Gas-liquid mixing type electrochemical reaction device for treating hydrogen or oxygen, and method for treating hydrogen or oxygen by using same

Abstract

Disclosed in the present invention is a gas-liquid mixing type electrochemical reaction device for treating hydrogen or oxygen. The gas-liquid mixing type electrochemical reaction device comprises an electrolytic cell, which mainly consists of an electrolytic cell body, an electrolytic anode, an electrolytic cathode and an electrolytic power supply, wherein the electrolytic anode is connected to a positive electrode of the electrolytic power supply, and the electrolytic cathode is connected to a negative electrode of the electrolytic power supply, characterized in that the electrolytic cell comprises a gas-liquid mixture source and / or at least one electrolytic-cell gas-liquid mixer, and an electrocatalytic component, which form a gas-liquid mixing type electrolytic cell; and the gas-liquid mixture source is connected to the electrolytic cell body by means of a liquid flow pipeline, and an outlet of the electrolytic-cell gas-liquid mixer faces or is located in the electrolytic cell body. Further disclosed in the present invention is a method for treating hydrogen or oxygen by using the gas-liquid mixing type electrochemical reaction device.

Description

A gas-liquid mixed electrochemical reaction device for treating hydrogen or oxygen and a method for treating hydrogen or oxygen Technical Field

[0001] The present invention belongs to the technical field of chemical reactions of substances, and particularly relates to a gas-liquid mixing electrochemical reaction device for treating hydrogen or oxygen and a method for treating hydrogen or oxygen. Background Art

[0002] With the development of industrial production technology, the use of electrochemical processes and equipment in an ever-increasing number of fields continues to expand. Many electrochemical processes, such as hydrogen production by alkaline water electrolysis and electrolytic treatment of organic wastewater or wastewater containing ammonia and nitrogen, require hydrogen purification or hydrogen removal in actual production.

[0003] In the electrolytic hydrogen production process, when pure water is used for electrolysis, the hydrogen produced by electrolysis often contains a small amount of oxygen, and the oxygen produced by electrolysis often contains a small amount of hydrogen. When hydrogen is produced using an aqueous solution containing chloride ions, the hydrogen produced by electrolysis often contains a small amount of oxygen and chlorine, and the oxygen produced by electrolysis often contains chlorine and a small amount of hydrogen. The typical process principle of hydrogen purification devices currently used in the electrolytic water hydrogen production process is to use a catalyst to accelerate the reaction of hydrogen and oxygen to form water to remove the small amount of oxygen in the hydrogen, or to use an adsorbent to separate hydrogen or oxygen from other gases. However, the catalysts and adsorbents used in these hydrogen purification devices are not only expensive and costly to use, but also generate waste.

[0004] On the other hand, existing technologies for treating waste liquid electrolysis typically discharge hydrogen gas into the atmosphere for safe disposal, but this poses a safety hazard due to leakage in the discharge pipe. Therefore, a safer and more cost-effective treatment method is needed.

[0005] Summary of the Invention

[0006] The first objective of the present invention is to provide a gas-liquid hybrid electrochemical reaction device for treating hydrogen or oxygen. This device utilizes a gas-liquid hybrid electrolytic cell to improve the gas solubility and mass transfer properties of the reactants, purifying the hydrogen or oxygen through electrochemical reactions or efficiently eliminating hydrogen. A second objective is to provide a gas-liquid hybrid electrochemical reaction device and a method for treating hydrogen or oxygen using the device, addressing the high cost of purifying hydrogen or oxygen in existing technologies and the safety issues associated with treating hydrogen and oxygen.

[0007] The first object of the present invention is achieved through the following technical solutions.

[0008] A gas-liquid mixing electrochemical reaction device for processing hydrogen or oxygen, comprising an electrolytic cell mainly composed of an electrolytic cell body, an electrolytic anode, an electrolytic cathode, and an electrolytic power supply, wherein the electrolytic anode is connected to the positive electrode of the electrolytic power supply, and the electrolytic cathode is connected to the negative electrode of the electrolytic power supply; the electrolytic cell is characterized in that it includes a gas-liquid mixture source and / or at least one electrolytic cell gas-liquid mixer, and an electrocatalytic component, forming a gas-liquid mixing electrolytic cell; the gas-liquid mixture source is connected to the electrolytic cell body by a liquid flow conduit, and the outlet of the electrolytic cell gas-liquid mixer is oriented toward or located in the electrolytic cell body; the electrocatalytic component adopts any one or more of the following methods:

[0009] Electrocatalytic method (1) At least one electrocatalytic component is built into the electrolytic cell body, the gas-liquid mixture source flows toward the electrocatalytic component and / or the electrolytic anode and / or the electrolytic cathode, and / or the outlet of the electrolytic cell gas-liquid mixer is directed toward the electrocatalytic component and / or the electrolytic anode and / or the electrolytic cathode;

[0010] Electrocatalytic method (2) improves the electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode, that is, at least one of the electrolytic anode and the electrolytic cathode is one or more parallel-connected electrodes, the gas-liquid mixture source flows toward the electrolytic anode and / or the electrolytic cathode with improved electrocatalytic performance structure, and / or the outlet of the electrolytic tank gas-liquid mixer is directed toward the electrolytic anode and / or the electrolytic cathode with improved electrocatalytic performance structure;

[0011] Electrocatalytic method (3): The electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode is improved, and the angle ɑ formed by a part or the whole of at least one of the electrolytic anode and the electrolytic cathode and the straight line of the gas-liquid mixture ejected from the outlet of the electrolytic tank gas-liquid mixer is greater than 0° and less than 90°, and the outlet of the electrolytic tank gas-liquid mixer is oriented toward the electrolytic anode and / or the electrolytic cathode with the improved electrocatalytic performance structure.

[0012] The gas-liquid mixture source is a pipe or tank that flows or stores a gas-liquid mixture of the gas to be reacted and the electrolyte, which is connected to the electrolytic cell body. The electrolytic cell gas-liquid mixer described in the present invention has an inlet and at least two outlets, or a structure having a liquid inlet, an air inlet, and an outlet. When the electrolytic cell gas-liquid mixer has an inlet and at least two outlets, the outlet extends into the electrolytic cell body and is used to disperse the reaction gas or gas-liquid mixture into the electrolyte in the electrolytic cell for gas-liquid mixing; when the electrolytic cell gas-liquid mixer has a liquid inlet, an air inlet, and an outlet, the liquid inlet is connected to the electrolytic cell body by a pipe, and the outlet faces or extends into the electrolytic cell body, and is used to input the electrolyte in the electrolytic cell into the gas-liquid mixer so that it is mixed with the reaction gas entering the gas-liquid mixer and then returned to the electrolytic cell.

[0013] The electrocatalytic components in the electrocatalytic structure (1) of the present invention are arranged in the electrolytic cell body and below the electrolyte liquid level, and are used to achieve electrochemical catalytic reaction under the action of electric field force. The specific electrocatalytic components are bipolar electrodes and / or insoluble conductors, and the specific number and location of the electrocatalytic components can be determined according to the performance of the process setting.

[0014] The bipolar electrode is an insoluble conductor placed between the electrolytic anode and cathode, not connected to an external power source, and immersed in the electrolyte. Its shape and size are not restricted. During electrolysis, the bipolar electrode, when placed in an electric field, can undergo an electrochemical reaction with the substance in that position without requiring direct electrical connection to the electrolytic power source. The end closest to the anode acts as a cathode, causing a reduction reaction on some reducible substances in the electrolyte, while the end closest to the cathode acts as an anode, causing an oxidation reaction on some oxidizable substances in the electrolyte. When multiple bipolar electrodes are used, each bipolar electrode is ideally an independent conductor with no electrical connection to each other. Under the action of the electric field, each bipolar electrode can independently perform its function, forming multiple inductive small cathodes and anodes to enhance the electrocatalytic effect.

[0015] Preferably, as shown in FIG4 , when more than one bipolar electrode is used, the central surface of the bipolar electrode conductor is partially coated with an insulating material to reduce the risk of the bipolar electrodes contacting each other and forming a single large bipolar electrode due to electrical conduction, thereby reducing the ability of each small bipolar electrode to independently perform its electrocatalytic function. Preferably, a powdered conductive material capable of flowing with the electrolyte is used as the bipolar electrode.

[0016] The insoluble conductor is directly conductively connected to the electrolytic anode or cathode, transforming the anode or cathode into an irregularly shaped electrode. This increases the electrode surface area and promotes the electrochemical reaction with the electrolyte, thereby achieving a catalytic effect. The insoluble conductor connected to the electrolytic anode is referred to as the insoluble anode conductor, while the insoluble conductor connected to the electrolytic cathode is referred to as the insoluble cathode conductor.

[0017] The present invention utilizes the characteristics of an insoluble conductor to introduce a reactive gas into the electrolyte for mixing, thereby achieving a highly efficient electrocatalytic electrochemical reaction. As shown in FIG5 , the insoluble conductor is insoluble or poorly soluble in the electrolyte it contacts, and its shape and size are not limited.

[0018] The gas-liquid mixture used in the present invention is derived from a gas-liquid mixture source and / or is generated by mixing the reacting gases into the electrolyte in the electrolytic cell gas-liquid mixer. When the gas-liquid mixing electrochemical reaction device of the present invention is used to purify hydrogen or oxygen, or to efficiently eliminate hydrogen, the reacting gases are hydrogen and / or oxygen, and possibly chlorine, other oxidizing gases, and other reducing gases. Oxygen and chlorine are oxidizing gases, and hydrogen is a reducing gas.

[0019] The electrolysis process of the present invention requires the combined participation of gas and electrolyte, with the chemical reaction being promoted by an electrocatalytic structure. The specific working principle is: the resulting gas-liquid mixture is brought into contact with at least one of the electrocatalytic components, electrolytic anode, and electrolytic cathode within a gas-liquid hybrid electrolytic cell, allowing the gas-liquid mixture containing an oxidizing gas to react with the negatively charged components of the gas-liquid hybrid electrolytic cell, and / or allowing the gas-liquid mixture containing a reducing gas to react with the positively charged components of the gas-liquid hybrid electrolytic cell. The presence of sufficient gas in the gas-liquid mixture promotes an electrochemical reaction in components with one charge, and the resulting electron gain and loss catalyzes a positive electrochemical reaction in components with the other charge, while preventing the substances in the electrolyte from being repeatedly reacted in components of both charges, resulting in consumption and reduced efficiency. Compared to liquid oxidants or reducing agents, the use of oxidizing or reducing gases can better catalyze electrochemical reactions, is less expensive, and does not increase the amount of electrolyte. In the gas-liquid hybrid electrolytic cell, when electrolysis is carried out, the negatively charged component is at least one of the electrolysis cathode, the end of the bipolar electrode that functions as the cathode, and the insoluble cathode conductor, and the positively charged component is at least one of the electrolysis anode, the end of the bipolar electrode that functions as the anode, and the insoluble anode conductor. That is, to achieve the aforementioned electrocatalytic effect, during the electrolysis process, an oxidizing gas is used to electrochemically react with the negatively charged component to seal the component, thereby ensuring that the reduced substance to be treated can undergo electrochemical oxidation treatment at the positively charged component; or a reducing gas is used to electrochemically react with the positively charged component to seal the component, thereby ensuring that the reduced substance to be treated can undergo electrochemical reduction treatment at the negatively charged component. During the electrolysis process, the positively charged components convert electrical energy into chemical energy, electrocatalytically oxidizing reducing substances in the electrolyte. They also oxidize oxygen, hydroxide ions, chloride ions, and other radicals in the electrolyte to produce large quantities of superoxide radicals (O2·), hydroxyl radicals (OH·), and / or chlorine radicals (Cl·), chloroxyl radicals (ClO·), and other oxidizing free radicals, rapidly oxidizing substances in the electrolyte requiring oxidation. Furthermore, the vacated negatively charged components convert electrical energy into chemical energy, electrocatalytically reducing oxidizing substances in the electrolyte. They also generate large quantities of hydrogen radicals (H·) or protons, which rapidly induce at least one of hydrogenolysis, hydrogenation, and reduction reactions on substances in the electrolyte requiring reduction.

