Integrated device for electrocatalytic reduction of carbon dioxide / carbon monoxide

Abstract

An integrated device for electrocatalytic reduction of carbon dioxide / carbon monoxide relates to the technical field of energy catalysis and comprises a reactor module, a gas-liquid passage module, an electrolyte passage module, a temperature control liquid passage module, a reaction circuit module and a control module. The reactor module comprises a cathode temperature control plate, a cathode plate, a membrane electrode, an anode plate and an anode temperature control plate; the gas-liquid passage module is used for providing raw material gas with adjustable temperature and humidity for a cathode reaction runner of the reactor module and outputting a reaction product; the electrolyte path module enables electrolyte to circulate in the anode reaction flow channel; the temperature control liquid passage module is used for controlling the temperature of the reactor module and the electrolyte storage tank; the reaction circuit module provides electric energy for the reactor module; and the control module is used for integrally controlling each module, monitoring the state of the device and recording operation data. The system has the advantages of being large in scale, capable of achieving integrated control, more convenient to use, more in controllable parameters, high in safety and the like.

Description

Technical Field

[0001] The invention relates to the field of energy catalysis technology, and in particular to an integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction. Background Art

[0003] Carbon dioxide / carbon monoxide electrocatalytic reduction technology can use the electricity converted by new energy to directly convert carbon dioxide / carbon monoxide into valuable chemicals such as ethylene and ethanol. This will not only help promote greenhouse gas emission reduction and help achieve the "dual carbon" goals, but also create considerable additional economic benefits. In recent years, research on carbon dioxide / carbon monoxide electrocatalytic reduction has progressed rapidly, but most of the research is still at the laboratory scale and urgently needs to be promoted towards industrial application.

[0004] Laboratory-scale carbon dioxide / carbon monoxide electrocatalytic reduction research requires relatively simple devices and control modules, which are generally built by researchers themselves; such self-built devices have a series of problems such as small scale, inability to integrate control, fewer controllable parameters, and low safety, making them difficult to use for large-scale carbon dioxide / carbon monoxide electrocatalytic reduction research. For example, Chinese patent CN115161677A discloses a temperature-controllable carbon dioxide electrolysis device, but it is small in scale and can only control the temperature of the electrolytic cell, and cannot control and detect other related parameters such as intake humidity, nor can it achieve integrated control of the entire device, and it does not have a safety module, making it difficult to ensure the safety of the operator. Summary of the invention

[0005] The purpose of the present invention is to solve the above problems in the prior art and to provide an integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction, which has the advantages of large scale, integrated control, more convenient use, more controllable parameters and higher safety.

[0006] In order to achieve the above object, the present invention adopts the following technical scheme:

[0007] An integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction, comprising a reactor module, a gas-liquid passage module, an electrolyte passage module, a temperature control liquid passage module, a reaction circuit module, and a control module;

[0008] The reactor module comprises a cathode temperature control plate, a cathode plate, a membrane electrode, an anode plate and an anode temperature control plate which are arranged in sequence; wherein the cathode plate is provided with a cathode reaction flow channel as a gas-liquid passage, the anode plate is provided with an anode reaction flow channel as an electrolyte passage, and temperature control flow channels are respectively provided between the cathode temperature control plate and the cathode plate, and between the anode temperature control plate and the anode plate;

[0009] The gas-liquid passage module is used to provide a feed gas with adjustable temperature and humidity to the cathode reaction flow channel of the reactor module, and output a reaction product;

[0010] The electrolyte passage module includes an electrolyte storage tank and a circulation pump, which form an electrolyte circulation passage, so that the electrolyte circulates in the anode reaction flow channel;

[0011] The temperature control liquid passage module includes a temperature control liquid pump and a temperature control flow channel connected to the outer layer of the electrolyte storage tank, which is used to control the temperature of the reactor module and the electrolyte storage tank;

[0012] The reaction circuit module includes a constant voltage and constant current instrument to provide electrical energy to the reactor module;

[0013] The control module includes an industrial control computer, industrial control software and a control circuit, which are used for integrated control and monitoring of device status and recording of operating data.

