. in Guangdong Province, China.
  • Detection sensors, automatic detection and feeding controllers, solid-liquid separators, electrolytic power supplies, valves, pumps and chemical raw materials are all commercially available products.
  • those skilled in the art can also select other products with similar performance to the above-mentioned products listed in the present invention according to conventional selection, and all of them can achieve the purpose of the present invention.
  • this embodiment uses the gap connection structure of FIG8 to separate the anode and cathode slot 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 slot areas.
  • the electrolytic cell 1 is a combination structure of high and low tank areas.
  • the bottom of the high tank area 2 and the bottom of the low tank area 3 are on the same horizontal line.
  • One side of the high tank area and one side of the low tank area are partially attached to each other, and the attachment position is the inter-tank solution communication gap 10.
  • the two are connected through the inter-tank solution communication gap 10.
  • the high tank area is used as the cathode tank area
  • the low tank area is used as the anode tank area.
  • the trough area of the cathode and the anode is 100 liters each.
  • the low-level trough area 3 is provided with a drain pipe 13.
  • a flow control valve 7 is installed on the drain pipe 13.
  • the low-level trough area 3 is also provided with a gas collecting tank cover and an exhaust pipe 9, and is circulatedly connected to the solid-liquid separator 24.
  • the insoluble anode is a titanium-based coated anode
  • the electrolytic cathode is a titanium plate
  • the output voltage of the electrolytic power supply can reach 9V.
  • 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.
  • the electrolytic power source 4 is turned on to allow the electrolytic cell with the high and low tank area combination structure to perform electrolytic operation.
  • the insoluble anode undergoes electrochemical reactions 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 at the cathode. During the process, some ions in the electrolyte migrate between the positive and negative tank areas.
  • the flow control valve 7 is finely adjusted to open and continuously discharge the electrolytically treated solution 29.
  • the collected solution is ferric chloride and cupric chloride solution.
  • the liquid level in the high-level tank area is continuously replenished to ensure normal electrolysis.
  • This embodiment shows that the use of the electrolysis device and method of the present invention can effectively temporarily separate the electrolytes in the anode and cathode tank areas, and electrolyze the solution containing a lower copper ion concentration to extract copper and electrolyze and oxidize the iron-containing acidic etching waste liquid to regenerate the copper etching agent ferric chloride.
  • the electrolytic cell of the high and low tank area combination structure of the present invention discharges an appropriate amount of anode electrolyte by adjusting the switch of the flow control valve 7, so that the electrolyte in the high tank area flows to the low tank area in a controlled manner to reduce the migration of trivalent iron ions generated in the anode tank area to the cathode tank area, thereby preventing the metal copper electrolyzed by the cathode from being reversely etched and dissolved.
  • this embodiment can effectively solve the problem of low reaction efficiency caused by both oxidation reaction and reduction reaction in the electrolyte when using an electrolytic cell without partitions.
  • concentration of copper ions contained in the cathode electrolyte is low, so sponge copper is electrolytically deposited and floats in the cathode electrolyte. Since there is no partition in the electrolytic cell structure of the present invention, there is no process problem of sponge copper powder damaging the electrolytic cell equipment.
  • the circuit board iron-containing acidic etching waste liquid 28 is electrolytically treated to extract copper, and 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.
  • this embodiment uses the high-low tank area combined structure electrolytic cell of Fig. 10, the volume of the cathode and anode tank areas is 100 liters each, and a liquid level meter 26 is installed in the cathode tank area. Two temporary storage tanks are also added.
  • 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 and bonded 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.
  • the high level tank area 2 is used as the cathode tank area
  • 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 to add the solution 28-2 that needs to be treated
  • 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
  • the insoluble anode of the electrolytic cell is a platinum plate anode
  • the electrolytic cathode is a titanium plate
  • the output voltage of the electrolytic power supply can reach 36 V.
  • the detection sensor 26 is a liquid level meter.
  • the solution 28-1 to be treated is ammonia alkaline copper chloride ammonia etching washing waste liquid of a circuit board, wherein the ammonia nitrogen content is 1700 mg/L and the copper ion concentration is 3 g/L.