[0020] When a gas-liquid mixture containing an oxidizing gas contacts a negatively charged component during electrolysis, taking sufficient oxygen as an example, the main electrochemical reaction that occurs is: O2+4H + +4e - →H2O.

[0021] When a gas-liquid mixture containing reducing gas contacts a positively charged component in the electrolysis process, taking sufficient hydrogen as an example, when the electrolyte contains organic matter, in addition to the organic matter reduction reaction, the main electrochemical reaction is: H2-2e - →2H + , or H2+2[OH] - -2e - →2H2O.

[0022] The present invention utilizes an external input gas as the gas source for the reaction. The external input gas is mixed with the electrolyte in the electrolytic cell and then sprayed into contact with the electrolytic electrodes and / or electrocatalytic components in the cell to initiate an electrochemical reaction. Therefore, the electrolysis power source applies a voltage between the electrolytic anode and the electrolytic cathode equal to or lower than the decomposition voltage of the electrolyte to perform the electrolysis operation, thereby preventing the generation of gas from the electrolytic anode and / or the electrolytic cathode, which could affect the treatment efficiency.

[0023] The electrolyte decomposition voltage is the voltage at which, under static conditions, the voltage applied by the electrolysis power source between the anode and cathode of the electrolytic cell's electrolyte just causes the electrolyte to electrolyze a very small amount of oxidizing gas or a very small amount of reducing gas. The electrolyte decomposition voltage is dependent on a variety of factors, including the electrolyte concentration, viscosity, temperature, the amount of gas involved in the reaction, the distance between the cathode and anode, and the materials used for the anode and cathode electrodes.

[0024] To prevent electrolytic gas from being deposited on the anode and / or cathode of a gas-liquid hybrid electrolyzer, the voltage applied between the anode and cathode by the electrolysis power supply during operation is required to be less than or equal to the electrolyte decomposition voltage. However, when sufficient reducing gas participates in the electrochemical reaction at the ends of positively charged components, making it difficult for the positively charged components to deposit oxidizing gas, or when sufficient oxidizing gas participates in the electrochemical reaction at negatively charged components, making it difficult for the negatively charged components to deposit reducing gas, the voltage applied between the anode and cathode by the electrolysis power supply of the electrolysis cell can be slightly higher than the electrolyte decomposition voltage. This is because the higher the voltage applied between the anode and cathode by the electrolysis power supply, the stronger the reducing or oxidizing properties of the cathode under these conditions. Therefore, for safety reasons, the voltage applied between the anode and cathode by the electrolysis power supply can be set to be slightly higher than the electrolyte decomposition voltage to increase the electrochemical reaction rate.

[0025] The material of the contact portion between the electrolytic cell and the electrolyte is selected from at least one of a polymer resin, a metal material lined with an insulating anti-corrosion sleeve, and a metal material coated with an insulating anti-corrosion coating. Preferably, when the electrolyte temperature is high, the electrolytic cell material is selected from polytetrafluoroethylene.

[0026] The surface of the electrolytic anode is selected from at least one material selected from the group consisting of gold, platinum, nickel, alloys containing at least one of the aforementioned metals, titanium-coated insoluble anodes, and graphite, and its shape and size are not limited. The surface of the electrolytic cathode is selected from at least one material selected from the group consisting of gold, platinum, silver, titanium, copper, nickel, alloys containing at least one of the aforementioned metals, stainless steel, and graphite, and its shape and size are not limited. The electrolytic power supply is a suitable electrolytic power supply that can meet the operating voltage and current density requirements of the gas-liquid hybrid cell during the electrolysis process.

[0027] The surface material of the bipolar electrode can be any conductive material that is insoluble or poorly soluble in the electrolyte it contacts, such as a metal, metal oxide, metal semiconductor, conductive graphite, activated carbon, etc. The appropriate bipolar electrode material is selected based on the conductor's performance in actual chemical reactions. Preferably, the surface of the bipolar electrode is made of at least one of gold, platinum, nickel, copper, cobalt, iron, nickel, molybdenum, tin, bismuth, aluminum, ruthenium, titanium, tantalum, an alloy containing at least one of the above metals, copper oxide, zinc oxide, aluminum oxide, an insoluble electrode with a titanium-based coating, activated carbon, or graphite. More preferably, the surface material of the bipolar electrode used in acidic electrolytes is at least one of gold, platinum, and graphite. When using a powdered conductive material that can flow with the electrolyte as the bipolar electrode, a liquid spray pipe is installed to prevent the powdered bipolar electrode from sinking to the bottom or corners of the tank.

[0028] The surface material of the insoluble conductor is any conductive material such as conductive metal, conductive metal oxide, semiconductor, etc. The appropriate insoluble conductor material is selected according to the performance of the conductor in the actual chemical reaction. Preferably, the material of the insoluble anode conductor is consistent with the material of the electrolytic anode. When the insoluble conductor is in contact with the electrolytic anode, its surface is a material selected from at least one of gold, platinum, nickel, an alloy containing at least one of the above metals, a titanium-based coated insoluble electrode, and graphite. More preferably, when the anode electrolyte is alkaline, the surface of the insoluble conductor arranged in the anode tank area is made of nickel material. When the insoluble conductor is in contact with the electrolytic cathode, its surface is a material selected from at least one of gold, platinum, silver, titanium, copper, nickel, an alloy containing at least one of the above metals, stainless steel, and graphite.

[0029] The gas-liquid mixture outlet of the electrolytic cell gas-liquid mixer is designed with the number of nozzles and the shape of the liquid spray according to the spraying object, so that the gas-liquid mixture sprayed from the outlet can effectively and fully contact at least one of the electrocatalytic component, the electrolytic anode, and the electrolytic cathode to achieve a better catalytic effect. The electrolytic cell gas-liquid mixer is a bubbling electrolytic cell gas-liquid mixer and / or a vacuum jet electrolytic cell gas-liquid mixer. From the perspective of safe production and gas-liquid mixing effect, it is preferred to use a vacuum jet electrolytic cell gas-liquid mixer, or a gas-liquid mixer combining the bubbling type and the vacuum jet type, as shown by number 9 in Figure 1. The material of the surface of the electrolytic cell gas-liquid mixer in contact with the electrolyte is selected from at least one of titanium, gold, platinum, nickel, conductive graphite, stainless steel, fiberglass, and polymer resin materials, and is specifically selected according to the chemical properties of the electrolyte and the gas participating in the reaction.

[0030] The present invention can be improved as follows: the electrolytic cell gas-liquid mixer is made of a conductive material and electrically connected to at least one of the electrolysis power source, the electrolysis anode or cathode, or the conductive wire connecting the electrolysis power source and the electrolysis anode or cathode. Its outlet is directly inserted into the electrolyte, making it an insoluble anode conductor or insoluble cathode conductor, serving as an electrocatalytic component to enhance catalytic efficiency. This is specifically shown as 9 in FIG1 .

[0031] The present invention can also be improved as follows: a sealed tank cover with a gas outlet is added to at least one tank area in the gas-liquid mixing electrolytic cell to provide a perforated seal for the electrolytic cell area. The gas outlet of the sealed tank cover is connected to the gas inlet of at least one electrolytic cell gas-liquid mixer and / or other common gas-liquid mixer, or is connected to the atmosphere, so that the gas in the sealed tank area is guided through a sealed tank outlet pipe to the electrolytic cell gas-liquid mixer and / or other exhaust gas treatment device and / or a device for recycling the gas, or is directly discharged through the sealed tank outlet. This is specifically shown as number 23 in Figure 1.

[0032] The present invention can also be improved as follows: an adjustable constant voltage electrolysis power supply is used as the electrolysis power supply of the gas-liquid mixed electrolysis cell to ensure a stable output voltage to meet production safety requirements.

[0033] The present invention can also be improved as follows: the gas-liquid hybrid electrolytic cell adopts a symmetrical three-divided cell structure to improve electrical efficiency. Specifically, two electrolytic electrodes of the same polarity are symmetrically arranged in the electrolytic cell body with the electrolytic electrode of the opposite polarity as the center. As shown in Figure 2, the electrolytic cell has a symmetrical electrolytic cathode combination.

[0034] The present invention can also be improved as follows: the gas-liquid hybrid electrolytic cell is improved by using a circular electrode distribution structure to improve the electrical efficiency of the electrochemical reaction. Specifically, the gas-liquid hybrid electrolytic cell uses a circular or polygonal electrolytic cell body, and the electrolytic anode or electrolytic cathode is set at the center of the electrolytic cell body as the central electrode, and one or more other corresponding electrodes are set around the central electrode. Figure 3 shows the circular electrode distribution structure of the electrolytic cell, where the anolyte and the catholyte are the same electrolyte, and the electrolytic anode or electrolytic cathode is installed at the center of the electrolytic cell. The electrolytic cathode or electrolytic anode electrodes on the periphery of the cell are separated by insulating partitions and are respectively connected to their own electrolytic power sources with the cell center electrode, forming a combination of multiple independent electrolytic cells in a common central electrode and electrolyte.