[0014] The gas-liquid passage module includes a raw gas source, two temperature-controlled humidifiers arranged in parallel, a hygrometer, and a gas-liquid separator, wherein the raw gas passes through the temperature-controlled humidifier and is detected by the hygrometer, and then enters the cathode reaction channel of the reactor module, and after the reaction, flows out from the cathode reaction channel and enters the gas-liquid separator; the two temperature-controlled humidifiers include a bubbling humidifier and a humidity generator.

[0015] The gas-liquid passage module also includes two groups of connected four-way valves, which are connected to the hygrometer, the three-way valve, the argon gas source, and the cathode reaction channel of the reactor module. The three-way valve is connected to two temperature-controlled humidifiers. By switching the four-way valve, the functions of detecting the humidified raw gas, the humidified raw gas entering the cathode reaction channel, and purging the hygrometer with argon are realized.

[0016] The gas product separated by the gas-liquid separator is switched to direction A through a three-way valve to connect to a volume flow meter for detecting the total volume flow of the gas product, and then switched to direction B to connect two flow stabilizing valves in parallel to divert the gas. The appropriate flow enters the online gas chromatograph for analysis, and the remaining gas is exhausted.

[0017] The electrolyte storage tank has a double-layer structure, the inner layer is used for the electrolyte passage module, and the outer layer is used for the temperature control liquid passage module. Both the electrolyte passage module and the temperature control liquid passage module can be connected to multiple storage tanks in series to achieve the function of quickly replacing the electrolyte.

[0018] The present invention also includes a safety module, which includes a protective cover, an exhaust fan and a gas alarm. The protective cover is used to isolate the toxic, harmful, flammable and explosive gases generated during the reaction from the operator; the exhaust fan is connected to the protective cover to extract the toxic, harmful, flammable and explosive gases from the protective cover; the gas alarm is placed outside the protective cover, and if a toxic, harmful, flammable and explosive gas leak is detected, an audible and visual alarm signal is issued and the reaction is shut down.

[0019] The reaction circuit module also includes a voltage inspection module for monitoring the voltage of the reactor module.

[0020] The cathode reaction channel, the anode reaction channel, the cathode temperature control channel, and the anode temperature control channel are in the shape of a straight line, a serpentine, a spiral, an interdigitated shape, or a grid.

[0021] The cathode plate and the anode plate are both equipped with thermocouples for real-time detection of reaction temperature.

[0022] The application of the integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction is used for carbon dioxide / carbon monoxide electrocatalytic reduction. Carbon monoxide / carbon dioxide gas undergoes an electrocatalytic reduction reaction at the cathode three-phase interface of the membrane electrode, and an electrocatalytic oxidation reaction occurs at the anode three-phase interface of the electrolyte membrane electrode. The electrocatalytic oxidation reaction and the electrocatalytic reduction reaction together constitute the overall reaction of carbon dioxide / carbon monoxide electrocatalytic reduction.

[0023] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0024] 1. It can be applied to both single electrolytic cells and electric stacks. It is large-scale and can process tons of carbon dioxide annually, laying a foundation for the construction of a carbon dioxide electrolysis engineering demonstration system.

[0025] 2. The integrated control, status monitoring, data collection and other functions of each module of the entire device can be fully realized on the industrial computer, which is more convenient to operate and is conducive to the promotion of the industrialization of carbon dioxide electrocatalytic reduction.

[0026] 3. Compared with similar technologies, it can realize functions such as precise control and detection of humidity, instant replacement of failed electrolyte, etc., and has better use effect.

[0027] 4. It is equipped with a safety module to promptly extract the toxic, harmful, flammable and explosive gases leaked and discharged from the reaction system, and has an alarm function to ensure the safety of the operator. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a structural schematic diagram of the present invention;

[0029] Figure 2 It is a control schematic diagram;

[0030] Figure 3 Real-time recording of results for voltage data;

[0031] Figure 4 is the total reaction current corresponding to different voltages and Faradaic efficiency of the reduction product;

[0032] Figure 5 The results are recorded for the temperature of the cathode plate and the anode plate. DETAILED DESCRIPTION

[0033] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer and more understandable, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments.

[0034] Example 1

[0035] See also Figure 1 This embodiment is an integrated device for electrocatalytic reduction of carbon dioxide / carbon monoxide, and the integrated device includes a reactor module, a gas-liquid passage module, an electrolyte passage module, a temperature control liquid passage module, a reaction circuit module, a control module and a safety module.