  • Sodium hydroxide is added to the 500 liters of washing waste liquid loaded in the temporary storage tank 23-2 to adjust the pH value of the solution to be treated to 11, thereby obtaining the solution 28-2 to be treated.
  • the electrolytic power source 4 is turned on to allow the electrolytic cell with the high and low cell area combination structure to perform electrolytic 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 cathode; during the electrolytic process, part of the ammonium and copper ions in the anode cell area migrate to the cathode cell area, and part of the chlorine 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.
  • This embodiment can illustrate that the electrolysis method and device of the present invention can be used to treat ammonia nitrogen-containing wastewater.
  • the chemical reaction formula is as follows: 3NaClO+2NH 3 ⁇ 3NaCl+3H 2 O+N 2 ⁇
  • the electrolytic cell of the high-low tank area combination structure of the present invention utilizes the gravity of the solution to make the solution in the high tank area have a tendency to flow to the low tank area, so as to reduce the migration of chlorine gas and sodium hypochlorite generated in the anode tank area to the cathode tank area for consumption. Therefore, this embodiment can effectively solve the problem of low reaction efficiency when using an electrolytic cell without a partition. In addition, since there is no partition on the electrolytic cell structure of the present invention, there is no process problem of sponge copper particles in the electrolyte adhering to the electrolytic cell partition to damage the electrolytic cell equipment.
  • the ammonia alkaline copper chloride ammonia etching and washing waste liquid is prepared and then electrolyzed to separate chlorine gas and generate The resulting sodium hypochlorite reacts with NH 3 to achieve the effect of removing ammonia nitrogen, so that the ammonia nitrogen impurity in the treated solution 29 is 340 mg/L.
  • this embodiment uses the electrolytic cell of the high-low tank area combination structure of FIG11 , and the volume of the cathode and anode tank areas thereof are 100 liters each.
  • the electrolytic cell 1 is a combination structure of high and low tank areas, the bottom of the high tank area 2 is higher than the bottom of the low tank area 3, and the bottom plate of the high tank area 2 is inclined toward the low tank area 3.
  • One side of the high tank area is partially connected to one side of the low tank area, and a connecting gap is provided at the fitting position.
  • An exhaust pipe 9-2 is provided in the high tank area 2.
  • An exhaust pipe 9-1 is provided in the low tank area 3, and the exhaust pipe is connected to a release chamber; and a discharge pipe 13 with a flow control valve 7 is provided.
  • Detection sensors 26-1 and 26-2, a hot and cold temperature exchanger 20, and a liquid circulation stirring device 18 are installed in the low tank area 3.
  • the high tank area 2 is used as the cathode tank area
  • the low 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
  • the detection sensor 26-2 is a thermometer.
  • the hot and cold temperature exchanger is used to control the temperature of the anode electrolyte at 10°C.
  • 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 prepared by electrolysis. The chemical reaction formula is as follows:
  • the electrolysis power source 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, and part of the sodium manganate in the anode tank area undergoes an electrochemical oxidation reaction to generate 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 a small amount of sodium manganate being reduced to manganese dioxide, wherein the manganese dioxide solid in the cathode tank area falls back into the anode tank area due to gravity.
  • the electrolytic cell of the high-low tank area combination structure of the present invention uses the gravity of the solution to make the solution in the high tank area have a tendency to flow to the low tank area, so as to reduce the sodium manganate and sodium permanganate generated in the anode tank area. Migrate to the cathode tank area and be consumed by electrochemical reduction. Therefore, this embodiment can effectively solve the problem of low reaction efficiency when using an electrolytic cell without a partition.
  • there is no partition in the electrolytic cell structure of the present invention there is no process problem that solids in the solid-liquid mixture electrolyte adhere to the electrolytic cell partition to hinder the electrolytic reaction and damage the electrolytic cell equipment.
  • 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.
  • this embodiment adopts an electrolytic cell with a high and low tank area combination structure as shown in FIG14 .