[0035] The present invention can also be improved as follows: an electrolyte ion current interrupter is added to cut off the path of the ion flow in the electrolyte that does not flow through the electrolytic anode and the electrolytic cathode during the electrolysis operation, so as to avoid the loss of useless work by forming a closed loop circuit with the electrolytic power supply. There are two methods for setting up the electrolyte ion current interrupter: the first is as shown in Figure 6, a tank with a multi-hole drip-type baffle is installed, or a pipe with an increased cross-sectional area with a multi-hole drip-type baffle is installed as the electrolyte ion current interrupter, and the electrolyte continuously flowing in the pipe is diverted thereto, thereby cutting off the path of the ion flow in the electrolyte in a drip flow manner; the second is as shown in Figure 7, at least two ion current interrupter temporary storage tanks are added as the electrolyte ion current interrupter, and the ion flow in the electrolyte is rotated to be interrupted in a rotating manner. Among them, the second method is to install a liquid level meter in the ion flow interruption temporary storage tank to control the pump of each current interruption temporary storage tank, so that the electrolyte in the tank is pumped into the gas-liquid mixed electrolyzer in rotation for chemical reaction between the ion flow interruption temporary storage tanks; the ion flow interruption temporary storage tank that is in rotation to pump the electrolyte in the tank into the electrolyzer does not receive the solution overflowed from the electrolyzer through the control valve, and the overflowed liquid of the gas-liquid mixed electrolyzer is drained to another ion flow interruption temporary storage tank for temporary storage, and the electrolyte is pumped into the gas-liquid mixed electrolyzer in rotation by two or more tanks to realize the short-circuit channel of cutting off the ion flow.

[0036] The present invention can also be improved as follows: the gas-liquid mixing electrolytic cell adopts a vertical structure, and the height of the electrolytic cell body of the electrolytic cell is increased. Since the present invention adopts gas-liquid mixing to carry out the reaction, and since the gas moves vertically upward in the electrolyte, increasing the vertical reaction chamber helps to improve the reaction efficiency and reduce the waste and loss caused by the unreacted gas escaping out of the gas-liquid mixing electrolytic cell. Preferably, the outlet of the electrolytic cell gas-liquid mixer is arranged at the bottom of the electrolytic cell body of the gas-liquid mixing electrolytic cell to spray the gas-liquid mixture upward from the bottom to the electrolytic anode and / or electrocatalytic component and / or electrolytic cathode. More preferably, at least two groups of independent electrolytic units are stacked in the gas-liquid mixing electrolytic cell. The electrolytic unit includes an electrolytic power supply, an electrolytic anode, an electrolytic cathode, an electrocatalytic component and / or an electrocatalytic performance structure improvement of at least one electrolytic electrode. Among them, it is preferred to arrange the electrolysis electrodes according to the chemical properties of the reaction gases: when the gas participating in the reaction is a reducing gas, they are arranged in the order of electrolysis anode, electrolysis cathode, electrolysis anode, and electrolysis cathode; when the gas participating in the reaction is an oxidizing gas, they are arranged in the order of electrolysis cathode, electrolysis anode, electrolysis cathode, and electrolysis anode, so that the gas-liquid hybrid electrolytic cell can fully exert the effect of its electrochemical reaction, as shown in the vertical electrolytic cell structure in Figure 12.

[0037] The present invention can also be improved by adding an ultrasonic generator to the electrolytic cell body and / or the electrolytic cell gas-liquid mixer. This utilizes the ultrasonic cavitation effect to fully disperse and dissolve bubbles in the electrolyte into the solution, thereby improving the efficiency of the oxidation or reduction reaction. Preferably, the ultrasonic generator is installed on the liquid flow pipe of the electrolytic cell gas-liquid mixer. This simple installation structure provides better gas-liquid mixing.

[0038] The present invention can also be improved as follows: two or more gas-liquid mixed electrolyzers are provided and connected to form a combination of two-stage or multi-stage gas-liquid mixed electrolyzers connected in series with gas pipelines, that is, the gas-liquid mixed electrochemical reaction devices of the front and rear stages are connected through gas pipelines, and the reaction gas escaping from the reaction process of the front-stage gas-liquid mixed electrolyzer is collected and drained to the rear-stage gas-liquid mixed electrolyzer for use as a reaction gas raw material, so that the treated gas can be further purified or completely eliminated.

[0039] The present invention can also be improved by adding an insulating bipolar electrode cage or isolation mesh frame. Multiple bipolar electrodes can be isolated and fixedly stacked in sections using insoluble insulating bipolar electrode cages or isolation mesh frames during use. This prevents the bipolar electrodes, which are fixedly stacked and immersed between the electrolytic anode and the electrolytic cathode, from displacement under the impact of the liquid flow and can function normally as electrocatalysts. The bipolar electrode cage, shown as 10 in FIG8 , is made of an insulating through-hole rubber mesh or porous mesh.

[0040] The present invention can also be improved as follows: a temporary storage tank is added for temporarily storing materials, and the temporary storage tank is connected to at least one other tank in the system through a pipeline for liquid flow.

[0041] The present invention can also be improved as follows: an overflow buffer tank is added, which is connected to at least one tank in the device of the present invention to solve the problem of liquid flow between tanks.

[0042] The present invention can also be improved by adding a hot / cold temperature exchanger, which is installed in at least one of the gas-liquid hybrid electrolytic cell, the temporary storage tank, and the electrolyte current cutoff tank. The hot / cold temperature exchanger is used to control the temperature of the electrolyte and adjust the temperature of the temporary storage solution, so that the temperature of each solution meets the process requirements, thereby achieving safe production and improving reaction efficiency.

[0043] The present invention can also be improved as follows: an automatic detection and feeding controller and a sensor are added, the detection signal output end of the sensor is connected to the detection signal input end of the automatic detection and feeding controller, and the control signal output end of the automatic detection and feeding controller is connected to the control signal input ends of the electrolysis power supply, valves, pumps, ultrasonic generators, hot and cold temperature exchangers, etc. in the device, so that the device performs sampling data processing according to a pre-programmed program during the production process and controls the addition of chemicals during the reaction process so that the reaction liquid meets the process reaction requirements and operates automatically and safely according to the pre-programmed program. The sensor is selected from at least one of an oxidation-reduction potentiometer (ORP meter), a pH meter, a liquid level gauge, a voltmeter, an ammeter, a thermometer, a chlorine concentration detection alarm, a hydrogen concentration detection alarm, a trace oxygen meter, and a trace hydrogen meter, and is installed in at least one of a gas-liquid hybrid electrolytic cell, a temporary storage tank, an overflow buffer tank, an electrolyte current cutoff tank, and a production workshop.

[0044] The present invention can also be improved as follows: an air pressure balancing connecting pipe is added, as shown by number 43 in Figure 13, specifically, according to the process requirements, two or more gas-liquid mixed electrolytic cells are connected through an air pressure balancing pipe, or the gas-liquid mixed electrolytic cell is connected to other cells through an air pressure balancing pipe, so that at least one exhaust port in the gas-liquid mixed electrolytic cell is directly or indirectly connected to the airway to achieve balance with the atmospheric pressure.

[0045] The present invention can also be improved by adding a bubble-containing reaction liquid flow guide, the direction and position of its liquid suction port being determined according to the design process of the gas-liquid mixing electrolytic cell. Preferably, the bubble-containing reaction liquid flow guide is located behind the electrode at the end of the electrolyte flow direction, connected to a liquid flow pump tube agitator, and pumps the untreated gas-liquid mixture back to the first reaction electrode in a circulating flow form to re-participate in the electrochemical reaction; as shown by reference numeral 52 in Figure 12.

[0046] The present invention can also be improved as follows: at least one hydrogen tail gas high altitude discharge pipe is added to the hydrogen exhaust system to discharge the hydrogen-containing tail gas safely at high altitude.

[0047] The present invention can also be improved as follows: when the gas being treated flows through a pipeline containing a solution of the gas, if the pipeline is made of an electrically insulating material, the pipeline can serve as the electrolytic cell body, and the gas-containing solution can serve as the gas-liquid mixture participating in the reaction. Under these conditions, the electrolytic anode and electrolytic cathode of a gas-liquid hybrid electrolytic cell, along with their electrocatalytic components, can be installed in the pipeline, transforming the pipeline space into a gas-liquid hybrid electrolytic cell for the electrochemical reaction; as shown by reference numeral 45 in FIG9 . If the pipeline is made of an electrically conductive material, an electrolytic cell spacer must be installed in the pipeline before the electrolytic electrodes and electrocatalytic components can be installed; as shown by reference numeral 51 in FIG11 . The electrolytic cell spacer, serving as the electrolytic cell body, is made of a polymer resin, preferably polytetrafluoroethylene.

[0048] The present invention can also be improved as follows: To save equipment space and optimize the control device, a gas scrubber and / or electrolyte isolation tank is used as the electrolytic cell body. The electrolytic electrodes and electrocatalytic components of the electrolytic cell are installed in the above-mentioned tanks. The flowing gas-liquid mixture is connected to the power supply to realize the function of a gas-liquid hybrid electrolytic cell. The gas scrubber and electrolyte isolation tank are made of polymer resin or metal, and the inner surface of the tank contacting the electrolyte is required to be coated with an anti-corrosion coating.

[0049] A second object of the present invention is to provide a method for treating hydrogen or oxygen using the above-mentioned gas-liquid hybrid electrochemical reaction device, which specifically comprises the following steps:

[0050] (1) using a gas-liquid hybrid electrochemical reaction device, using an aqueous electrolyte solution as the electrolyte of a gas-liquid hybrid electrolytic cell in the device, and turning on an electrolysis power supply to perform electrolysis;

[0051] (2) introducing a treated gas containing hydrogen and / or oxygen into the electrolyte by at least one of the following two methods:

[0052] ① Inputting a gas-liquid mixture containing the gas to be processed from a gas-liquid mixture source into the gas-liquid mixing electrolytic cell;

[0053] ② Start the electrolytic cell gas-liquid mixer to mix the treated gas with the electrolyte to form a gas-liquid mixture and send it to the gas-liquid mixing electrolytic cell, or directly form a gas-liquid mixture in the gas-liquid mixing electrolytic cell;

[0054] The gas-liquid mixture is brought into contact with at least one of the electrolytic anode, electrolytic cathode, and electrocatalytic component in the gas-liquid hybrid electrolytic cell, and an electrocatalytic effect is exerted to electrochemically oxidize or reduce the treated gas in the electrolyte, resulting in a reaction in which hydrogen is oxidized to generate water and / or a reaction in which oxygen is reduced to generate water.

[0055] In step (2), a gas-liquid mixture source inputs a gas-liquid mixture containing the gas to be treated into the gas-liquid mixing electrolytic cell. The gas-liquid mixture containing the gas to be treated is obtained by mixing the gas to be treated with liquid in the previous process and flowing together with the electrolyte in the pipeline.

[0056] The present invention uses external input gas as the gas source for the reaction. Therefore, the electrolysis power supply applies a voltage between the electrolysis anode and the electrolysis cathode equal to or lower than the decomposition voltage of the electrolyte to perform the electrolysis operation, thereby preventing the electrolysis of gas from being deposited on the electrolysis anode and / or the electrolysis cathode, thereby affecting the treatment efficiency.