[0036] The reactor module is composed of a single combination of cathode temperature control plate 21, cathode plate 22, membrane electrode 33, anode plate 24 and anode temperature control plate 23, that is, a single electrolytic cell. In other embodiments, multiple combinations can also be formed to form a stack.

[0037] The shapes of the cathode plate 22, the anode plate 24, the cathode temperature control plate 21, and the anode temperature control plate 23 can be square, rectangular, circular, etc.; the materials of the cathode plate 22, the anode plate 24, the cathode temperature control plate 21, and the anode temperature control plate 23 can be metals such as titanium, titanium alloy, gold, stainless steel, or conductive materials such as graphite. The side of the cathode plate 22 and the anode plate 24 that are in contact with the membrane electrode 33 can be plated with a protective layer such as gold or platinum for protection. Specifically, in this embodiment, the cathode plate 22, the anode plate 24, the cathode temperature control plate 21, and the anode temperature control plate 23 are all square and made of titanium metal. The flow channel surface of the cathode plate 22 is plated with gold, and the flow channel surface of the anode plate 24 is plated with platinum.

[0038] The cathode plate 22, the anode plate 24, the cathode temperature control plate 23, and the cathode reaction channel, the anode reaction channel, the cathode temperature control channel, and the anode temperature control channel on the anode temperature control plate 23 may be in the shape of a straight line, a serpentine, a spiral, an interdigitated or a grid shape. Specifically, in this embodiment, a serpentine cathode reaction channel is engraved on the cathode plate 22 as a gas-liquid passage, and the channel has an inlet 26 and an outlet 31; a straight anode reaction channel is engraved on the anode plate 24 as an electrolyte passage, and the channel has an inlet 27 and an outlet 30. The flow field dimensions of the cathode reaction channel and the anode reaction channel are both .

[0039] The reaction circuit module mainly includes a constant voltage and constant current instrument 20 and a voltage inspection module 53. The positive and negative electrodes of the constant voltage and constant current instrument 20 and the voltage inspection module 53 are respectively connected to the cathode plate 22 and the anode plate 24 through wires.

[0040] A temperature control channel for a temperature control liquid is provided between the cathode temperature control plate 21 and the cathode plate 22, and the channel has an inlet 25 and an outlet 32. A temperature control channel for a temperature control liquid is provided between the anode temperature control plate 24 and the anode plate 23, and the channel has an inlet 29 and an outlet 28. The cathode plate 22 and the anode plate 24 are both provided with thermocouples 51 and 52, which can realize real-time detection of the reaction temperature.

[0041] The membrane electrode 33 is composed of a cathode gas diffusion layer, a cathode catalyst layer, a solid electrolyte membrane, an anode catalyst layer, and an anode gas diffusion layer arranged in sequence, and is the core of the reactor module. The anode and cathode gas diffusion layers are composed of porous materials, which can be carbon cloth, carbon paper or porous metal materials, including but not limited to nickel foam, titanium mesh, titanium fiber felt, etc. The solid electrolyte membrane can be an anion exchange membrane, a cation exchange membrane or a bipolar membrane, etc.

[0042] In this embodiment, the cathode gas diffusion layer of the membrane electrode 33 is made of carbon paper, the anode gas diffusion layer is made of titanium fiber felt, the cathode catalyst layer is made of copper-based catalyst, and the anode catalyst layer is made of Catalyst, solid electrolyte membrane uses anion exchange membrane.

[0043] The gas-liquid passage module includes a gas-liquid input part and a product output part.

[0044] The gas-liquid input part includes gas sources 1, 2, 3, inlet gas flow meters 4, 5, 6, a humidity generator 12, a bubbling humidifier 13, a hygrometer 19, and is connected by necessary pipelines, a four-way connector 10, a three-way valve 11, a three-way valve 15, four-way valves 17, 18, etc., and the end is connected to the cathode reaction channel inlet 26, for inputting carbon monoxide / carbon dioxide gas of required temperature and humidity, and an electrocatalytic reduction reaction occurs on the cathode three-phase interface of the membrane electrode 33.