  • the bottom of the high-level tank area 2 of the electrolytic cell is higher than the bottom of the low-level tank area 3, wherein the high-level tank area 2 is used as the anode tank area, and the low-level tank area 3 is used as the cathode tank area.
  • One side of the high-level tank area is partially bonded to one side of the low-level tank area, and a gap 10 for connecting the solution between the tanks is provided at the bonding position.
  • the bottom of the high-level tank area 2 is also connected to the low-level tank area 3 through a small pipe 11 for connecting the solution between the tanks.
  • a bipolar electrode 12 is placed in the small pipe 11 for connecting the solution between the tanks.
  • 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 respectively added in the two tank areas.
  • the high-level tank area 2 and the low-level tank area 3 are also respectively provided with a feed port.
  • 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 connected to the temporary storage tank 23-1 provided 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 .
  • the insoluble anode used in the electrolytic cell is an electrode with a surface coated with gold metal
  • the electrolytic cathode is platinum metal
  • the output voltage of the electrolytic power supply can reach 80 V.
  • the detection sensors 26-1 and 26-3 are thermometers
  • the detection sensors 26-2 and 26-4 are ORP meters
  • the detection sensors 26-5 and 26-6 are liquid level meters.
  • the temporary storage tank 23-3 in this embodiment is used to collect the solution 29-3 that has been oxidized in the high-level tank area and put it into the low-level tank area for reduction reaction treatment.
  • the combined processor of the temporary storage tank 23-1 and the vacuum ejector 21 is used to collect the oxygen escaping from the high-level tank area for recycling, and the solution 29-2 that has been electrolytically reduced is oxidized with oxygen to obtain the solution 29-1.
  • Such a process flow can meet the needs of separate electrochemical treatment of each electrolyte in the high-low tank area combined structure electrolytic cell.
  • the solution 28 to be treated in this embodiment is the alkaline degreasing waste liquid produced when electroplating parts are cleaned. Its COD The value is 31000mg/L and the solution volume is 400L.
  • This embodiment can illustrate that the use of the electrolysis method and device of the present invention using the "oxidation-reduction-oxidation" treatment process can effectively degrade the COD of organic wastewater.
  • the flow control valve 7-2 is opened according to the process requirements to start the pump 31-4 to guide part of the solution in the high-level tank area through the current-breaking isolator 45-2 into the temporary storage tank 23-3.
  • the flow control valve 7-2 and the pump 31-4 are closed, and then the solution 28 to be treated is added to the high-level tank area until the liquid level reaches the set value of the detection sensor 26-5.
  • the stirring devices 17 and 18 are shut down according to the process control, and the flow control valve 7-1 is opened, and the pump 31-3 is started 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.
  • the flow control valve 7-1 When the liquid level in the high-level tank area drops to the liquid level setting value of the detection sensor 26-6, the flow control valve 7-1 is closed and the pump 31-5 is turned on to add the electrolytic 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 the detection sensor 26-5, and then the electrolysis power supply 4 is turned on again and the stirring devices 17 and 18 are started to continue the operation until the treatment of the solution 28 is completed.
  • the pump 31-2 is turned on to pump the electrolytic solution 29-2 in the temporary storage tank 23-2 into the temporary storage tank 23-1, and the vacuum ejector 21 is used to absorb the oxygen escaping from the anode tank area of the electrolytic tank for oxidation reaction.
  • the electrolytic cell of the high-low tank area combination structure of the present invention reduces the electrolyte in the cathode tank area from entering the anode tank area by utilizing the gravity of the solution to make the solution in the high tank area have a tendency to flow to the low tank area and controls the flow control valve of the two tank area drain pipes to temporarily and effectively separate the electrolyte in the cathode and anode tank areas. Therefore, this embodiment can effectively solve the problem of low reaction efficiency when using an electrolytic cell without separation.
  • the alkaline degreasing waste liquid produced when the electroplated parts are cleaned is sent to Electrochemical treatment was carried out, and the treated solution 29-1 was sampled and tested from the temporary storage tank 23-1. It was found that the COD value in the waste liquid was reduced from the original 31000 mg/L to 13500 mg/L, achieving the purpose of degrading the organic waste liquid.
