CN116024584B - Carbon dioxide electrocatalytic device with self-cleaning function - Google Patents
Carbon dioxide electrocatalytic device with self-cleaning function Download PDFInfo
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- CN116024584B CN116024584B CN202211610322.9A CN202211610322A CN116024584B CN 116024584 B CN116024584 B CN 116024584B CN 202211610322 A CN202211610322 A CN 202211610322A CN 116024584 B CN116024584 B CN 116024584B
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Abstract
The invention discloses a carbon dioxide electrocatalytic device with a self-cleaning function, which comprises a control module, a cleaning module, a detection module and at least two electrolysis modules, wherein the air inlet end of an air path structure of each electrolysis module is respectively connected with a carbon dioxide air source and the cleaning module through an air inlet side three-way valve, and the air outlet end of the air path structure is respectively connected with the detection module and a cleaning liquid recovery device through an air outlet side three-way valve; the cleaning module comprises an acidic cleaning liquid supply source, a clear water supply source, a nitrogen gas source and an electric control four-way valve, the detection module comprises gas analysis instruments which are in one-to-one correspondence with the electrolysis modules, the acidic cleaning liquid supply source, the clear water supply source and the nitrogen gas source are respectively connected to three inlet ends of the electric control four-way valve, and the gas circuit structure of each electrolysis module is connected to the outlet of the electric control four-way valve in parallel. The invention realizes the online automatic switching of the electrolytic module in the working state and the cleaning state, thereby combining with the online cleaning system.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a carbon dioxide electrocatalysis device with a self-cleaning function.
Background
CO 2 Electrocatalytic reduction to synthesis gas is CO 2 One of the effective ways to realize carbon neutralization by recycling utilization, wherein Gas Diffusion Electrode (GDE) technology can break through the limit of gas solubility, is gradually rising in the field of carbon dioxide electroreduction. Neutral in useOr alkaline medium and gas diffusion electrode, and can realize hundred milliampere level current density to practical level. The electrolysis unit sequentially comprises a cathode plate, a working electrode (cathode), an alkaline ion exchange membrane, a counter electrode (anode) and an anode plate from one side of the cathode to one side of the anode, wherein catalysts are coated on the working electrode and the counter electrode to realize electrocatalytic reduction reaction, the insides of the cathode plate and the anode plate are opposite, and simultaneously, the insides of the cathode plate and the anode plate are respectively provided with a corresponding cathode runner and an anode runner which are used for introducing C0 2 The latter gas is used to feed the electrolyte for the reaction.
When the electrocatalytic device with the structure is adopted to carry out the electrocatalytic reduction reaction of carbon dioxide, a small amount of K in the electrolyte + The plasma cations can enter the cathode region through the ion exchange membrane, and the cathode region in the technology does not have electrolyte, so that salt crystals such as potassium carbonate, potassium bicarbonate and the like can be formed, and the precipitated salt crystals are attached to the cathode plate and the working electrode, so that the gas flow and the effective catalytic area of the surface of the working electrode are influenced, and the catalytic reduction reaction efficiency of carbon dioxide is reduced. In the prior art, most of electrolytic devices with salt precipitation problem are disassembled, and then the cathode plate and the working electrode are taken out for cleaning treatment. Therefore, the disassembly and cleaning processes are tedious and time-consuming, and the catalytic layer on the surface of the working electrode is easy to damage or other parts of the device are easy to damage due to repeated disassembly and cleaning, so that the service life of the electrocatalytic device is shortened. Finally, the prior art does not combine the detection and judgment of the salt precipitation problem with the cleaning and recovery operation of the electrocatalytic device to realize automatic operation, so that the problem of reaction efficiency is difficult to find in time, the device is caused to operate at lower efficiency, the device cannot be cleaned in time and the device is recovered to operate, the overall working efficiency of the electrocatalytic device is caused to be lower, and more efforts are consumed by operators in the aspects of monitoring the reaction process and cleaning and dismounting the device.