[0045] Specifically, in the gas-liquid input part, the pipeline after the raw gas passes through the inlet flowmeters 4, 5, and 6 can be connected in parallel to two temperature-controlled humidifiers with different design principles, wherein 12 is a humidity generator, and the required water is extracted from the pure water storage tank 8 by the injection pump 9 and injected into the humidity generator, and 13 is a bubbling humidifier, and the required water is extracted from the pure water storage tank 8 by the centrifugal pump 14 and injected into the bubbling humidifier. The three-way valves 11 and 15 are used to control the gas to pass through one of the temperature-controlled humidifiers to generate gas with the required humidity.

[0046] More specifically, the pipeline after the raw gas passes through the temperature-controlled humidifier can be connected to the hygrometer 19 and the straight pipeline 49 in parallel, and the four-way valve 17 or 18 is used to control the gas to pass through one of the ways, while the other way is connected to the outside through the inlet 51 and the outlet 50. When the humidified raw gas passes through the hygrometer 19, the hygrometer 19 can display the gas temperature and humidity. When the humidified raw gas passes through the straight pipeline 49, the hygrometer 19 is connected to the outside through the inlet 51 and the outlet 50. The moisture inside the cavity of the hygrometer 19 can be purged and removed by opening the valve 7 and inputting the gas source 1, thereby protecting the internal components of the hygrometer 19 and improving its sensitivity and service life. The four-way valves 17 and 18 have four interfaces A, B, C, and D, and the valves can switch between two states, one of which is AB connection and CD connection, and the other is AD connection and BC connection.

[0047] The product output part includes a gas-liquid separator 42, a volume flow meter 47, 55, a flow stabilizing valve 44, 45, a three-way valve 43 and a three-way connector 46, and an online gas chromatograph 48. The front end of the gas-liquid separator 42 is connected to the cathode reaction channel outlet 31, and pure water is extracted from the pure water storage tank 8 by a centrifugal pump 16 and injected into the gas-liquid separator 42. The gas product produced by the electrocatalytic reduction reaction is washed when passing through the gas-liquid separator 42 to collect the liquid product. The liquid product separated by the gas-liquid separator 42 can be discharged directly from the liquid outlet 56. The gas product separated by the gas-liquid separator 42 passes through the three-way valve 43 in turn, switches to the A direction to connect the volume flow meter 55, which is used to detect the total volume flow of the gas product, switches to the B direction to connect two flow stabilizing valves 44, 45 in parallel, and diverts the gas. The appropriate flow of the diversion is detected by the volume flow meter 47 and then connected to the online gas chromatograph 48 for analysis, and the remaining gas is emptied through the volume flow meter 55.

[0048] The electrolyte passage module includes the inner layer of electrolyte storage tanks 37 and 38, electrolyte circulation pump 34, electrolyte replenishment tank 40, electrolyte replenishment pump 39, and is connected by necessary pipelines, three-way valves, etc., and the two ends are respectively connected to the anode reaction channel inlet 27 and outlet 30 to form a circulation passage. Specifically, the electrolyte replenishment pump 39 extracts electrolyte from the electrolyte replenishment tank 40 and injects it into the electrolyte storage tank 37 or 38. The electrolyte in the electrolyte storage tank 37 or 38 enters the anode reaction channel inlet 27 under the action of the electrolyte circulation pump 34, and an electrocatalytic oxidation reaction occurs on the anode three-phase interface of the membrane electrode 33, and its gas-liquid product flows out from the anode reaction channel outlet 30 and returns to the inner layer of the electrolyte storage tank 37 or 38. The electrocatalytic oxidation reaction and the aforementioned electrocatalytic reduction reaction together constitute the overall reaction of carbon dioxide / carbon monoxide electrocatalytic reduction.

[0049] The electrolyte can be a liquid such as sodium hydroxide solution, potassium hydroxide solution, sodium bicarbonate solution, potassium bicarbonate solution, pure water, or a mixture of any of them.

[0050] The electrolyte storage tanks 37 and 38 are both double-layer structures, the inner layer of which is used for the electrolyte passage module and has a gas pressure relief valve; the outer layer of which is used for the temperature control liquid passage module.