  • this embodiment is based on an electrolytic cell having a U-tube combination structure as shown in FIG16 .
  • the bottom of the anode tank area 48 and the bottom of the cathode tank area 49 of the electrolytic cell 1 are located on the same horizontal line and are connected through a small inter-tank solution communication pipe 11, on which a valve 30-1 is provided, and bubble barriers are provided at both ends of the pipe opening; the volume of the 200-liter cathode tank area 49 is about twice the volume of the anode tank area 48.
  • Both the anode tank area 48 and the cathode tank area 49 are provided with a drain pipe with a flow control valve.
  • Detection sensors 26-1, 26-2 and 26-3, 26-4 are respectively provided in the anode and cathode tank areas.
  • the anode tank area 48 and the cathode tank area 49 are respectively connected to the large-scale storage tank-type temporary storage tanks 23-1 and 23-2 through the overflow buffer tank.
  • the temporary storage tank 23-3 is a pH adjustment tank, in which detection sensors 26-5 and 26-6 are provided, which are respectively connected to the inlet of the cathode tank area 49 and the anode tank area 48 through the solid-liquid separators 24-1 and 24-2; the two solid-liquid separators perform solid-liquid separation on the solution 28-2 to remove solid impurities in the organic waste liquid.
  • the detection sensors 26-1, 26-3, 26-5, 26-7 and 26-8 are level meters, 26-2 and 26-4 are thermometers, and 26-6 is a pH meter.
  • the configured pumps 31-1 and 31-4 are variable frequency pumps for circulating flow control and for balancing and stabilizing the liquid level of the electrolyte in the positive and negative electrode tanks during the flow of the solution.
  • the output voltage of the electrolytic power supply 4 is selected to be a product that can reach 120V.
  • 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 part of the chloride ions so that the chloride ion concentration in the solution drops to below 2 g/L before it can enter the biochemical pool for further biochemical treatment according to the process requirements.
  • the solution 28-1 to be treated is a raw organic waste liquid containing a relatively high chloride ion concentration.
  • 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, and after mixing, the solution 28-2 to be treated is obtained.
  • Pumps 31-5 and 31-6 are turned on to respectively add the solution 28-2 to be treated into the anode and cathode tanks 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 and the cathode tank respectively; after reaching the set liquid level, pumps 31-5 and 31-6 are turned off, and circulating pumps 31-1 and 31-4 are started, valve 30-1 is opened and electrolysis power supply 4 is turned on to perform electrolysis operation; during the electrolysis process, chloride ions are enriched in the anode tank 48 and chlorine gas is electrolyzed, and chloride ions in the cathode tank 49 migrate to the anode tank 48 under the action of the electric field force, so that The chloride ions in the cathode electrolyte are reduced and hydrogen is electrolyzed at the cathode.
  • 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 the dynamic balance of the positive and negative electrolytes in the flow, so that the bubble-containing solution can quickly precipitate the bubbles through the liquid flow.
  • the electrolytic cell of the U-tube combined structure of the present invention utilizes the anode cell area and the cathode cell area and the temporary storage tank connected thereto as the liquid flow generated by the circulation of the electrolyte, effectively preventing the electrolytes in the cathode and anode cell areas from mixing, so that the electrolytes in the cathode and anode cell areas are temporarily and effectively separated, and the chlorine generated on the anode is prevented from entering the cathode cell 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 separation.
  • the above operation can be used to remove chlorine from organic wastewater containing a high concentration of chloride ions.
  • the chloride ion concentration of solution 29-2 after electrolysis is detected to be 1.93 g/L, and it can enter the biochemical treatment tank for the next step of treatment according to the process requirements.
  • FIG6 it is a device and process flow chart of Example 6.
  • This embodiment adopts an electrolytic cell with a combination structure of two high and low tank areas, that is, the bottom of the high tank area is higher than the bottom of the low tank area, and the high tank area is used as the cathode tank area.