Disclosure of Invention
The invention aims to provide a carbon dioxide electrocatalytic device with a self-cleaning function, which is used for solving the technical problems that in the prior art, the salt precipitation problem of a cathode region in an electrolysis unit is difficult to clean under the conditions of not stopping carbon dioxide reaction and not disassembling an electrolysis module, and the cleaning and the conversion of the electrolysis module in a cleaning state and a normal working state cannot be automatically completed, so that the defects that the whole cleaning and disassembling process needs complicated manual operation, is long in time consumption and easy to damage device parts, and the whole device cannot realize continuous work of carbon dioxide reduction treatment are overcome.
The carbon dioxide electrocatalytic device with the self-cleaning function comprises a control module, a cleaning module, a detection module and at least two electrolysis modules, wherein the air inlet end of an air path structure of each electrolysis module is respectively connected with a carbon dioxide air source and the cleaning module through an air inlet side three-way valve, the air outlet end of the air path structure is respectively connected with the detection module and a cleaning liquid recovery device through an air outlet side three-way valve, and two ends of a liquid path structure of each electrolysis module are respectively connected with an electrolyte supply source and a pipeline for outputting liquid products; the cleaning module comprises an acid cleaning liquid supply source, a clear water supply source, a nitrogen gas source and an electric control four-way valve, the detection module comprises gas analysis instruments which are in one-to-one correspondence with the electrolytic modules, the acid cleaning liquid supply source, the clear water supply source and the nitrogen gas source are respectively connected to three inlet ends of the electric control four-way valve, the gas path structures of the electrolytic modules are connected in parallel to the outlet of the electric control four-way valve, the control module is used for receiving detection data of the gas analysis instruments and judging whether the electrolytic modules are cleaned or not, and controlling the air inlet side three-way valve and the air outlet side three-way valve to realize conversion between working states and cleaning states of the corresponding electrolytic modules according to judging results and cleaning feedback signals, and controlling the cleaning modules to complete the cleaning process in the cleaning states.
Preferably, each electrolysis module comprises an electrolysis unit adopting a GDE technology, an air inlet pipe, an air outlet pipe, a liquid inlet pipe, a liquid outlet pipe and a corresponding power supply circuit, wherein the outlet end of the electric control four-way valve is connected with a cleaning main pipe, a plurality of cleaning branch pipes are connected in parallel to the outlet of the cleaning main pipe, the air inlet pipe of each electrolysis module is correspondingly connected with the outlet end of one air inlet side three-way valve, a plurality of carbon dioxide branch pipes are connected in parallel to a carbon dioxide air source, the carbon dioxide branch pipes and the cleaning branch pipes are in one-to-one correspondence, the two inlet ends of each air inlet side three-way valve are respectively connected with one carbon dioxide branch pipe and one cleaning branch pipe, each liquid outlet pipe is respectively connected with the inlet end of one corresponding air outlet side three-way valve, the two outlet ends of each air outlet side three-way valve are respectively connected with a corresponding gas analysis instrument and a corresponding cleaning liquid recovery pipe, the gas analysis instrument is connected with a gas product output pipe, the cleaning liquid recovery pipe is connected with a cleaning liquid recovery device, the liquid inlet pipe is connected with an electrolyte supply source and is provided with a liquid inlet switch valve, and the liquid outlet pipe is externally output a liquid product and oxygen and is provided with a liquid switch valve.
Preferably, the control module comprises a detection judging unit, a passage switching unit and a cleaning control unit.
The detection judging unit is used for receiving data output by the gas analysis instrument, calculating the concentration ratio of carbon monoxide to carbon dioxide, comparing the concentration ratio with a set threshold value, judging that the corresponding electrolysis module of the corresponding gas analysis instrument needs to be converted into a cleaning state when the concentration ratio is lower than the set ratio, and outputting a judging result.
The passage switching unit is used for changing the air passage structure of the corresponding electrolytic module through the air inlet side three-way valve and the air outlet side three-way valve according to the judging result and the cleaning feedback signal, controlling the on-off of a power supply circuit of the corresponding electrolytic module, and controlling the on-off of the liquid passage structure of the corresponding electrolytic module through the liquid inlet switch valve and the liquid outlet switch valve, so that the corresponding electrolytic module is switched between a working state and a cleaning state.