[0057] To prevent electrolytic gas from being deposited on the anode and / or cathode of a gas-liquid hybrid electrolyzer, the voltage applied between the anode and cathode by the electrolysis power supply during operation is required to be less than or equal to the electrolyte decomposition voltage. However, when sufficient reducing gas participates in the electrochemical reaction at the ends of positively charged components, making it difficult for the positively charged components to deposit oxidizing gas, or when sufficient oxidizing gas participates in the electrochemical reaction at negatively charged components, making it difficult for the negatively charged components to deposit reducing gas, the voltage applied between the anode and cathode by the electrolysis power supply of the electrolysis cell can be slightly higher than the electrolyte decomposition voltage. This is because the higher the voltage applied between the anode and cathode by the electrolysis power supply, the stronger the reducing or oxidizing properties of the cathode under these conditions. Therefore, for safety reasons, the voltage applied between the anode and cathode by the electrolysis power supply can be set to be slightly higher than the electrolyte decomposition voltage to increase the electrochemical reaction rate.

[0058] When the method of the present invention is used to purify hydrogen or oxygen, it is usually used to remove oxygen from hydrogen obtained by electrolytic hydrogen production process, also known as oxygen in hydrogen, or to remove hydrogen from oxygen obtained by electrolytic hydrogen production process, also known as hydrogen in oxygen. The hydrogen containing impurities or the oxygen containing impurities is mixed with the electrolyte through the gas-liquid mixer of the electrolyzer and sprayed onto at least one of the electrolytic anode, electrolytic cathode, and electrocatalytic component. Since the gas-liquid mixture containing the above-mentioned gases contains both oxidizing gas and reducing gas, the impurities therein can be consumed by a joint reaction, that is, oxygen and hydrogen generate water through electrochemical reaction. Specifically, during electrolysis, an oxidation reaction of hydrogen occurs at the positively charged component in the gas-liquid hybrid electrolyzer, and a reduction reaction of oxygen and / or other oxidizing gas impurities occurs at the negatively charged component, thereby achieving the removal of oxygen impurities and other oxidizing gas impurities in hydrogen, or the removal of hydrogen impurities in oxygen. The detailed electrochemical reaction is shown below:

[0059] Positively charged components: H2-2e -→2H +

[0060] Negatively charged parts: O2+4H + +4e - →2H2O

[0061] Cl2+2H + +2e - →2HCl (when containing chlorine impurities)

[0062] When the method of the present invention is used to eliminate hydrogen waste gas, the electrolyte contains an oxidant, and the hydrogen waste gas is passed through the gas-liquid hybrid electrolytic cell to undergo an electrochemical reaction, where it reacts with the oxidant to produce water. Specifically, during electrolysis, an oxidation reaction of hydrogen occurs at the positively charged components of the gas-liquid hybrid electrolytic cell, and a reduction reaction of the hydrogen-oxidizing oxidant occurs at the negatively charged components. The oxidant is selected from at least one of oxygen, ozone, hydrogen peroxide, persulfate, percarbonate, perborate, permanganate, chlorate, perchlorate, sodium hypochlorite, and chlorine, and is used alone or in combination. Preferably, hydrogen peroxide is used as the oxidant. The detailed electrochemical reaction is shown below.

[0063] The reaction at the positively charged component is: H2-2e - →2H +

[0064] When using different hydrogen oxidants, the reactions at the electronegative components are:

[0065] When using oxygen, O2+4H + +4e - →2H2O

[0066] When using ozone, O3+6H + +6e - →3H2O

[0067] When using hydrogen peroxide, H2O2+2H + +2e - →2H2O

[0068] When using persulfate, S2O8 2- +2H + +2e - →SO4 2- +H2SO4

[0069] When using percarbonate, 2CO3 2- ·3H2O2+6H + +6e - →2CO3 2- +6H2O

[0070] When using perborate, 4BO3 - +8H + +8e - →B4O7 2- +2OH - +3H2O

[0071] When using chlorate, ClO3 - +6H + +6e - →Cl - +3H2O

[0072] When using perchlorate, ClO4 - +8H + +6e - →Cl - +4H2O

[0073] When using hypochlorite, ClO - +2H + +2e - →Cl - +H2O

[0074] When using permanganate, MnO4 - +3H + +3e - →MnO2+OH - +H2O

[0075] When using chlorine, Cl2+2H + +2e - →2HCl

[0076] As a preferred embodiment of the present invention, based on the decomposition voltage value measured in the static state of the electrolyte in the gas-liquid hybrid electrolytic cell used, the voltage applied by the electrolytic power supply between the electrolytic anode and the electrolytic cathode can be adjusted to be slightly higher than the decomposition voltage value of the electrolyte in the process of purifying hydrogen containing oxygen impurities and treating hydrogen waste gas to increase the chemical reaction rate. In the process of purifying oxygen containing hydrogen impurities, the voltage applied by the electrolytic power supply between the electrolytic anode and the electrolytic cathode can be lower than the decomposition voltage value of the electrolyte to prevent hydrogen electrodeposition at the electrolytic cathode.

[0077] The present invention can be improved as follows: the electrolytic electrodes in the gas-liquid mixed electrolytic cell are arranged in such a way that the electrolytic anode first faces the liquid flow of the gas-liquid mixture, and the gas-liquid mixture containing hydrogen is first oxidized by the electrolytic anode so that H2 loses electrons and becomes H + Proton, H + As the liquid flows to the electrolytic cathode, an electrochemical reaction occurs and combines with O2 to form water. + An arrangement of electrolysis electrodes in which protons move along the liquid flow improves reaction efficiency.

[0078] The present invention can also be improved as follows: in order to reduce the energy consumption of electrolysis, an electrolyte current cut-off tank is used to solve the short-circuit problem of the ion flow in the electrolyte.

[0079] The present invention can also be improved as follows: in order to improve the oxygen or hydrogen impurity removal effect, or to treat the hydrogen waste gas to be eliminated more thoroughly, two or more gas-liquid hybrid electrolytic cells can be used in a series combination to treat the treated gas step by step, so that the purified gas has a higher purity, or the treatment effect of the hydrogen waste gas to be eliminated is more thorough.

[0080] The present invention can also be improved as follows: a sensor is installed at the part in contact with the electrolyte in the gas-liquid mixed electrolytic cell for detection and monitoring, so that the reaction process can be safely controlled, and an automatic detection and feeding controller is provided to enable the device to automatically operate according to a pre-programmed program.

[0081] Compared with the prior art, the present invention has the following beneficial effects:

[0082] 1. The present invention adopts a gas-liquid hybrid electrochemical reaction device, which can treat and solve the problem of oxygen impurities in the gas-liquid mixture of hydrogen and electrolyte overflowing from the existing alkaline water electrolyzer. Specifically, the gas-liquid hybrid electrochemical reaction device is installed in the gas-liquid circulation pipe to purify and deoxygenate the hydrogen; it can also treat and solve the problem of hydrogen impurities in the gas-liquid mixture of oxygen and electrolyte overflowing from the existing alkaline water electrolyzer. The gas-liquid hybrid electrochemical reaction device is installed in the gas-liquid circulation pipe to eliminate the hydrogen impurities in the gas-liquid mixture; the dangerous hydrogen waste gas produced in the process of using electrolysis to treat waste liquid can be safely eliminated by installing a gas-liquid hybrid electrochemical reaction device in the on-site workshop, thereby effectively solving the safety problem of flammable and explosive waste hydrogen.

[0083] 2. The gas-liquid hybrid electrochemical reaction device of the present invention has a simple structure, low equipment investment cost, high economic benefits, and a safe and reliable process. It is very suitable for technical upgrading and transformation of existing hydrogen or oxygen processing equipment.

[0084] 3. The method of the present invention can purify hydrogen and / or oxygen and eliminate hydrogen waste gas; moreover, no new pollution sources are added during the gas purification process or the process of eliminating hydrogen waste gas. Compared with the existing process that uses high-cost catalysts or adsorbents and produces waste, the process of the present invention is more in line with environmental protection requirements.

[0085] 4. The gas-liquid mixed electrochemical reaction device is used for gas treatment, which has low energy consumption and high safety.

[0086] 5. The gas-liquid hybrid electrochemical reaction device can be flexibly customized in size and has a high degree of automation. The device structure can adopt an independent electrolytic cell or the electrolytic electrode and its electrocatalytic components can be directly installed on the liquid flow pipeline or in the gas scrubber to form an electrolytic cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0087] FIG1 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 1 of the present invention.

[0088] FIG2 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 2 of the present invention.

[0089] FIG3 is a schematic diagram of a gas-liquid hybrid electrolytic cell with a circular electrode distribution structure according to Example 7 of the present invention; wherein (A) is a cross-sectional view of (B) at NN.

[0090] FIG4 is a schematic diagram of a bipolar electrode.

[0091] FIG5 is a schematic diagram of an insoluble electrode.

[0092] FIG6 is a schematic diagram of a tank with a multi-hole drip-type baffle as an electrolyte ion current interrupter.

[0093] FIG7 is a schematic diagram of two ion current interruption temporary storage tanks serving as electrolyte ion current interrupters, both of which are equipped with liquid level gauges.

[0094] FIG8 is a schematic diagram of a bipolar electrode insulation cage.

[0095] FIG9 is a schematic diagram of a gas-liquid hybrid electrolytic cell using a pipe as the electrolytic cell body.

[0096] FIG10 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 3 of the present invention.

[0097] FIG11 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 4 of the present invention.

[0098] FIG12 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 5 of the present invention.

[0099] FIG13 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device according to Example 6 of the present invention.

[0100] FIG14 is a schematic diagram of the device of Comparative Example 2.

[0101] Reference numerals: 1-electrolysis cell, 2-electrolyte, 3-electrolysis anode, 4-electrolysis cathode, 5-electrolysis power supply, 6-bipolar electrode, 7- Vacuum jet electrolytic cell gas-liquid mixer, 8-bubbling electrolytic cell gas-liquid mixer, 9-vacuum jet and bubbling combined electrolytic cell gas-liquid mixer, 10-bipolar electrode insulation mesh box, 11-insulated through-hole support baffle, 12-gas washing tank, 13-ordinary bubbling gas-liquid mixer, 14-ordinary vacuum jet gas-liquid mixer, 15-ordinary spray tower gas-liquid mixer, 16-cold and hot temperature exchanger, 17-liquid flow pump tube agitator, 18-temporary storage tank, 19-insoluble anode conductor, 20-insoluble cathode conductor, 21-gas-liquid mixed liquid flow pipeline, 22-hydrogen tail gas high altitude discharge pipe, 23-sealed tank cover for leaving holes for escaped gas from electrolytic cell reaction, 24-hydrogen, 25-oxygen, 26-ozone, 27-chlorine, 28-oxidant, 29-clean water, 3 0-electrolyte solution, 31-escape gas from reaction liquid, 32-valve, 33-pump, 34-gas pressure pump, 35-electrical insulator, 36-conductor, 37-conductive connecting line, 38-automatic detection and feeding controller, 39-sensor, 40-gas-liquid separator, 41-insulating partition plate in electrolytic cell, 42-electrolyte ion flow cut-off trough (device), 43-air pressure balance connecting pipe, 44-flame arrester, 45-pipeline for mixed flow of treated gas and electrolyte, 46-treated gas scrubber, 47-trace hydrogen analyzer, 48-trace oxygen analyzer, 49-hydrogen to be treated, 50-oxygen to be treated, 51-electrolytic cell spacer, 52-bubble-containing reaction liquid flow guide cover, 53-hydrogen air pump, 54-cathode spray pipe, 55-bridge, 56-oxygen-containing solution.