[0051] The temperature control liquid passage module includes a temperature control liquid pump 41 with a constant temperature liquid storage container and the outer layer of the electrolyte storage tanks 37 and 38, and is connected by necessary pipelines, three-way valves, etc., and the two ends are respectively connected to the anode temperature control flow channel inlet 29 and the cathode temperature control flow channel outlet 32, and the anode temperature control flow channel outlet 28 is directly connected to the cathode temperature control flow channel inlet 25 through a pipeline, together forming a circulation passage. Under the action of the temperature control liquid pump 41, the temperature control liquid successively passes through the anode temperature control flow channel, the cathode temperature control flow channel, and the outer layer of the electrolyte storage tank 37 or 38, controls the temperature of the reactor module and the electrolyte storage tank, and returns to the constant temperature storage container attached to the temperature control liquid pump 41.

[0052] The temperature control liquid can be one of pure water, aqueous solution or organic solvents such as ethanol.

[0053] Preferably, in the electrolyte passage module, the inner layers of two electrolyte storage tanks 37 and 38 can be connected in parallel at the same time, and the three-way valves 35, 36 and 54 can be used to control the electrolyte to be pumped out from the inner layer of one of the electrolyte storage tanks and circulate back to the inner layer of the electrolyte storage tank. At the same time, the outer layers of the two electrolyte storage tanks 37 and 38 are connected to the temperature control liquid passage module at the same time in series mode. After a certain reaction time, the failed electrolyte can be quickly replaced by switching the electrolyte storage tanks; while the temperature control liquid passage module does not need to be switched.

[0054] The control module is composed of an industrial control computer, industrial control software and a control circuit. Figure 2 , can control the inlet gas flowmeter 4, 5, 6, the temperature-controlled humidifier, the hygrometer 19, the constant pressure and constant current instrument 20, the voltage inspection module 53, the electrolyte circulation pump 34, the temperature-controlled liquid pump 41, the volume flowmeter 47, 55, and can record the operation data history.

[0055] The safety module is composed of a protective cover, an exhaust fan, a gas alarm, etc. The protective cover is used to separate the toxic, harmful, flammable and explosive gases contained in the reactants and products from the operator. The exhaust fan can extract the toxic, harmful, flammable and explosive gases. The gas alarm is placed outside the protective cover. Once the toxic, harmful, flammable and explosive gas leaks, the inlet gas flow meter 4, 5, 6 and the constant pressure and constant current meter 20 are automatically closed immediately, and an alarm is given in the form of sound, light, etc. to ensure the personal safety of the operator.

[0056] In this embodiment, the operations are as follows:

[0057] Turn on the electrolyte replenishing pump to extract electrolyte from the electrolyte replenishing tank, and inject the electrolyte into the electrolyte storage tank 37 or 38 by adjusting the three-way valve 54, and adjust the three-way valves 35, 36 and 54 to control the electrolyte to be pumped out from the inner layer of the electrolyte storage tank 37, and finally circulate back to the inner layer of the electrolyte storage tank.

[0058] Turn on the power supply and the main control switch of the device, turn on the exhaust fan and the gas alarm in the safety module. Turn on the gas source 2, set the inlet gas flow meter 5, and make the flow rate of carbon dioxide gas Adjust the three-way valve 11 and the three-way valve 15 to allow the carbon dioxide gas to flow through the humidity generator 12, and increase the temperature of the carbon dioxide gas to , the humidity increases to 80%. Adjust the four-way valve 17 and the four-way valve 18 to allow the humidified carbon dioxide to pass through the hygrometer 19, observe the humidity display, and wait for it to stabilize at about 80% for a period of time; then adjust the four-way valve 17 and the four-way valve 18 to allow the humidified carbon dioxide to directly enter the cathode reaction flow channel inlet 26 through the straight-through pipe 49, enter the cathode reaction flow channel, and flow out from the cathode reaction flow channel outlet 31. At this time, the hygrometer 19 is connected to the outside world, and the valve 7 is opened to input the gas source 1 to purge it through the inlet 51 and the outlet 50.

[0059] In electrocatalysis In the reduction reaction, the cathode uses As Catalyst, mix the catalyst with ionomer and spray it on On the carbon paper, the loading amount is The anode uses As an oxygen evolution reaction catalyst, it was mixed with ionomer and sprayed on platinum-coated titanium fiber felt of the same size, with a loading of .use The anion exchange membrane is used as the diaphragm. Install the electrolytic cell components in order and connect the corresponding pipelines after completion.