The cleaning control unit is used for sequentially opening and closing the cleaning liquid valve, the clear water valve and the nitrogen valve after the channel switching is finished, controlling the electric control four-way valve to sequentially select the corresponding inlet end to be opened, realizing the effect of sequentially inputting the acid cleaning liquid, the clear water and the nitrogen into the gas channel structure of the electrolysis module in the cleaning state, and sending a cleaning feedback signal to the channel switching module after the cleaning is finished.
Preferably, the electrolytic module is a bipolar electrolytic tank and comprises a plurality of electrolytic units, each electrolytic unit in the same electrolytic module is connected in parallel to the gas path structure and the liquid path structure of the electrolytic module, and each electrolytic unit is connected in series to the power supply circuit of the electrolytic module.
Preferably, the acidic cleaning solution supply source, the clean water supply source and the nitrogen gas source are respectively and correspondingly provided with a cleaning solution valve, a clean water valve and a nitrogen valve, the cleaning solution valve, the clean water valve and the nitrogen valve adopt on-off valves and/or flow regulating valves, and the cleaning solution valve, the clean water valve and the nitrogen valve are controlled by a control module.
Preferably, the liquid outlet pipes of the two electrolysis modules are connected in parallel to a liquid product main pipe, the liquid product main pipe is connected to an inlet of a gas-liquid separator, and a gas path outlet and a liquid path outlet of the gas-liquid separator respectively output oxygen and liquid products outwards.
Preferably, the method for cleaning the carbon dioxide electrocatalytic device during operation comprises the following steps:
firstly, collecting detection data, detecting and obtaining concentration data of carbon monoxide and carbon dioxide in a gas product output by a corresponding electrolysis module by a gas analysis instrument, and conveying the concentration data to a detection judging unit;
judging whether each electrolysis module needs to be cleaned or not, respectively calculating the concentration ratio of carbon monoxide to carbon dioxide output by each electrolysis module according to the concentration data received by the detection judging unit, judging that the corresponding electrolysis module needs to be cleaned when the concentration ratio of carbon monoxide to carbon dioxide is lower than a set threshold value, and collecting the results into a final judging result after the judgment of all the electrolysis modules is completed and outputting the final judging result to the channel switching unit;
step three, switching the control passage to switch the corresponding electrolytic module from the working state to the cleaning state, determining the electrolytic module to be switched to the cleaning state by the passage switching unit according to the determination result, opening the passages of the corresponding electrolytic module connected to the cleaning module and the cleaning liquid recovery device, closing the passages from the corresponding electrolytic module to a carbon dioxide gas source and a gas analysis instrument, closing the corresponding power supply circuit, a liquid inlet switch valve and a liquid outlet switch valve, stopping the operation of the corresponding electrolytic module, and outputting a signal to the cleaning control unit;
step four, cleaning the cathode region of the corresponding electrolytic module, after receiving the signals of the passage switching unit, the cleaning control unit sequentially opens and correspondingly switches the communicating object at the inlet end of the electric control four-way valve according to the sequence from the acid electrolyte supply source and the clean water supply source to the nitrogen gas source, sequentially inputs acid cleaning liquid, clean water and nitrogen gas into the electrolytic module to be cleaned to complete the cleaning step, and then sends cleaning feedback signals to the passage switching unit;
step five, switching control channels to convert the corresponding electrolytic modules from a cleaning state to a working state; the passage switching unit is used for closing the passages of the cleaning module and the cleaning liquid recovery device according to the cleaning feedback signal, opening the passages from the corresponding electrolytic module to the carbon dioxide gas source and the gas analysis instrument, and simultaneously opening the corresponding power supply circuit, the corresponding liquid inlet switch valve and the corresponding liquid outlet switch valve, so that the flow is ended.
Preferably, the step two further includes a second judging step, when determining whether the number of the electrolytic modules to be cleaned is equal to the number of all the electrolytic modules after determining the judging result of whether each electrolytic module to be cleaned is required, if yes, selecting the electrolytic module with the highest concentration ratio to be temporarily not converted into the cleaning state, otherwise, converting all the electrolytic modules to be cleaned into the cleaning state, and then outputting the final judging result according to the judging result.