[0102] In the drawings and the following embodiments, multiple components of the same component type in a device are represented by "reference numerals." For example, electrolytic cell body 1-1 refers to one electrolytic cell body, and electrolytic cell body 1-2 refers to another electrolytic cell body. When there are three or more components of the same component type, "~" is used for abbreviation. For example, electrolytic cell bodies 1-1, 1-2, and 1-3 are referred to as electrolytic cell bodies 1-1 to 1-3, or 1-1 to 3. DETAILED DESCRIPTION

[0103] The present invention will be further described below through specific embodiments.

[0104] The gas-liquid mixing electrolytic cell, mixed gas separation cell, electrolytic anode, electrolytic cathode, bipolar electrode, bipolar electrode insulation cage, electrolytic cell gas-liquid mixer, liquid flow pump and agitator, temporary storage tank, insoluble anode conductor, insoluble cathode conductor, and electrolyte current interrupter used in the embodiments of the present invention are all manufactured by Yegao Environmental Protection Equipment Manufacturing Co., Ltd. in Foshan, Guangdong, China. The trace oxygen analyzer, trace hydrogen analyzer, sensors, automatic detection and feeding controller, valves, pumps, and chemical raw materials are all commercially available products.

[0105] In addition to the above-mentioned products, those skilled in the art may also select other products with similar properties to the above-mentioned products listed in the present invention according to routine selection, and all of them can achieve the purpose of the present invention.

[0106] Example 1

[0107] As shown in Figure 1, it is Example 1 of the gas-liquid mixed electrochemical reaction device of the present invention. The device is a separate gas-liquid mixed electrolytic cell.

[0108] The gas-liquid hybrid electrolytic cell comprises an electrolytic cell body 1, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, a bipolar electrode 6, and a combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. The electrolytic cell body 1 is equipped with an insoluble anode conductor 19, which is directly electrically connected to the electrolytic anode; the bipolar electrode 6; and an insoluble cathode conductor 20, which is directly electrically connected to the electrolytic cathode. Furthermore, the electrolytic cell body 1 is equipped with a bipolar electrode insulating mesh box 10 for holding the bipolar electrode 6 and an insulating through-hole support baffle 11. The bipolar electrode 6, insoluble anode conductor 19, and insoluble cathode conductor 20 serve as electrocatalytic components. A sealed cell cover 23 is provided on the top of the electrolytic cell body 1 to provide a hole for escaping gases from the electrolytic cell reaction. The electrolytic cell gas-liquid mixer 9 of the vacuum jet and bubbling type is connected to the electrolytic cell body 1 via a pump 33 as a liquid flow pipeline, and its outlet faces the electrolytic anode 3 and the insoluble anode conductor 19.

[0109] The electrolytic anode, electrolytic cathode, insoluble anode conductor, and insoluble cathode conductor are all made of nickel metal. The inner wall of the pipe of the electrolytic tank gas-liquid mixer, which contacts the electrolyte, is plated with a platinum conductor and is conductively connected to the positive electrode of the electrolytic power supply 5, so that the gas-liquid mixer 9 becomes an insoluble anode conductor, serving as an electrocatalytic component.

[0110] The electrolyte 2 in the gas-liquid hybrid electrolytic cell is a sodium hydroxide solution with a pH of 12. In this embodiment, the gas being processed is hydrogen 49 containing oxygen impurities. The gas escaping from the electrolytic cell cover after the electrochemical reaction is purified hydrogen 24. Gas concentration is expressed in vol%.

[0111] The decomposition voltage of a pH 12 sodium hydroxide solution was measured to be 0.5 V under static conditions of the electrolyte in the electrolytic cell.

[0112] A method for treating oxygen in hydrogen using a gas-liquid hybrid electrochemical reaction device is performed according to the following steps:

[0113] 1. Pour the electrolyte 2 into the electrolytic cell 1, turn on the electrolytic power supply 5 and adjust the electrolytic power supply to apply a voltage of 0.5V between the electrolytic anode and the electrolytic cathode.

[0114] 2. Start the pump 33 to send the untreated hydrogen 49 containing oxygen impurities into the gas-liquid mixer 9 of the electrolytic cell to mix with the electrolyte 2 to form a gas-liquid mixture, and then spray the gas-liquid mixture onto the electrolytic anode and the insoluble anode conductor; when the hydrogen encounters the electrolytic anode, the insoluble anode conductor, and the anode end of the bipolar electrode, hydrogen H2 loses electrons and becomes H + Electrochemical reaction of protons, oxygen is obtained at the cathode, insoluble cathode conductor, and cathode end of bipolar electrode and reacts with H + Combined with the electrochemical reaction that produces water.

[0115] 3. After 30 minutes of stable electrochemical reaction, trace oxygen concentrations in the hydrogen gas 49 to be processed, which is input into the electrolytic cell, and in the hydrogen gas 24 escaping from the electrolytic cell by reaction were sampled and tested using a trace oxygen analyzer 48. The calculated results showed that the oxygen content in the hydrogen gas 49 to be processed was 0.9%, while the oxygen content in the hydrogen gas 24 after purification was 0.2%.

[0116] Example 2

[0117] As shown in Figure 2, it is a second embodiment of the gas-liquid mixing electrochemical reaction device of the present invention. The device is a separate gas-liquid mixing electrolytic cell.

[0118] The gas-liquid mixing electrolytic cell comprises an electrolytic cell body 1, an electrolytic anode 3, electrolytic cathodes 4-1 and 4-2, an electrolytic power supply 5, and vacuum jet electrolytic cell gas-liquid mixers 7-1 and 7-2. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathodes 4-1 and 4-2 are connected to the negative electrode of the electrolytic power supply 5. The electrolytic cell body 1 is provided with an insoluble anode conductor 19, which is directly electrically connected to the electrolytic anode, and insoluble cathode conductors 20-1 and 20-2, which are directly electrically connected to the electrolytic cathode. The insoluble anode conductor 19 and insoluble cathode conductors 20-1 and 20-2 serve as electrocatalytic components. A sealing cap 23 is provided on the top of the electrolytic cell body 1 to allow for escape of gases from the electrolytic cell reaction. The vacuum jet electrolytic cell gas-liquid mixers 7-1 and 7-2 are connected to the electrolytic cell body as liquid flow pipes through pumps 33-1 and 33-2 respectively, and their outlets are directed toward the electrolytic anode 3 and the insoluble anode conductor 19, and are also provided with ultrasonic generators (not shown).

[0119] The electrolytic anode material is a titanium-based coated insoluble anode, the electrolytic cathode is stainless steel, the insoluble anode conductor material is a conductor with a gold-plated surface, and the insoluble cathode conductor material is stainless steel.

[0120] The electrolyte 2 in the gas-liquid hybrid electrolytic cell is a sulfuric acid solution with a pH of 4. In this embodiment, the gas being processed is unprocessed oxygen 50 containing hydrogen impurities, with a hydrogen impurity concentration of 1.2%. The gas escaping the cell cover during the electrochemical reaction is purified oxygen 25. Gas concentration is expressed in vol%.

[0121] The decomposition voltage of the sulfuric acid solution with pH 4 was measured to be 0.7V in a gas-liquid mixed electrolytic cell when the electrolyte was static.

[0122] A method for treating hydrogen in oxygen using a gas-liquid hybrid electrochemical reaction device is performed according to the following steps:

[0123] 1. Add the electrolyte 2 into the electrolytic cell 1, turn on the electrolytic power supply 5 and adjust the electrolytic power supply to apply a voltage of 0.5V between the electrolytic anode and the electrolytic cathode.

[0124] 2. Start pumps 33-1 and 33-2 and adjust the openings of valves 32-1 and 32-2 to introduce oxygen 50 containing hydrogen impurities into the electrolytic cell gas-liquid mixers 7-1 and 7-2 to mix with electrolyte 2 to form a gas-liquid mixture. The gas-liquid mixture is sprayed onto the electrolytic anode and insoluble anode conductor; hydrogen H2 loses electrons and becomes H2 when it encounters the electrolytic anode and insoluble anode conductor. + Electrochemical reaction of protons, in addition, the electrolytic cathode and insoluble cathode conductor both generate oxygen to obtain electrons and react with H + Combined into an electrochemical reaction of water.

[0125] 3. After 30 minutes of stable electrochemical reaction, trace hydrogen analyzer 47 was used to perform artificial trace hydrogen content sampling on the oxygen gas 50 to be processed input into the electrolytic cell and the oxygen gas 25 escaping from the electrolytic cell. The test results showed that the hydrogen content of the oxygen gas 50 to be processed was 1.2%, and the hydrogen impurity concentration of the oxygen gas 25 after purification was 0.4%.

[0126] Example 3

[0127] FIG10 shows a third embodiment of a gas-liquid mixed electrochemical reaction device according to the present invention, which includes a gas-liquid mixed electrolytic cell and two temporary storage cells 18 .

[0128] The gas-liquid mixing electrolytic cell is a circular electrode distribution structure, which includes an electrolytic cell body 1, electrolytic anodes 3-1 to 3-8, an electrolytic cathode 4, electrolytic power supplies 5-1 to 5-8, a vacuum jet electrolytic cell gas-liquid mixer 7, a bubbling electrolytic cell gas-liquid mixer 8-1 to 8-8, and a sealed tank cover 23 for leaving holes for escaped gas from the electrolytic cell reaction. The electrolytic cathode is arranged at the center of the electrolytic cell body 1 as the central electrode, and various electrolytic anodes are arranged around it. The electrolytic anodes 3-1 to 3-8 are respectively connected to the positive electrodes of the corresponding electrolytic power supplies 5-1 to 5-8, and the electrolytic cathode 4 is connected to the negative electrodes of each electrolytic power supply 5-1 to 5-8; the electrolytic anodes and electrolytic cathodes are both connected in parallel and built as parallel electrodes. The electrolytic cell body 1 is equipped with a hot and cold temperature exchanger 16, insoluble anode conductors 19-1 to 19-8 directly conductively connected to the electrolytic anode, an insoluble cathode conductor 20 directly conductively connected to the electrolytic cathode, and a sensor 39-1. The vacuum jet electrolytic cell gas-liquid mixer 7 passes through pump 33-1, then through temporary storage tank 18-1 and pump 33-2, and / or through temporary storage tank 18-2 and pump 33-3, and then through bubbling electrolytic cell gas-liquid mixers 8-1 to 8-8, connected to the electrolytic cell body by liquid flow pipes. The outlets of the bubbling electrolytic cell gas-liquid mixers 8-1 to 8-8 face the electrolytic anodes 3-1 to 3-8 and insoluble anode conductors 19-1 to 19-8, respectively. Sensors 39-2 and 39-3 are installed in temporary storage tank 18-1, and sensors 39-4 and 39-5 are installed in temporary storage tank 18-2. A sealing slot cover 23 for leaving holes for escaped gas from the electrolytic cell reaction is provided on the top of the electrolytic cell body 1, and a trace hydrogen analyzer 47 is provided at the tail gas outlet.