[0060] Will The potassium bicarbonate solution is added to the inner layer of the electrolyte storage tank 37 and 38 as the electrolyte, and a sufficient amount of pure water is added to the temperature control liquid pump 41 as the temperature control liquid. Adjust the electrolyte circulation pump 34 and set the electrolyte flow rate to ; Adjust the temperature control liquid pump 41, set the temperature to 60 ℃, and the flow rate to .

[0061] After ensuring that the cathode gas and the anode electrolyte are fully circulated and the membrane electrode is wetted, the constant voltage and constant current instrument 20 is set to the constant current mode, and the current settings are 4.5 A, 9 A, 18 A, 27 A, 36 A, 45 A, 54 A, 72 A and 90 A in sequence, and the reaction is carried out for 600 seconds at each current value.

[0062] The reaction product flows out through the cathode reaction channel outlet 31 and is separated into gaseous and liquid products in the gas-liquid separator 42. The liquid product is collected through the liquid outlet 56, and then the components are quantitatively analyzed using nuclear magnetic resonance. The gaseous product flows through the three-way valve 43. When it is switched to direction A, all gases are discharged, and the rear end is connected to the volume flow meter 55 for detecting the flow rate of the gas at the outlet of the electrolytic cell. After switching to direction B, the gas flows through the steady flow valves 44 and 45 for diversion, and the gas volume flow suitable for entering the chromatogram is connected to the volume flow meter 47 through the outlet of the steady flow valve 45, and the gas chromatograph is connected at its outlet for quantitative analysis of the composition of the gaseous product.

[0063] After each potential reaction is completed, the liquid product in the gas-liquid separator needs to be collected through the liquid outlet 56. After the collection is completed, water is replenished from the pure water storage tank 8 to the gas-liquid separator 42, and the opening time of the centrifugal pump 16 is controlled to accurately adjust the amount of replenishment. At the same time, the electrolyte in the electrolyte storage tank 37 is discharged from the outlet, and the electrolyte is pumped into the electrolyte storage tank 38 by the replenishment pump, and the amount of replenishment is accurately controlled by adjusting the time of the electrolyte replenishment pump 39. By adjusting the three-way valves 35, 36 and 54, the electrolyte is pumped out from the inner layer of the electrolyte storage tank 38, and circulated back to the inner layer of the electrolyte storage tank for the next potential test. The electrolyte storage tanks 37 and 38 are used alternately.

[0064] The voltage data during the reaction process is recorded in real time by the voltage inspection module 53. Figure 3 shown. Figure 4 Shows different currents The Faradaic efficiency of the reduction products, among which the Faradaic efficiency of carbon monoxide is maintained above 90% in a wide potential range. Figure 5 The temperature of the cathode and anode plates of the electrolytic cell during the reaction is shown. The plate temperature is basically maintained at around 60°C, indicating that the temperature in the reaction area remains stable during the reaction.

[0065] Example 2

[0066] The conditions are the same as those in Example 1, but before the constant voltage and constant current instrument 20 applies current, the three-way valve 11 and the three-way valve 15 are adjusted to allow the carbon dioxide gas to flow through the bubbling humidifier 13, and the temperature of the bubbling humidifier is set to , the humidity of carbon dioxide gas is Set the temperature of the electrolytic cell to , so that the temperature of carbon dioxide gas increases to At this time, according to the saturated vapor pressure data at different temperatures, the theoretical humidity of the gas should be 80%.

[0067] Adjust the four-way valve 17 and the four-way valve 18 to allow the humidified carbon dioxide to pass through the hygrometer 19 and observe whether the humidity displayed is the theoretical value. If there is a deviation, adjust the temperature of the bubbling humidifier until it stabilizes at about 80% and can last for a period of time. The subsequent process is the same as that of Example 1.

[0068] Example 3

[0069] The conditions are the same as those in Example 1, but the reactor module is a multiple combination of cathode temperature control plate 21, cathode plate 22, membrane electrode 33, anode plate 24 and anode temperature control plate 23, i.e., a stack. The stack contains 5 cells in total. The flow rate of carbon dioxide gas is set to , the electrolyte flow rate is , the temperature control water flow is The other parameters are the same as those in Example 1.

[0070] Example 4

[0071] The conditions are the same as those in Example 1. The inlet gas flow meter 6 is turned on. The feed gas is carbon monoxide and the electrolyte is of potassium hydroxide solution.