The invention has the following advantages: according to the scheme, at least two electrolysis modules are arranged in the device, each electrolysis module can independently complete reduction treatment of carbon dioxide, meanwhile, an online cleaning system is arranged, and cleaning of the corresponding electrolysis module is completed through a series of cleaning actions of sequentially inputting acid cleaning liquid to clean salt crystals, inputting clear water to wash the acid cleaning liquid, inputting nitrogen to air-dry residual moisture and the like into a cathode region of an electrolysis unit with a salt precipitation problem. Meanwhile, the device realizes pipeline switching before cleaning of different electrolytic modules by using the control module through pipeline system design and arrangement of the electric control four-way valve and the electric control three-way valves related to the cleaning system, so that the corresponding electrolytic modules can be switched to be connected with the cleaning system and a recovery device communicated with cleaning liquid in a cleaning state, and thus, the online automatic switching of the electrolytic modules in the working state and the cleaning state is realized, and the online cleaning system is combined, so that the device can complete the online automatic switching of the electrolytic modules in the cleaning state and the working state and complete online automatic cleaning by using the control module under the condition that the electrolytic modules do not need to be manually disassembled and assembled, thereby not only ensuring better cleaning efficiency, but also keeping the continuous treatment of the whole device on carbon dioxide, and greatly improving the working efficiency of the whole device. Meanwhile, the whole switching cleaning process automatically starts operation through on-line monitoring of gas products, the degree of automation is high, and human errors caused by manpower consumption and manual monitoring are reduced.
Drawings
FIG. 1 is a schematic view of an electrolytic module in a carbon dioxide electrocatalytic apparatus with self-cleaning function according to the present invention.
FIG. 2 is a schematic view of an electrolytic cell in the middle of the structure shown in FIG. 1.
Fig. 3 is a schematic structural diagram of a carbon dioxide electrocatalytic apparatus with self-cleaning function according to the present invention.
Fig. 4 is a block diagram of the control system of the carbon dioxide electrocatalytic apparatus shown in fig. 3.
Fig. 5 is a flowchart of a method for cleaning the carbon dioxide electrocatalytic apparatus shown in fig. 3.
The marks in the drawings are: 1. an electric control three-way valve I, an electric control three-way valve II, an electric control three-way valve 3, an electric control three-way valve III, an electric control three-way valve 4, an electric control three-way valve IV, an electric control three-way valve 5, a gas analysis instrument I, a gas analysis instrument II, an electric control four-way valve 7, an electric control four-way valve 8, an electrolysis module I, an electrolysis module 9 and an electrolysis module II, 10, a gas-liquid separator 11, an electrolysis unit 12, a cathode plate 13, a bipolar plate 14, an anode plate 15, a cathode runner 16, a working electrode 17, an insulating gasket 18, an alkaline ion exchange membrane 19 and a counter electrode.
Detailed Description
The following detailed description of the embodiments of the invention, given by way of example only, is presented in the accompanying drawings to aid in a more complete, accurate, and thorough understanding of the inventive concepts and aspects of the invention by those skilled in the art.
As shown in fig. 1-5, the invention provides a carbon dioxide electrocatalytic device with a self-cleaning function, which comprises a control module, a cleaning module, a detection module and at least two electrolysis modules, wherein an air inlet end of an air path structure of each electrolysis module is respectively connected with a carbon dioxide air source and the cleaning module through an air inlet side three-way valve, an air outlet end of the air path structure is respectively connected with the detection module and a cleaning liquid recovery device through an air outlet side three-way valve, and two ends of a liquid path structure of each electrolysis module are respectively connected with an electrolyte supply source and a pipeline for outputting liquid products; the cleaning module comprises an acidic cleaning liquid supply source, a clear water supply source, a nitrogen gas source and an electric control four-way valve 7, the detection module comprises a gas analysis instrument corresponding to the first electrolytic module 8, the acidic cleaning liquid supply source, the clear water supply source and the nitrogen gas source are respectively connected to three inlet ends of the electric control four-way valve 7, the gas circuit structure of each electrolytic module is connected to the outlet of the electric control four-way valve 7 in parallel, and the control module is connected to control the electrolytic module, the cleaning module and the detection module.