[0129] The electrolytic anode material is an insoluble anode with a titanium-based coating, the electrolytic cathode is titanium, the insoluble anode conductor material is conductive graphite, and the insoluble cathode conductor material is titanium.

[0130] The temporary storage tanks 18-1 and 18-2 are ion flow interruption temporary storage tanks, which are used to interrupt the ion flow of the electrolyte and short-circuit it. The electrolyte is pumped into the electrolytic tank in rotation through the level gauges 39-2 and 39-4.

[0131] The sensor 39-1 is a thermometer, 39-2 and 39-4 are liquid level gauges, and 39-3 and 39-5 are ORP meters. The ORP meter is used to monitor the concentration of hydrogen peroxide.

[0132] The electrolyte in the gas-liquid hybrid electrolytic cell is a 6% solution of neutral sodium sulfate. The oxidant 28 used in this embodiment is hydrogen peroxide. The untreated hydrogen gas 49 is hydrogen waste gas, with a gas concentration expressed in ppm, including a hydrogen concentration of 27,000 ppm. The gas escaping the cell cover from the electrolytic cell reaction is hydrogen tail gas 24 after hydrogen quenching treatment.

[0133] The electrolyte decomposition voltage of a 6% sodium sulfate solution measured in a gas-liquid mixed electrolytic cell under static electrolyte conditions was 0.4V.

[0134] A method for treating hydrogen waste gas using a gas-liquid hybrid electrochemical reaction device is performed according to the following steps:

[0135] 1. Add electrolyte 2 to the electrolytic cell 1, monitor the concentration of hydrogen peroxide in the solution 30 through sensors 39-3 and 39-5, turn on 8 electrolytic power supplies 5 and adjust the electrolytic power supply to apply 1V between the electrolytic anode and the electrolytic cathode.

[0136] 2. Start pump 33-1 and, under the control of sensors 39-1 and 39-2, start pumps 33-2 and 33-3 in turn to achieve a short-circuit path that cuts off the ion flow in the electrolyte;

[0137] The hydrogen gas 49 to be treated is introduced into the gas-liquid mixer 7 of the electrolytic cell and mixed with the electrolyte 2 to form a gas-liquid mixture, which is then sprayed onto 8 independent electrolytic anodes and insoluble anode conductors. When the hydrogen gas encounters the electrolytic anodes and insoluble anode conductors, hydrogen H2 loses electrons and becomes H + The electrochemical reaction of protons, the other electrolytic cathode, insoluble cathode conductor both have oxygen in hydrogen peroxide get electrons and react with H + The electrochemical reaction of the water is combined, and the temperature of the reaction liquid is controlled to 30° C. by the thermometer 39 - 1 and the hot-cold temperature exchanger 16 during the reaction.

[0138] 3. After 30 minutes of stable electrochemical reaction, the output data of the trace hydrogen analyzer 47 is read as 4100 ppm, that is, the hydrogen concentration of the hydrogen tail gas 24 escaping from the electrolytic cell reaction is 4100 ppm.

[0139] Example 4

[0140] As shown in Figure 11, Example 4 of the gas-liquid hybrid electrochemical reaction device of the present invention is shown. The device includes a gas-liquid hybrid electrolyzer and a gas-liquid separator 40. The process for processing hydrogen in this device is as follows: the hydrogen from the alkaline water electrolysis hydrogen production electrolyzer and the gas-liquid mixture of the overflowed electrolyte pass through the gas-liquid hybrid electrolyzer to remove oxygen and impurities, and then are channeled to the gas-liquid separation tank 40 to separate the hydrogen 24 from the electrolyte. According to the process design, the electrolyte after gas-liquid separation is pumped back to the alkaline water electrolysis hydrogen production electrolyzer by pump 33 for recycling. The hydrogen escapes from the gas-liquid separation tank exhaust pipe and is collected after detection.

[0141] The gas-liquid hybrid electrolyzer comprises an electrolyzer body, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power source 5, and a gas-liquid mixture source. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power source 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power source 5. In this embodiment, an electrolytic cell spacer 51 is provided in the hydrogen-side overflow pipe of the alkaline water electrolysis hydrogen production electrolyzer, serving as the electrolytic cell body of the gas-liquid hybrid electrolyzer. The hydrogen gas flowing in the pipe from the alkaline water electrolysis hydrogen production electrolyzer and the gas-liquid mixture of the overflowing electrolyte serve as the gas-liquid mixture source. The electrolytic cell spacer 51, serving as the electrolytic cell body, also includes an insoluble anode conductor 19 directly conductively connected to the electrolytic anode and an insoluble cathode conductor 20 directly conductively connected to the electrolytic cathode. Both of these serve as electrocatalytic components.

[0142] The gas outlet of the gas separator 40 is provided with a trace hydrogen analyzer 47 , and the liquid outlet of the gas separator 40 is provided with a valve and a pump.

[0143] The electrolytic anode and the insoluble anode conductor are made of nickel, the electrolytic cathode and the insoluble cathode conductor are made of platinum, and the electrolytic cell spacer 51 is made of polytetrafluoroethylene.

[0144] The electrolyte 2 in the gas-liquid hybrid electrolytic cell is a 30% potassium hydroxide solution at 80°C. The gas being processed in this embodiment is hydrogen gas 49 containing oxygen impurities. The gas concentration is expressed in Vol%, with the oxygen impurity being 1.3%. The gas escaping from the gas-liquid separation tank is hydrogen gas 24 after purification in this embodiment.

[0145] The decomposition voltage of the electrolyte at 80°C was measured and found to be 0.2V.

[0146] A method for treating oxygen in hydrogen using a gas-liquid hybrid electrochemical reaction device is performed according to the following steps:

[0147] 1. Allow the hydrogen from the alkaline water electrolysis hydrogen production cell and the gas-liquid mixture overflowing from the electrolyte to flow through a gas-liquid hybrid electrolyzer. Turn on the electrolysis power supply 5 and apply a voltage 0.3V higher than the electrolyte decomposition voltage to the electrolysis anode and electrolysis cathode. The gas-liquid mixture at a temperature of 80°C flows through the gas-liquid hybrid electrolyzer. The electrolysis anode and insoluble anode conductor cause the hydrogen H2 in the electrolyte to undergo an electrochemical reaction, losing electrons and converting it into H + Protons, electrolytic cathode and insoluble cathode conductor make oxygen O2 in the electrolyte generate electrons and react with H + Combined into an electrochemical reaction of water.

[0148] 2. After 30 minutes of electrochemical deoxygenation and impurity removal, the hydrogen 24 at the exhaust port of the gas-liquid separation tank 40 was sampled and tested using a trace oxygen analyzer 48. The calculated oxygen impurity content was 0.6%. The purification result showed that the original oxygen impurity concentration was reduced from 1.3% to 0.6%.

[0149] Example 5

[0150] FIG12 shows a fifth embodiment of the gas-liquid hybrid electrochemical reaction device of the present invention, which includes a gas-liquid hybrid electrolytic cell, a temporary storage cell 18 , an automatic detection and feeding controller 38 , and an electrolyte ion current interrupter 42 .

[0151] The gas-liquid mixing electrolytic cell adopts a vertical structure, with three independent electrolytic units installed in layers above and below. Specifically, it includes an electrolytic cell body 1, electrolytic anodes 3-1, 3-2 and 3-3, electrolytic cathodes 4-1, 4-2 and 4-3, electrolytic power supplies 5-1, 5-2 and 5-3, and an electrolytic cell gas-liquid mixer 9 that combines vacuum jet and bubbling types. The electrolytic anodes 3-1, 3-2 and 3-3 are respectively connected to the positive poles of the electrolytic power supplies 5-1, 5-2 and 5-3, and the electrolytic cathodes 4-1, 4-2 and 4-3 are respectively connected to the negative poles of the electrolytic power supplies 5-1, 5-2 and 5-3. The electrolytic cell body 1 is provided with a liquid flow pump tube agitator 17, insoluble anode conductors 19-1 to 19-3 directly conductively connected to the electrolytic anode, and insoluble cathode conductors 20-1 to 20-3 directly conductively connected to the electrolytic cathode. In addition, an insulating through-hole support baffle 11 is provided between each electrolytic electrode; the insoluble anode conductor and the insoluble cathode conductor are electrocatalytic components.

[0152] The electrolytic cell gas-liquid mixer 9, which is a combination of vacuum jet and bubbling types, is connected to the electrolytic cell body as a liquid flow pipeline through a pump 33, and its outlet is directed toward the electrolytic anode 3-1 and the insoluble anode conductor 19-1. The gas-liquid mixture then flows upward through the through holes of the insulating through-hole support baffle 11 to other electrolytic anodes and insoluble anode conductors in sequence.

[0153] When the electrolyte flow rises above the terminal electrode within the electrolytic cell 1, a bubble-containing reaction liquid deflector 52 is installed. This deflector is connected to the liquid pump pipe agitator 17, which pumps the gas-liquid mixture back to the bottom of the electrolytic cell to re-engage in the electrochemical reaction. A trace hydrogen analyzer 47 is installed on the hydrogen escape pipe at the top of the electrolytic cell 1. This hydrogen escape pipe is also connected to the hydrogen exhaust high-altitude discharge pipe 22, which is topped with a flame arrester 44. The liquid outlet of the electrolytic cell 1 is connected to the electrolyte ion current interrupter 42 for liquid flow, allowing the combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9 to be connected to the electrolytic cell body through the electrolyte ion current interrupter 42, valve 32-1, and pump 33-1 for liquid flow, with its outlet facing the electrolytic electrodes and electrocatalytic components.

[0154] The electrolyte ion current interrupter 42 is provided with a hot and cold temperature exchanger 16 and four sensors 39 - 1 to 39 - 4 , and the overflow port of the electrolyte ion current interrupter 42 is connected to the temporary storage tank 18 .

[0155] The electrolytic cell is a vertical electrolytic cell made of stainless steel. The inner surface in contact with the electrolyte is coated with insulating anti-corrosion material. Three independent electrolytic units are installed in the upper and lower layers.

[0156] The electrolytic anode, electrolytic cathode, insoluble anode conductor and insoluble cathode conductor are all conductive graphite.