  • the device of this embodiment specifically includes an electrolytic cell 1-1, an electrolytic cell 1-2, an electrolytic cell area sealing tank cover 8-1 to 8-4, a bipolar electrode 12, an impeller stirring device 17, a liquid circulation stirring device 18, a gas-liquid separator 19, a vacuum ejector 24, a spray tower 22, three temporary storage tanks, multiple sensors 26, an automatic detection and feeding controller 27, and two hydrogen high-altitude safety discharge pipes 46.
  • the output voltage of the electrolytic power supply 4-1 can reach 160V
  • the output voltage of the electrolytic power supply 4-2 can reach 180V.
  • the electrolytic cell 1-1 has a structure as shown in FIG12
  • the electrolytic cell 1-2 has a structure as shown in FIG14 , wherein one side of the high-level cell areas 2-1 and 2-2 of the electrolytic cell 1-1 and the low-level cell areas 3-1 and 3-2 are partially bonded to each other, and the bonding positions are provided with inter-cell solution communication gaps 10-1 and 10-2.
  • the communication gaps at the bonding positions of the two cell areas of the electrolytic cell 1-1 are provided with bubbles.
  • the barrier 37-1 is a filter cloth used to prevent gas from passing through the tank area.
  • the bottom of the high-level tank area 2 of the electrolytic tank 1-2 is also connected to the low-level tank area 3 through a small inter-tank solution communication pipe 11.
  • a bipolar electrode 12 is placed in the inter-tank solution communication pipe 11, and a gap is left between the bipolar electrode 12 and the pipe wall.
  • the top of the high-level tank area 2-1 is provided with a gas collecting tank cover 8-1 and an exhaust pipe 9-3, and the top of the low-level tank area 3-1 is sealed as a gas collecting tank cover and is provided with exhaust pipes 9-1 and 9-2; wherein the exhaust pipes 9-1 and 9-2 are both provided with a release chamber and are connected with a gas-liquid separator 19, which is specifically a three-way pipe.
  • the top of the high-level tank area 2-2 is provided with a gas collecting tank cover 8-4 and an exhaust pipe 9-5, and the top of the low-level tank area 3-2 is provided with a gas collecting tank cover 8-3 and an exhaust pipe 9-4.
  • the low-level tank area 3-1 is provided with a drain pipe of a flow control valve 7-1, and the liquid outlet of the gas-liquid separator 19 is connected to the drain pipe and leads to the temporary storage tank 23-2.
  • the temporary storage tank 23-2 is provided with a vacuum ejector 21, and the temporary storage tank 23-2 is connected to the temporary storage tank 23-1 through a liquid pipeline, and is connected to the spray tower 22 provided in the temporary storage tank 23-1 through a gas pipeline.
  • the vacuum ejector 21 is used to attract 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 a second-stage oxygen oxidation reaction.
  • the low-level tank area 3-2 is provided with a discharge pipe of a flow control valve 7-2, which is connected to the feed port of the high-level tank area 2-1.
  • the feed port of the high-level tank area 2-2 is connected to the temporary storage tank 23-3 through the solid-liquid separator 24.
  • the solid-liquid separator 24 filter is used to filter solid impurities in the solution 28 to be treated.
  • Detection sensors 26-3 are ORP meters
  • 26-4 are ORP meters
  • 26-5 are liquid level meters installed in the low-level tank area 3-1 and the high-level tank area 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.
  • detection sensors 26-6 as an ORP meter, 26-7 as an ORP meter and 26-8 as a liquid level meter are installed, wherein the insoluble anode 5-2 is a titanium-based coating electrode, and the electrolysis cathode 6-2 is a nickel plate; wherein the bipolar electrode particles in the connecting pipe are conductive graphite.
  • the automatic detection and feeding controller 27 is used for operating program control of the whole set of equipment.
  • 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.
  • the solution 28 to be treated in this embodiment is an organic waste liquid containing acrylic acid, and its COD is 120000 mg/L.
  • This embodiment uses the device of the present invention to mainly 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.
  • the automatic detection feed controller 27 controls the opening of the flow control valve 7-2, and the electrolytically oxidized solution 29-3 is slowly pumped to the high-level tank area 2-1 by starting pumps 31-5 and 31-4 for 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.