Each electrolysis module comprises an electrolysis unit 11 adopting GDE technology, an air inlet pipe, an air outlet pipe, a liquid inlet pipe, a liquid outlet pipe and a corresponding power supply circuit, the outlet end of the electric control four-way valve 7 is connected with a cleaning main pipe, a plurality of cleaning branch pipes are connected in parallel to the outlet of the cleaning main pipe, the air inlet pipe of each electrolysis module is correspondingly connected with the outlet end of one air inlet side three-way valve, a plurality of carbon dioxide branch pipes are connected in parallel to the carbon dioxide air source, the carbon dioxide branch pipes are in one-to-one correspondence with the cleaning branch pipes, the two inlet ends of each air inlet side three-way valve are respectively connected with one carbon dioxide branch pipe and one cleaning branch pipe, each liquid outlet pipe is respectively connected with the inlet end of one corresponding air outlet side three-way valve, the two outlet ends of each air outlet side three-way valve are respectively connected with a corresponding gas analysis instrument and a corresponding cleaning liquid recovery pipe, the gas analysis instrument is connected with a gas product output pipe, the cleaning liquid recovery pipe is connected with a cleaning liquid recovery device, the liquid inlet pipe is connected with an electrolyte supply source and is provided with a liquid inlet switch valve, the liquid outlet pipe is externally outputs a liquid product and oxygen, the liquid switch valve is provided with a liquid switch valve, the two inlet ends of each gas outlet pipe are respectively connected with the corresponding three-way valve, the two outlet side three-way valve and the cleaning three-way valve are connected with the corresponding three-way valve, the cleaning three-way valve and the cleaning module is used for judging the state and the cleaning module to realize the cleaning state and the cleaning module.
In this embodiment, the electrolytic modules are two electrolytic modules, namely an electrolytic module one 8 and an electrolytic module two 9. Correspondingly, the three-way valve at the air inlet end is an electric control three-way valve I1 and an electric control three-way valve II 2 respectively, the three-way valve at the air outlet side is an electric control three-way valve III 3 and an electric control three-way valve IV 4 respectively, the power supply circuits of the two electrolysis modules are an electrolysis circuit I and an electrolysis circuit II correspondingly, and the two gas analysis instruments are a gas analysis instrument I5 and a gas analysis instrument II 6 respectively. The acid cleaning liquid supply source, the clear water supply source and the nitrogen gas source are respectively controlled by a cleaning liquid valve, a clear water valve and a nitrogen valve to control whether to open and supply flow, and the cleaning liquid valve, the clear water valve and the nitrogen valve are controlled by a control module. The liquid outlet pipes of the two electrolysis modules are connected in parallel to a liquid product main pipe, the liquid product main pipe is connected to the inlet of the gas-liquid separator 10, and the gas path outlet and the liquid path outlet of the gas-liquid separator 10 respectively output oxygen and liquid products outwards.
The electrolytic module is a bipolar electrolytic tank and comprises a plurality of electrolytic units 11, wherein the polar plates of the electrolytic module comprise bipolar plates 13, a cathode plate 12 and an anode plate 14 which are respectively arranged at two ends, the bipolar plates 13 are arranged between the cathode plate 12 and the anode plate 14, and the polar plates are connected to the power supply circuit in series; the working electrode 16, the insulating gasket 17, the alkaline ion exchange membrane 18, the insulating gasket 17 and the counter electrode 19 which are used as a cathode are sequentially arranged between the adjacent polar plates from the cathode side to the anode side, and the polar plates, the working electrode 16, the insulating gasket 17, the alkaline ion exchange membrane 18, the insulating gasket 17 and the counter electrode 19 at the two sides form an electrolytic unit 11.