[0157] Four sensors are installed in the electrolyte ion flow channel 42, and its exhaust port is connected to the air intake port of the electrolytic cell gas-liquid mixer 9 through a pipeline.

[0158] The sensor 39-1 is a thermometer used to control the operation of the hot and cold temperature exchanger 16, the sensor 39-2 is an ORP meter used to control the pump 33-2 to add oxidant, the sensor 39-3 is a hydrometer used to control the pump 33-9 to add clean water 29 to maintain the salt content of the electrolyte 2, and the sensor 39-4 is a pH meter used to control the pump 33-4 to add sulfuric acid 30-3 to keep the pH of the electrolyte 2 at 6.

[0159] The electrolyte 2 in the gas-liquid hybrid electrolytic cell is a saline sulfuric acid solution with a pH of 6. The decomposition voltage of the electrolyte is 0.6 V as measured by the static state of the electrolyte in the electrolytic cell.

[0160] The oxidant 28 used in this embodiment is a mixture of sodium chlorate, sodium perchlorate, and sodium persulfate. The gas treated in this embodiment is untreated hydrogen 49, specifically hydrogen waste gas, whose gas concentration is expressed in ppm. The hydrogen concentration is as high as 32,000 ppm and contains trace amounts of chlorine, Cl2. This is because the untreated hydrogen is electrochemically treated in a conventional filter cloth separator electrolytic cell on organic waste liquid containing chloride ions, resulting in the hydrogen escaping from the cathode cell containing extremely trace amounts of chlorine. This embodiment eliminates the hydrogen waste gas, using various sensors and a trace hydrogen analyzer 47 for process monitoring and control. The remaining hydrogen tail gas after electrochemical treatment is discharged from a high-altitude exhaust pipe.

[0161] A method for treating hydrogen waste gas using a gas-liquid hybrid electrochemical reaction device is performed according to the following steps:

[0162] 1. Connect the overflow port of the electrolytic cell 1 to the electrolyte ion flow channel 42 through a pipe, install the sensor and equip it with an automatic detection and feeding controller 38 to assemble a complete device.

[0163] 2. The prepared electrolyte is added to the electrolytic cell 1 and the cell 42, respectively. The device is powered on to enable the automatic feeding controller 38 to process the data detected by the sensors on site. Under normal circumstances, an operation command is issued to start the pump 33-1 and the liquid flow pump tube agitator 17, and the hydrogen gas 49 to be processed is introduced into the electrolytic cell gas-liquid mixer 9 to mix with the electrolyte to form a gas-liquid mixture, which is then sprayed onto the electrolytic anode and the insoluble anode conductor.

[0164] Turn on the hot and cold temperature exchanger 16 and the trace hydrogen analyzer 47, and turn on the three electrolysis power supplies 5-1, 5-2, and 5-3 to start the electrolysis operation. During the process, the thermometer controls the electrolyte temperature, the sensor 39-2 controls the pump 33-2 to add the oxidant, the sensors 39-2 and 39-3 control the pump 33-3 to add clean water, and the sensors 39-2 and 39-4 control the pump 33-4 to add sulfuric acid 30-3. The ORP meter of the sensor 39-2 is controlled at 300-400 mV, and the electrochemical reaction occurs as follows:

[0165] Electrolytic anode and insoluble anode conductor: H2-2e - →2H +

[0166] Electrolytic cathode and insoluble cathode conductor: NaClO3+6H + +6e - →NaCl+3H2O NaClO4+8H + +8e - →NaCl+4H2O Na2S2O8+2H + +2e -→NaSO4+H2SO4

[0167] Among them, the hydrogen waste gas 47 contains a very small amount of Cl2, so the following electrochemical reaction will occur: Cl2+2H + +2e - →2HCl.

[0168] 3. During the electrochemical reaction, as the reaction raw materials are continuously fed into the device from the outside, waste brine 30-2 is drained into the temporary storage tank 18 for temporary storage, and hydrogen waste gas 47 is input for continuous electrochemical reaction. The trace hydrogen analyzer 47 detects that the concentration of hydrogen 24 at the outlet is 1940 ppm.

[0169] From the data comparison of hydrogen content in hydrogen waste gas before and after treatment, the hydrogen concentration in the hydrogen to be treated 49 is 32000ppm, and the hydrogen concentration of the discharged hydrogen gas after the electrolytic cell is used to eliminate the hydrogen waste gas is 1940ppm.

[0170] Example 6

[0171] As shown in FIG13 , this is Example 6 of the gas-liquid mixed electrochemical reaction device of the present invention, wherein the device includes two gas-liquid mixed electrolytic cells.

[0172] A gas-liquid mixing electrolytic cell includes an electrolytic cell body 1-1, an electrolytic anode 3-1, an electrolytic cathode 4-1, an electrolytic power supply 5-1, a combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9-1, and a sealed cell cover 23-1 with holes for retaining escaped gas from the electrolytic cell reaction. The electrolytic anode 3-1 is connected to the positive electrode of the electrolytic power supply 5-1, and the electrolytic cathode 4-1 is connected to the negative electrode of the electrolytic power supply 5-1. The electrolytic anode 3-1 and the electrolytic cathode 4-1 are one or more parallel electrodes, wherein the angle formed between at least one electrode component and the gas-liquid mixture ejection line of the electrolytic cell gas-liquid mixer 9-1 is greater than 0° and less than 90°. The electrolytic cell 1-1 is equipped with an insoluble anode conductor 19-1, directly conductively connected to the electrolytic anode; a bipolar electrode 6-1; and an insoluble cathode conductor 20-1, directly conductively connected to the electrolytic cathode. A bipolar insulating mesh cage 10-1 is also provided for housing the bipolar electrode 6-1, along with an insulating through-hole support plate 11-1. The bipolar electrode 6-1, insoluble anode conductor 19-1, and insoluble cathode conductor 20-1 serve as electrocatalytic components. A combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9-1 is connected to the electrolytic cell 1-1 via a pump 33-1 as a liquid flow conduit, with its outlet directed toward the electrolytic anode 3-1, insoluble anode conductor 19-1, and bipolar electrode 6-1.

[0173] The second gas-liquid hybrid electrolytic cell comprises an electrolytic cell body 1-2, an electrolytic anode 3-2, an electrolytic cathode 4-2, an electrolytic power supply 5-2, a combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9-2, a sealed cell cover 23-2 for retaining holes for escaped gas from the electrolytic cell reaction, an insoluble anode conductor 19-2, a bipolar electrode 6-2, an insoluble cathode conductor 20-2, a bipolar electrode insulating mesh box 10-2, and an insulating through-hole support baffle 11-2. The bipolar electrode 6-2, insoluble anode conductor 19-2, and insoluble cathode conductor 20-2 are electrocatalytic components. The installation locations of these components in the second gas-liquid hybrid electrolytic cell are the same as those in the first gas-liquid hybrid electrolytic cell.

[0174] A pressure balancing connecting pipe 43 is provided between the sealed tank covers 23-1 and 23-2 for leaving holes for escaped gas from the reaction of the two gas-liquid mixing electrolytic cells to balance the gas pressures in the two tanks. The gas outlet of one of the gas-liquid mixing electrolytic cells is connected to the gas inlet of the vacuum jet and bubbling electrolytic cell gas-liquid mixer 9-2 of the second gas-liquid mixing electrolytic cell. The gas outlet of the second gas-liquid mixing electrolytic cell is provided with a trace oxygen analyzer 48 and a gas pressure pump 34.

[0175] In this embodiment, the two gas-liquid hybrid electrolyzers are connected in series via reaction gas pipelines, providing two-stage gas processing. Specifically, the escaping gas from the first gas-liquid hybrid electrolyzer is directed to the second gas-liquid hybrid electrolyzer, where the gas-liquid mixer 9-2 continues to participate in the electrochemical reaction.

[0176] The electrolytic anode 3-1 is platinum, the electrolytic anode 3-2 is a conductive material with a gold-plated surface, the electrolytic cathode 4-1 is nickel, the electrolytic cathode 4-2 is stainless steel, the insoluble anode conductors 19-1 and 19-2 are both nickel, and the insoluble cathode conductors 20-1 and 20-2 are both gold-plated.

[0177] The electrolyte in the two gas-liquid hybrid electrolytic cells is a potassium hydroxide solution with a pH of 9. The decomposition voltage of the electrolyte is 0.8 V according to the measurement of the two electrolytic cells under the condition of static electrolyte.

[0178] The gas to be processed 50 in this embodiment is oxygen gas containing hydrogen impurities. The gas concentration is expressed in Vol%, and the hydrogen impurity content in the oxygen gas to be processed 50 is 1.1%.

[0179] A method for treating hydrogen impurities in oxygen using a gas-liquid hybrid electrochemical reaction device is performed according to the following steps:

[0180] 1. Electrolyte is added to electrolytic cells 1-1 and 1-2, respectively. Pumps 33-1 and 33-2 are activated. Electrolytic power supplies 5-1 and 5-2 are turned on and the voltages of both electrolytic anodes and cathodes are adjusted to 0.7 V. External oxygen 50 to be processed is introduced into the gas-liquid mixer 9-1 of electrolytic cell 1-1 to mix with the electrolyte 2 to form a gas-liquid mixture. The gas-liquid mixture is then sprayed onto the electrolytic anode 3-1 and the insoluble anode conductor 19-1 to participate in the electrochemical reaction within the electrolytic cell 1-1.

[0181] The tail gas from the reaction in the electrolytic cell body 1-1 is drained into the gas-liquid mixer 9-2 of the electrolytic cell body 1-2 and sprayed onto the electrolytic anode and the insoluble anode conductor, sprayed onto the electrolytic anode 3-2 and the insoluble anode conductor 19-2, and then enters the electrolytic cell body 1-2 to continue participating in the electrochemical reaction. The electrochemical reaction formula of the electrolyte in the two cells is as follows:

[0182] Electrolytic anode, bipolar electrode anode end and insoluble anode conductor: H2-2e→2H +

[0183] Electrolytic cathode, bipolar electrode cathode end and insoluble cathode conductor: O2+4H + +4e - →2H2O

[0184] 2. After being processed by the two electrolytic cells, the untreated oxygen 50 escapes from the exhaust port of the electrolytic cell body 1-2. The trace hydrogen analyzer 47 installed on the exhaust pipe detects that the hydrogen impurity value in the discharged oxygen is 0.3%. The oxygen 25 discharged from the exhaust pipe is pressurized by the gas pressure pump 34 and collected at a remote location.

[0185] According to the test data, after the gas treatment method of two electrolytic cells connected in series, the hydrogen impurity content of the oxygen to be treated 50 is reduced from the original 1.1% to 0.3%.