  • 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 feed 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 turned on to replenish the electrolytically treated solution 29-3 in the overflow buffer tank 25 into the high-level tank area 2-1 for a reduction reaction again.
  • the pumps 31-1 and 31-3 are started to operate so that the vacuum ejector 21 and the spray tower 22 absorb the oxygen released from the electrolytic tank and the gas-liquid separator to perform a two-stage oxidation reaction on the electrolytically treated solution 29-2.
  • the automatic detection feed controller 27 controls the valve 30-1 to open to discharge part or all of the treated solution 29-1.
  • the COD concentration of the solution 29-1 is 45000 mg/L after detection, which is the final treated solution.
  • the electrolytic cell of the high-low tank area combination structure of the present invention reduces the electrolyte in the cathode tank area from entering the anode tank area by utilizing the gravity effect on the solution to make the solution in the high tank area have a tendency to flow to the low tank area and to control the electrolyte in the high tank area to flow to the low tank area, so that the electrolyte in the cathode and anode tank areas are temporarily and effectively separated. Therefore, this embodiment can effectively solve the problem of low reaction efficiency when using an electrolytic cell without separation.
  • the acrylic acid-containing waste liquid is subjected to a process of reduction ⁇ oxidation ⁇ reduction ⁇ oxidation ⁇ oxidation
  • the technical problem of electrolyte cross-linking foaming is solved during the electrochemical reaction and the COD value of the original solution can be degraded from as high as 120,000 mg/L to 45,000 mg/L.
  • FIG. 7 it is a device and process flow chart of Example 7.
  • This embodiment adopts the electrolytic cell with the U-shaped tube partition structure of FIG. 17 .
  • this embodiment combines the electrolysis device of the present invention with the hydrogenation device in Chinese Patent Application No. 202310394209.X “A method and device for using hydrogen to participate in organic reactions under normal pressure” to manufacture a new and efficient hydrogen-rich water machine.
  • This embodiment mainly includes an electrolytic cell with 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 metal surfaces to ensure that the produced hydrogen-rich water contains no or little heavy metal ions.
  • the bottom of the anode tank area 48 and the bottom of the cathode tank area 49 of the electrolytic cell 1 are located on the same horizontal line, and the two are connected and attached to each other.
  • a connecting gap 10 is provided only at the lower part of the partition where the two are attached.
  • a gate 47 is installed at the connecting gap, and a bubble barrier 37 is provided.
  • the anode tank area 48 and the cathode tank area 49 are both provided with drainage pipes, and flow control valves 7-2 and 7-1 are respectively installed.
  • a hydrogenation device and a detection sensor 26-1 are installed in the cathode tank area 49 of the electrolytic cell 1; the detection sensor 26-1 is an ORP meter, which is used to safely monitor the reduction value of hydrogen-rich water.
  • the detection sensor 26-2 and the detection sensor 26-3 are installed in the anode tank area, which are an ORP meter and a liquid level meter respectively. During the electrolysis process, the detection and control of each detection sensor are used to achieve that the manufactured hydrogen-rich water meets the drinking water standard.
  • the electrolytic cell adopts the structure of Figure 17.
  • the utilization and treatment of the anode electrolysis gas and the cathode electrolysis gas can be separated, so that the anode electrolyte produces a chlorine-containing disinfectant washing liquid, and the cathode electrolyte produces hydrogen-rich water that meets the drinking water standard.
  • the working voltage of the electrolysis power supply used in this embodiment is 24V.
  • the cathode tank area 49 of the electrolytic cell 1 and the hydrogenation device component 41 are combined to form a hydrogenation device.
  • the hydrogenation device adopts the equipment for safely treating hydrogen by an electro-oxidation process in Chinese Patent No. ZL202220949622.9 "A device for safely treating hydrogen by an electrochemical process", specifically a hydrogen oxidation electrolytic cell.