The cathode runner 15 is arranged on the inner side of the cathode plate 12 and the side of the bipolar plate 13 facing the anode, the anode runner is arranged on the inner side of the anode plate 14 and the side of the bipolar plate 13 facing the cathode, the air inlet pipe comprises an air inlet main pipe and a plurality of air inlet branch pipes connected to the air inlet main pipe in parallel, the air outlet pipe comprises an air outlet main pipe and a plurality of air outlet branch pipes connected to the air outlet main pipe in parallel, the liquid inlet pipe comprises a liquid inlet main pipe and a plurality of liquid inlet branch pipes connected to the liquid inlet main pipe in parallel, and the liquid outlet pipe comprises a liquid outlet main pipe and a plurality of liquid outlet branch pipes connected to the liquid outlet main pipe in parallel. The inlet and outlet of each cathode runner 15 are respectively communicated with a corresponding air inlet branch pipe and a corresponding air outlet branch pipe, the liquid inlet switch valve is arranged on the liquid inlet main pipe, and the liquid outlet switch valve is arranged on the liquid outlet main pipe. The inlet and the outlet of each anode runner are respectively communicated with a corresponding liquid inlet branch pipe and a corresponding liquid outlet branch pipe, the air inlet main pipes of the two electrolysis modules are correspondingly connected to the first electric control three-way valve 1 and the second electric control three-way valve 2, the air outlet main pipes of the two electrolysis modules are correspondingly connected to the third electric control three-way valve 3 and the fourth electric control three-way valve 4, the liquid inlet main pipes are connected to an electrolyte supply source, and the liquid outlet main pipes are connected to a liquid product main pipe in parallel. In the above structure, each of the electrolytic cells 11 in the same electrolytic module is connected in parallel to the gas path structure and the liquid path structure of the electrolytic module, while each of the electrolytic cells 11 is connected in series to the power supply circuit of the electrolytic module.
The gas analysis instrument can adopt an infrared spectrometer or other detection devices capable of detecting the concentration of carbon monoxide and carbon dioxide in the gas product, analyzes and detects the gas components conveyed by the gas outlet pipe, and outputs the concentration of the carbon monoxide and the concentration of the carbon dioxide to the control module. The control module comprises a detection judging unit, a passage switching unit and a cleaning control unit, wherein the detection judging unit is used for receiving data output by the gas analysis instrument, calculating the concentration ratio of carbon monoxide to carbon dioxide, comparing the concentration ratio with a set threshold value, and judging that the electrolytic module corresponding to the corresponding gas analysis instrument needs to be converted into a cleaning state to clean salt precipitation in a cathode region when the concentration ratio is lower than the set ratio. The access switching unit is used for changing the gas path structure of the corresponding electrolytic module through the gas inlet side three-way valve and the gas outlet side three-way valve according to the judging result and the cleaning feedback signal, controlling the on-off of the power supply circuit of the corresponding electrolytic module and controlling the on-off of the liquid path structure of the corresponding electrolytic module through the liquid inlet switching valve and the liquid outlet switching valve, thereby realizing the switching of the corresponding electrolytic module in a working state and a cleaning state. The cleaning control unit is connected with and controls the cleaning liquid valve, the clear water valve, the nitrogen valve and the electric control four-way valve 7, and is used for sequentially opening and closing the cleaning liquid valve, the clear water valve and the nitrogen valve after the channel switching is completed, controlling the electric control four-way valve 7 to sequentially select the corresponding inlet end to be opened, realizing the effect of sequentially inputting acid cleaning liquid, clear water and nitrogen into the gas channel structure of the electrolysis module in the cleaning state, and sending a cleaning feedback signal to the channel switching module after the cleaning is completed.
The cleaning method of the device in the running process specifically comprises the following steps:
step one, collecting detection data. In the working process, the two electrolysis modules are in a working state, the electrolysis modules are electrified, the air inlet pipe inputs carbon dioxide from a carbon dioxide air source through the air inlet side three-way valve, the carbon dioxide enters the cathode flow channels 15 of the electrolysis units 11 to contact the working electrodes 16 and complete electrocatalytic reduction reaction under the action of a catalyst, the generated gas product flows out from the air outlet pipe, enters the corresponding gas analysis instrument through the air outlet side three-way valve and is discharged, the gas analysis instrument detects and obtains concentration data of carbon monoxide and carbon dioxide in the gas product output by the corresponding electrolysis module in the process, and the concentration data are transmitted to the detection and judgment unit.
And step two, judging whether each electrolytic module needs to be cleaned or not. And the concentration data received by the detection judging unit has a corresponding relation with the electrolytic modules, the concentration ratio of carbon monoxide to carbon dioxide output by each electrolytic module is calculated respectively, when the concentration ratio of carbon monoxide to carbon dioxide is lower than a set threshold value by 10%, the corresponding electrolytic modules are judged to need to be cleaned to wash salt crystals precipitated by reaction, the results are collected into a final judging result after the judgment of all the electrolytic modules is completed, and the final judging result is output to the passage switching unit, wherein the judging result comprises the numbers of all the electrolytic modules which need to be converted into a cleaning state. As in the present embodiment: only if the concentration data of the first gas analysis instrument 5 shows that the concentration ratio of carbon monoxide to carbon dioxide is lower than 10%, it is determined that the first electrolysis module 8 needs to be converted into a cleaning state.