[0072] Example 5

[0073] The conditions are the same as those in Example 1. The inlet gas flow meters 4 and 5 are turned on. The raw gas is a mixture of carbon dioxide and Ar. The electrolyte is of potassium bicarbonate solution.

[0074] The present invention also has the following outstanding beneficial effects:

[0075] The electrolytic cell of the present invention is composed of components such as a cathode temperature control plate, a cathode plate, a membrane electrode, an anode plate, and an anode temperature control plate. These components can be combined in single or multiple combinations to adapt to applications of different scales. Therefore, the design of the electrolytic cell of the present invention has good scalability. It can be used as a single electrolytic cell or in multiple combinations to form a stack to meet larger-scale production needs. This design enables the electrolytic cell to be flexibly applied to experiments and production scenarios of different scales.

[0076] The present invention is provided with a temperature control liquid passage module, and the temperature of the reactor module and the electrolyte storage tank is controlled by circulating the temperature control liquid through a temperature control liquid pump. At the same time, the temperature control humidifier in the gas-liquid passage module can accurately adjust the temperature and humidity of the gas entering the electrolytic cell to ensure the stability and optimization of the reaction conditions.

[0077] The present invention is provided with a voltage inspection module, which is connected to the cathode plate and the anode plate through a wire, and can monitor the voltage change in the reaction process in real time to ensure the stability and safety of the reaction process.

[0078] The cathode plate and the anode plate of the present invention are engraved with flow channels of specific shapes (such as serpentine, straight, etc.). These flow channel designs help to accelerate the diffusion rate of bubbles on the electrode surface, improve the mass transfer efficiency, and thus promote the reaction.

[0079] The product output part of the present invention includes components such as a gas-liquid separator, a product gas volume flow meter, a flow stabilizing valve, and a three-way valve, which can effectively separate the gas product and the liquid product generated by the electrocatalytic reduction reaction and perform quantitative detection. The gas product after diversion is analyzed by a gas chromatograph to achieve accurate quantitative detection of the product. This design helps to accurately evaluate the reaction efficiency and product distribution, and provides data support for optimizing the reaction conditions.

[0080] The electrolyte passage module of the present invention is connected to the inner layers of two electrolyte storage tanks in parallel, and the circulation path of the electrolyte is controlled by a three-way valve. When the electrolyte in one of the storage tanks fails, it can be quickly switched to the other storage tank to achieve rapid replacement of the electrolyte.

[0081] The double-layer structure of the electrolyte storage tank of the present invention makes the temperature control liquid passage and the electrolyte passage independent of each other. The temperature control liquid passage is responsible for controlling the temperature of the reaction module, while the electrolyte passage is responsible for the circulation and renewal of the electrolyte. This design improves the flexibility and stability of the system.

[0082] The present invention uses two sets of four-way valves, which have four interfaces and two switching states, and can flexibly control the flow path of gas between the temperature-controlled humidifier, the hygrometer and the straight-through pipeline. This design enables the system to accurately control the temperature and humidity conditions of the gas according to different experimental requirements.

[0083] When the humidified raw gas passes through the hygrometer, the hygrometer can display the temperature and humidity information of the gas in real time. When the raw gas passes through the straight-through pipeline, the inside of the hygrometer cavity can be purged and cleared by opening the valve to protect the internal components of the hygrometer from contamination and extend its service life.

[0084] The present invention can significantly improve the efficiency and stability of the electrocatalytic reduction reaction and reduce fluctuations and uncertainties in the reaction process by precisely controlling the temperature and humidity of the electrolytic cell and the multi-point voltage monitoring function.

[0085] The present invention ensures that toxic, harmful, flammable and explosive gases are promptly extracted during the reaction process through the design of the safety module, and has an alarm function to ensure the personal safety of the operator. At the same time, the system's stable control and multi-point monitoring functions also help prevent potential safety hazards.