  • It includes 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 arranged in 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 electrolytic cell is directly arranged in the hydrogen source electrolytic cell, and the hydrogen oxidation electrolytic anode and the oxygen-consuming electrolytic cathode are installed in the hydrogen source electrolytic cell body at a spatial position close to the hydrogen source electrolytic cathode, and in the hydrogen oxidation electrolytic cell body, the hydrogen oxidation electrolytic anode and the oxygen-consuming electrolytic cathode are installed in the hydrogen source electrolytic cell body.
  • the anode for hydrogen oxidation electrolysis and the cathode for oxygen consumption electrolysis are connected via the bridge.
  • the electrolytic cell 1 of the present invention is used as the hydrogen source electrolytic cell.
  • the hydrogenation device in the cathode tank area further electrochemically catalyzes the hydrogen to remove oxidizing substances in the tap water, and fully utilizes the trace amount of hydrogen raw materials to produce hydrogen-rich water.
  • the electrolysis power supply 4 is turned off and the gate 47 is closed.
  • the electrolytic cell of the U-tube combination structure of the present invention is equipped with a gate and a bubble barrier at the connecting gap and a flow control valve on the drain pipe to effectively prevent the electrolytes in the cathode and anode tanks from mixing, so that the electrolytes in the cathode and anode tanks are temporarily and effectively separated.
  • the chlorine generated on the anode is prevented from entering the cathode tank area and being electrochemically reduced to chloride ions, and the hydrogen generated on the cathode is prevented 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.
  • the use cost and replacement cost of the electrolytic cell partition can be saved.
  • 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.
  • Example 7 As shown in FIG. 7 , the device diagram of Example 7 is adopted.
  • the detection sensor 26-1 is a liquid level meter
  • 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;
  • Exhaust pipe 9-1 and Chinese patent number ZL202220949622.9 "A method for safely treating hydrogen by electrochemical process"
  • the device for safely treating hydrogen by an electro-oxidation process in the "Equipment for Treating” is connected to treat the hydrogen tail gas;
  • the hydrogen introduction device used is a gas-liquid mixing device;
  • the hydrogenation device adopts the device for participating in organic reactions using hydrogen at normal pressure in Chinese patent application 202310394209.X "A method and device for participating in organic reactions using hydrogen 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 with an exhaust gas outlet or 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, and the conductor 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 produce a hydrogen enrichment area in the anaerobic reactor, and its hydrogen production electro
  • the hydrogen production electrolysis device described in the patent application is provided with an electrolytic cell separator 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, and the electrolytic cathode is placed in the cathode cell area and connected to the negative electrode of the electrolytic power supply; and the cathode cell area and the space in the anaerobic reactor where the hydrogen activation anode is placed are combined into an integral space.
  • the electrolytic cell 1 of the present invention replaces the electrolytic cell provided with an electrolytic cell separator and is used as the hydrogen production electrolytic device in the hydrogenation device.
  • 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.
  • 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.
  • the electrolysis power supply 4 is turned off and the gate 47 is closed.
  • the electrolytic cell of the U-tube combination structure of the present invention is equipped with a gate and a bubble barrier at the connecting gap and a flow control valve on the drain pipe to effectively prevent the electrolytes in the cathode and anode tanks from mixing, so that the electrolytes in the cathode and anode tanks are temporarily and effectively separated.
  • the chlorine generated on the anode is prevented from entering the cathode tank area and being electrochemically reduced to chloride ions, and the hydrogen generated on the cathode is prevented 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.
  • the use cost and replacement cost of the electrolytic cell partition can be saved.
  • the chloride ion concentration of the solution in the cathode tank area was measured to drop 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.
  • the solution to be treated in Example 1 is electrolyzed using an electrolytic cell without partitions.
  • the electrolytic anode is an insoluble anode, specifically a titanium-based coating anode; and the electrolytic cathode is a titanium plate.
  • the solution to be treated is 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.
  • an electrochemical reaction occurs on the insoluble anode in which the 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 cathode is the electrolysis of metallic copper.
  • some of the trivalent iron ions generated on the electrolysis anode touch the electrolysis cathode and are electrochemically reduced, and some of the trivalent iron ions corrode and dissolve the metallic copper electrolyzed at the cathode, resulting in low reaction efficiency.