In the step, a second judging step may be further provided, that is, after determining whether the number of the electrolytic modules to be cleaned is equal to the number of all the electrolytic modules after determining the judging result of whether each electrolytic module needs to be cleaned, if yes, the electrolytic module with the highest concentration ratio is selected to be temporarily not converted into the cleaning state, otherwise, all the electrolytic modules to be cleaned are converted into the cleaning state, and then the final judging result is output. Therefore, at least one electrolysis module in the whole carbon dioxide point catalytic device can work, and the whole system is prevented from being completely stopped, so that the stability of the whole system is prevented from being influenced.
And step three, switching control channels to convert the corresponding electrolytic modules from the working state to the cleaning state. The passage switching unit determines the electrolysis modules which need to be converted into the cleaning state according to the judging result, closes the inlet ends connected with the carbon dioxide gas source in the air inlet side three-way valves corresponding to the electrolysis modules, opens the inlet ends connected with the cleaning branch pipes, closes the outlet ends connected with the gas analysis instrument in the corresponding air outlet side three-way valves, opens the outlet ends connected with the cleaning liquid recovery pipe, and simultaneously closes the corresponding power supply circuit, the liquid inlet switch valve and the liquid outlet switch valve to stop the operation of the corresponding electrolysis modules. As in the present embodiment: the first electric control three-way valve 1 is switched to be communicated with the cleaning branch pipe to the air inlet pipe for inputting the acid cleaning liquid, the third electric control three-way valve 3 is switched to be communicated with the air outlet pipe to the cleaning liquid recovery pipe, and meanwhile the first electrolytic circuit, the first liquid inlet switch valve and the first liquid outlet switch valve are closed. The passage switching unit sends a signal to the cleaning control unit after the state transition is completed.
And step four, cleaning the cathode area corresponding to the electrolytic module. After receiving the signals of the passage switching unit, the cleaning control unit sequentially opens and correspondingly switches the communicating object at the inlet end of the electric control four-way valve 7 according to the sequence from the acid electrolyte supply source and the clean water supply source to the nitrogen gas source, sequentially inputs acid cleaning liquid, clean water and nitrogen gas to the electrolytic module to be cleaned to complete the cleaning step, and then sends a cleaning feedback signal to the passage switching unit.
The cleaning process specifically comprises the following steps: the electric control four-way valve 7 is switched to be communicated with an acid cleaning solution supply source and a cleaning main pipe, then a cleaning solution valve is opened to convey acid cleaning solution, which is usually weak acidic cleaning solution such as dilute hydrochloric acid or oxalic acid, to the cathode region of each electrolysis unit 11 in the electrolysis module to be cleaned, and the acid cleaning solution enters the cathode flow channel 15 and contacts the working electrode 16, is dissolved by salt crystallization reaction on the surfaces of the two materials, is discharged from the exhaust pipe, and enters the cleaning solution recovery device through a cleaning solution recovery pipe. After the set first time, the cleaning control unit switches the electric control four-way valve 7 to be communicated with the clean water supply source and the cleaning main pipe, simultaneously closes the cleaning liquid valve and opens the clean water valve, and clean water is input into each cathode area to flush the residual acid cleaning liquid in the cathode area to the cleaning liquid recovery device. Then after a set second time, the cleaning control unit switches the electric control four-way valve 7 to be communicated with a nitrogen gas source and a cleaning main pipe, simultaneously closes a clean water valve and opens the nitrogen valve to continuously convey nitrogen to the cathode region, clean water remained in the cathode region after the previous cleaning is air-dried by the nitrogen, the nitrogen can not influence a catalyst or electrolyte, and the nitrogen containing water vapor is finally discharged from the cleaning liquid recovery device. And finally, after the set third time, the cleaning control unit closes the nitrogen valve and sends a cleaning feedback signal to the passage switching unit to indicate that the cleaning is completed.