[0186] Example 7

[0187] The gas-liquid mixing electrochemical reaction device shown in FIG3 is Example 7 of the present invention. It is a gas-liquid mixing electrolytic cell with a circular electrode distribution structure, comprising an electrolytic cell body 1, electrolytic anodes 3-1 to 3-8 and electrolytic cathodes 4, or electrolytic anodes 3 and electrolytic cathodes 4-1 to 4-8, electrolytic power supplies 5-1 to 5-8, electrolytic cell gas-liquid mixers 9-1 to 9-8 combining vacuum jet and bubbling types, and a sealed cell cover 23 with holes for leaving escaping gas from the electrolytic cell reaction. Within the electrolytic cell body 1, an electrolytic anode or electrolytic cathode is positioned at the center of the cell body as a central electrode, and a plurality of corresponding electrodes of the other type are positioned around it. Electrolytic anodes 3-1 to 3-8 are connected to the positive electrodes of corresponding electrolytic power sources 5-1 to 5-8, respectively, and electrolytic cathodes 4 are connected to the negative electrodes of each electrolytic power source 5-1 to 5-8, or electrolytic anode 3 is connected to the positive electrodes of each electrolytic power source 5-1 to 5-8, and electrolytic cathodes 4-1 to 4-8 are connected to the negative electrodes of each electrolytic power source 5-1 to 5-8, respectively. The electrolytic cell body 1 is provided with insoluble anode conductors 19-1 to 19-8 that are directly electrically connected to the electrolytic anodes and insoluble cathode conductors 20 that are directly electrically connected to the electrolytic cathodes, or with insoluble anode conductors 19 that are directly electrically connected to the electrolytic anodes and insoluble cathode conductors 20-1 to 20-8 that are directly electrically connected to the electrolytic cathodes. The electrolytic cell gas-liquid mixers 9-1 to 9-8, which are a combination of vacuum jet and bubbling types, are connected to the electrolytic cell body as liquid flow pipes after passing through pumps 33 and valves 32-1 to 32-8, and their outlets are respectively directed toward the electrolytic anodes 33-1 to 3-8 and the insoluble anode conductors 19-1 to 19-8, or toward the electrolytic cathodes 4-1 to 4-8 and the insoluble cathode conductors 20-1 to 20-8.

[0188] Comparative Example 1

[0189] This comparative example adopts the method of Example 1, except that only a common electrolysis anode and a common electrolysis cathode are used and no electrocatalytic component is used.

[0190] After 30 minutes of stable electrochemical reaction, a trace oxygen analyzer 48 was used to sample and detect the trace oxygen content concentration of the hydrogen gas 49 to be processed input into the electrolytic cell and the hydrogen gas 24 escaping from the electrolytic cell. The detection and calculation results showed that the oxygen content of the hydrogen gas 49 to be processed was 0.9%, and the oxygen content of the hydrogen gas 24 after purification was 0.8%.

[0191] Comparative Example 2

[0192] Comparative Example 2 is a basic implementation method for safely treating hydrogen through an electrooxidation process in the prior art. As shown in Figure 14, the apparatus employed includes an electrolytic cell 1, a monolithic conductor, a hydrogen pump 53, and a cathode spray pipe 54. The monolithic conductor serves as the electrolytic anode 3 and is connected to the electrolytic cathode 4 via a bridge to form an electrochemical reaction electrode pair, which is immersed in the electrolyte of the electrolytic cell 1. The hydrogen pump 53 is used to directly pump waste gas hydrogen into the electrolytic cell, mixing the waste gas hydrogen with the electrolyte to produce a hydrogen-containing electrolytic mixed liquid. A cathode spray pipe 54 is installed at the other end of the conductor, and an oxygen-containing solution 56 is sprayed toward the other end of the conductor through the cathode spray pipe 54. The end closest to the hydrogen pump 53 serves as the electrolytic anode 3, and the other end, where the oxygen-containing solution 56 is sprayed, serves as the electrolytic cathode 4.

[0193] Specifically, the method for safely treating hydrogen by an electro-oxidation process in this comparative example includes the following steps:

[0194] (1) A hydrogen-containing electrolytic mixed solution is produced near one end of the conductor in the electrolytic cell body 1 by a hydrogen pump.

[0195] (2) While carrying out step (1), an oxygen-containing solution 56 is sprayed onto the electrolytic cathode 4 in the hydrogen oxide electrolytic cell body 1 through the cathode liquid spray pipe 54, so that the entire area of ​​the electrolytic anode 3 and the electrolytic cathode 4 is immersed in the electrolyte in the electrolytic cell body 1.

[0196] (3) The electrochemical reaction occurs at the electrolysis anode 2, causing hydrogen to lose electrons and transform into hydrogen ions. The electrochemical reaction occurs at the electrolysis cathode 4, causing the oxidizing substance to gain electrons and causing a portion of it to combine with hydrogen ions to form water.

[0197] The electrolyte 2 is an alkaline solution with sodium hydroxide as the main component, and the oxygen-containing solution 56 is a mixture of sodium hydroxide aqueous solution and oxygen.

[0198] The material of the entire conductor is gold, platinum, silver, copper, titanium and / or alloys containing any of the above metals and / or titanium substrate coating electrodes and / or conductive graphite and / or stainless steel.

[0199] The hydrogen gas to be treated, pumped in by the hydrogen pump 53, had a hydrogen concentration of 27,000 ppm. After 30 minutes of stable electrochemical reaction, the hydrogen concentration of the treated tail gas was measured using a trace hydrogen analyzer. The trace hydrogen analyzer output data showed 16,500 ppm, indicating that the hydrogen concentration of the hydrogen tail gas 24 escaping from the electrolytic cell reaction was 16,500 ppm, indicating a treatment efficiency less than 50% of the treatment efficiency of Example 3 of the present invention.

[0200] By comparing the result data of Example 1 and Comparative Example 1, and Example 3 and Comparative Example 2, it can be seen that the combination of the gas-liquid mixing source / electrolyzer gas-liquid mixer and the electrocatalytic structure adopted in the present invention can achieve significant electrochemical reaction electrocatalysis and efficiently process hydrogen and oxygen.

[0201] The embodiments of the present invention can achieve production with lower energy consumption when the electrochemical reaction is performed at a voltage less than or equal to the electrolyte decomposition voltage, or when the electrochemical reaction is performed at a voltage slightly higher than the electrolyte decomposition voltage when there is sufficient gas participating in the reaction so that it is difficult for electrical components to electrolyze gas.

Claims

1. A gas-liquid mixed electrochemical reaction device for treating hydrogen or oxygen, comprising an electrolytic cell mainly composed of an electrolytic cell body, an electrolytic anode, an electrolytic cathode, and an electrolytic power supply, wherein: The electrolysis anode is connected to the positive electrode of the electrolysis power supply, and the electrolysis cathode is connected to the negative electrode of the electrolysis power supply. The electrolytic cell is characterized in that it includes a gas-liquid mixture source and / or at least one electrolytic cell gas-liquid mixer, and an electrocatalytic component, forming a gas-liquid mixing electrolytic cell. The gas-liquid mixture source is connected to the electrolytic cell body by a liquid flow pipe, and the outlet of the electrolytic cell gas-liquid mixer is oriented toward or located in the electrolytic cell body. The electrocatalytic component adopts any one or more of the following methods: Electrocatalytic method (1) At least one electrocatalytic component is built into the electrolytic cell body, the gas-liquid mixture source flows toward the electrocatalytic component and / or the electrolytic anode and / or the electrolytic cathode, and / or the outlet of the electrolytic cell gas-liquid mixer is directed toward the electrocatalytic component and / or the electrolytic anode and / or the electrolytic cathode; Electrocatalytic method (2) improves the electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode, that is, at least one of the electrolytic anode and the electrolytic cathode is one or more parallel-connected electrodes, the gas-liquid mixture source flows toward the electrolytic anode and / or the electrolytic cathode with improved electrocatalytic performance structure, and / or the outlet of the electrolytic tank gas-liquid mixer is directed toward the electrolytic anode and / or the electrolytic cathode with improved electrocatalytic performance structure; Electrocatalytic method (3): The electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode is improved, and the angle ɑ formed by a part or the whole of at least one of the electrolytic anode and the electrolytic cathode and the straight line of the gas-liquid mixture ejected from the outlet of the electrolytic tank gas-liquid mixer is greater than 0° and less than 90°, and the outlet of the electrolytic tank gas-liquid mixer is oriented toward the electrolytic anode and / or the electrolytic cathode with the improved electrocatalytic performance structure.

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

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

4. The gas-liquid hybrid electrochemical reaction device according to claim 3, characterized in that: The electrocatalytic component is a bipolar electrode and / or an insoluble conductor; The bipolar electrode refers to an insoluble conductor that is disposed between the electrolysis anode and the electrolysis cathode, is not connected to an external power source, and is immersed in the electrolyte; the insoluble conductor is directly conductively connected to the electrolysis anode or the electrolysis cathode, so that the electrolysis anode or the electrolysis cathode becomes an electrode of irregular shape, wherein the insoluble conductor connected to the electrolysis anode is called an insoluble anode conductor, and the insoluble conductor connected to the electrolysis cathode is called an insoluble cathode conductor.

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

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

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

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

9. A method for treating hydrogen or oxygen using the gas-liquid hybrid electrochemical reaction device according to claim 1, characterized in that: The following steps are involved: (1) using a gas-liquid hybrid electrochemical reaction device, using an aqueous electrolyte solution as the electrolyte of a gas-liquid hybrid electrolytic cell in the device, and turning on an electrolysis power supply to perform electrolysis; (2) introducing a treated gas containing hydrogen and / or oxygen into the electrolyte by at least one of the following two methods: ① Inputting a gas-liquid mixture containing the gas to be processed from a gas-liquid mixture source into the gas-liquid mixing electrolytic cell; ② Start the electrolytic cell gas-liquid mixer to mix the treated gas with the electrolyte to form a gas-liquid mixture and send it to the gas-liquid mixing electrolytic cell, or directly form a gas-liquid mixture in the gas-liquid mixing electrolytic cell; The gas-liquid mixture is mixed with at least one of the electrolytic anode, electrolytic cathode and electrocatalytic component in the gas-liquid mixed electrolytic cell. A component contacts and exerts an electrocatalytic effect to electrochemically oxidize or reduce the gas being processed in the electrolyte, causing hydrogen to be oxidized to generate water and / or oxygen to be reduced to generate water.

10. The method for treating hydrogen or oxygen according to claim 9, characterized in that: When purifying hydrogen or oxygen, the hydrogen or oxygen containing impurities is mixed with the electrolyte through the gas-liquid mixer of the electrolytic cell and contacts at least one of the electrolytic anode, electrolytic cathode, and electrocatalytic component. The impurities therein are consumed through the joint reaction and water is generated through the electrochemical reaction.

11. The method for treating hydrogen or oxygen according to claim 10, characterized in that: When the hydrogen waste gas is eliminated, the oxidant contained in the electrolyte is allowed to pass through the gas-liquid hybrid electrolytic cell to undergo an electrochemical reaction and react with the oxidant to generate water.

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