  • the electrolytic cell with an electrolytic cell separator is used to electrolyze the solution to be treated in Example 1.
  • the electrolytic cell separator is an anion exchange membrane.
  • the electrolytic anode is an insoluble anode, specifically a titanium-based coating anode; and the electrolytic cathode is a titanium plate.
  • the solution to be treated is 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.
  • the insoluble anode undergoes electrochemical reactions in which the 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 cathode is the electrolysis of metallic copper.
  • sponge copper is electrolyzed, and fine copper particles float with the electrolyte and adhere to the electrolytic cell separator.
  • the bipolar electrode grows into a needle due to the concentrated current passing through, piercing and damaging the separator.

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Mechanical Engineering (AREA)
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  • Hydrology & Water Resources (AREA)
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  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La divulgation concerne un appareil d'électrolyse ayant une structure de communication à fente séparant des compartiments d'anode et de cathode. L'appareil d'électrolyse comprend une cellule électrolytique, une anode d'électrolyse, une cathode d'électrolyse et une alimentation électrique d'électrolyse, et est caractérisé en ce qu'une structure de communication à fente est disposée dans la cellule électrolytique, la structure de communication à fente divisant la cellule électrolytique en un compartiment d'anode et un compartiment de cathode, au moins un compartiment étant pourvu d'au moins un tuyau de drainage ayant une valve de régulation de débit utilisée pour commander les conditions d'écoulement en temps réel de l'électrolyte dans chaque compartiment en fonction du débit ; l'anode d'électrolyse est disposée dans le compartiment d'anode et connectée à une électrode positive de l'alimentation électrique d'électrolyse, et la cathode d'électrolyse est disposée dans le compartiment de cathode et connectée à une électrode négative de l'alimentation électrique électrolytique. Le présent appareil d'électrolyse permet d'obtenir efficacement une division fonctionnelle de compartiments d'anode et de cathode dans la cellule électrolytique sans utiliser de séparateur de cellule électrolytique, ce qui facilite une réaction d'électrolyse et réduit le coût de fonctionnement de l'appareil d'électrolyse. La divulgation concerne également un procédé d'électrolyse mis en œuvre à l'aide de l'appareil d'électrolyse.
PCT/CN2024/074790 2023-01-31 2024-01-30 Appareil d'électrolyse ayant une structure de communication à fentes séparant des compartiments d'anode et de cathode, et procédé d'électrolyse associé Ceased WO2024160212A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119220996A (zh) * 2024-12-03 2024-12-31 福建德尔科技股份有限公司 一种全氟三丁胺制备装置与制备工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012179569A (ja) * 2011-03-02 2012-09-20 Panasonic Corp 電解槽および当該電解槽を備える電解水生成装置
CN103014746A (zh) * 2013-01-06 2013-04-03 东北电力大学 一种电解法制备液体高铁酸盐装置及其工艺
CN103787490A (zh) * 2013-11-22 2014-05-14 浙江工商大学 一种用于处理有机氟废水的生物电化学反应器及有机氟废水的处理方法
CN105004709A (zh) * 2015-04-13 2015-10-28 中国地质大学（武汉） 一种液体放电微等离子体激发源装置及等离子体激发方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012179569A (ja) * 2011-03-02 2012-09-20 Panasonic Corp 電解槽および当該電解槽を備える電解水生成装置
CN103014746A (zh) * 2013-01-06 2013-04-03 东北电力大学 一种电解法制备液体高铁酸盐装置及其工艺
CN103787490A (zh) * 2013-11-22 2014-05-14 浙江工商大学 一种用于处理有机氟废水的生物电化学反应器及有机氟废水的处理方法
CN105004709A (zh) * 2015-04-13 2015-10-28 中国地质大学（武汉） 一种液体放电微等离子体激发源装置及等离子体激发方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119220996A (zh) * 2024-12-03 2024-12-31 福建德尔科技股份有限公司 一种全氟三丁胺制备装置与制备工艺

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