Claims

1. An integrated device for the electrocatalytic reduction of carbon dioxide / carbon monoxide, characterized in that: It includes a reactor module, a gas-liquid passage module, an electrolyte passage module, a temperature control liquid passage module, a reaction circuit module, and a control module; The reactor module comprises a cathode temperature control plate, a cathode plate, a membrane electrode, an anode plate and an anode temperature control plate which are arranged in sequence; wherein the cathode plate is provided with a cathode reaction flow channel as a gas-liquid passage, the anode plate is provided with an anode reaction flow channel as an electrolyte passage, and temperature control flow channels are respectively provided between the cathode temperature control plate and the cathode plate, and between the anode temperature control plate and the anode plate; The gas-liquid passage module is used to provide a feed gas with adjustable temperature and humidity to the cathode reaction flow channel of the reactor module, and output a reaction product; The electrolyte passage module includes an electrolyte storage tank and a circulation pump, which form an electrolyte circulation passage, so that the electrolyte circulates in the anode reaction flow channel; The temperature control liquid passage module includes a temperature control liquid pump and a temperature control flow channel connected to the outer layer of the electrolyte storage tank, which is used to control the temperature of the reactor module and the electrolyte storage tank; The reaction circuit module includes a constant voltage and constant current instrument to provide electrical energy to the reactor module; The control module is used for integrated control and monitoring of device status and recording of operating data.

2. The integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction according to claim 1, characterized in that: The gas-liquid passage module includes a raw gas source, two temperature-controlled humidifiers arranged in parallel, a hygrometer, and a gas-liquid separator, wherein the raw gas passes through the temperature-controlled humidifier and is detected by the hygrometer, and then enters the cathode reaction channel of the reactor module, and after the reaction, flows out from the cathode reaction channel and enters the gas-liquid separator; the two temperature-controlled humidifiers include a bubbling humidifier and a humidity generator.

3. The integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction according to claim 2, characterized in that: The gas-liquid passage module also includes two groups of connected four-way valves, which are connected to the hygrometer, the three-way valve, the argon gas source, and the cathode reaction channel of the reactor module. The three-way valve is connected to two temperature-controlled humidifiers. By switching the four-way valve, the functions of raw gas humidity detection, raw gas entering the cathode reaction channel, and argon gas purging the hygrometer are realized.

4. The integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction according to claim 2, characterized in that: The gas product separated by the gas-liquid separator is switched to direction A through a three-way valve to connect to a volume flow meter for detecting the total volume flow of the gas product, and then switched to direction B to connect two flow stabilizing valves in parallel to divert the gas. The appropriate flow enters the online gas chromatograph for analysis, and the remaining gas is exhausted.

5. The integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction according to claim 1, characterized in that: The electrolyte storage tank has a double-layer structure, the inner layer is used for the electrolyte passage module, and the outer layer is used for the temperature control liquid passage module. Both the electrolyte passage module and the temperature control liquid passage module can be connected to multiple storage tanks in series to achieve the function of quickly replacing the electrolyte.

6. The integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction according to claim 1, characterized in that: It also includes a safety module, which includes a protective cover, an exhaust fan and a gas alarm. The protective cover is used to isolate the toxic, harmful, flammable and explosive gases generated during the reaction from the operator; the exhaust fan is connected to the protective cover to extract the toxic, harmful, flammable and explosive gases from the protective cover; the gas alarm is placed outside the protective cover, and if a toxic, harmful, flammable and explosive gas leak is detected, it will emit an audible and visual alarm signal and shut down the reaction.

7. The integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction according to claim 1, characterized in that: The reaction circuit module also includes a voltage inspection module for monitoring the voltage of the reactor module.

8. The integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction according to claim 1, characterized in that: The cathode reaction channel, the anode reaction channel, the cathode temperature control channel, and the anode temperature control channel are in the shape of a straight line, a serpentine, a spiral, an interdigitated shape, or a grid.

9. The integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction according to claim 1, characterized in that: The cathode plate and the anode plate are both equipped with thermocouples for real-time detection of reaction temperature.

10. The use of the integrated device for carbon dioxide / carbon monoxide electrocatalytic reduction according to claim 1, characterized in that: Used for the electrocatalytic reduction of carbon dioxide / carbon monoxide, the carbon monoxide / carbon dioxide gas undergoes an electrocatalytic reduction reaction at the cathode three-phase interface of the membrane electrode, and the electrocatalytic oxidation reaction occurs at the anode three-phase interface of the electrolyte membrane electrode. The electrocatalytic oxidation reaction and the electrocatalytic reduction reaction together constitute the overall reaction of the electrocatalytic reduction of carbon dioxide / carbon monoxide.

Images