The cleaning solution valve, the clean water valve and the nitrogen valve adopt a switch valve and/or a flow regulating valve, as in the embodiment: because only one electrolysis module is cleaned in the cleaning state to ensure that the whole system continuously reduces carbon dioxide, the electrolysis module cleaned each time is one, and the cleaning liquid valve, the clear water valve and the nitrogen valve all adopt switch valves. In other embodiments, if there are more than two electrolytic modules, the number of electrolytic modules in the cleaning state may vary from one to a plurality, and the flow rate of each substance provided in the cleaning manifold may also be adaptively varied in order to ensure the cleaning effect on each cleaning module within the same time threshold. For the embodiments, the cleaning liquid valve, the clean water valve and the nitrogen valve are all flow regulating valves capable of regulating flow, and after the cleaning control unit is started, the opening degree of each flow regulating valve is regulated according to the number of the electrolysis modules to be cleaned to control the flow of cleaning liquid, clean water and nitrogen so as to meet the cleaning requirement in the set time.
And fifthly, switching control channels to switch the corresponding electrolytic modules from the cleaning state to the working state. After receiving the cleaning feedback signal, the channel switching module controls the air inlet side three-way valve which is opened by the inlet end of the connecting cleaning branch pipe, closes the inlet end of the connecting cleaning branch pipe and opens the inlet end of the connecting carbon dioxide air source, simultaneously opens the outlet end of the connecting gas analysis instrument in the corresponding air outlet side three-way valve and closes the outlet end of the connecting cleaning liquid recovery pipe, then opens the corresponding power supply circuit, the liquid inlet switching valve and the liquid outlet switching valve, and reverts the operation of the corresponding electrolysis module to convert the operation into the working state. As in the present embodiment: the first electronic control three-way valve 1 is switched to communicate a carbon dioxide gas source to the gas inlet pipe for inputting carbon dioxide, the third electronic control three-way valve 3 is switched to communicate the gas outlet pipe to the first gas analysis instrument 5, and the first electrolytic circuit, the first liquid inlet switch valve and the first liquid outlet switch valve are simultaneously opened. The flow of cleaning the electrolytic module and recovering the work is finished.
While the invention has been described above with reference to the accompanying drawings, it will be apparent that the invention is not limited to the above embodiments, but is capable of being modified or applied to other applications without modification, as long as various insubstantial modifications of the inventive concept and technical solutions are adopted, all within the scope of the invention.
Claims (7)
1. The utility model provides a carbon dioxide electrocatalytic arrangement with self-cleaning function which characterized in that: the device comprises a control module, a cleaning module, a detection module and at least two electrolysis modules, wherein the air inlet end of an air path structure of each electrolysis module is respectively connected with a carbon dioxide air source and the cleaning module through an air inlet side three-way valve, the air outlet end of the air path structure is respectively connected with the detection module and a cleaning liquid recovery device through an air outlet side three-way valve, and the two ends of a liquid path structure of each electrolysis module are respectively connected with an electrolyte supply source and a pipeline for outputting liquid products; the cleaning module comprises an acid cleaning liquid supply source, a clear water supply source, a nitrogen gas source and an electric control four-way valve (7), the detection module comprises a gas analysis instrument corresponding to the first electrolytic module (8), the acid cleaning liquid supply source, the clear water supply source and the nitrogen gas source are respectively connected to three inlet ends of the electric control four-way valve (7), the gas path structure of each electrolytic module is connected in parallel to the outlet of the electric control four-way valve (7), the control module is used for receiving detection data of each gas analysis instrument and judging whether each electrolytic module is cleaned, the air inlet side three-way valve and the air outlet side three-way valve are controlled according to the judging result and a cleaning feedback signal to realize conversion between the corresponding electrolytic module in a working state and a cleaning state, and the cleaning module is controlled to complete the cleaning process in the cleaning state;
each electrolysis module comprises an electrolysis unit (11) adopting a GDE technology, an air inlet pipe, an air outlet pipe, a liquid inlet pipe, a liquid outlet pipe and a corresponding power supply circuit, the outlet end of the electric control four-way valve (7) is connected with a cleaning main pipe, a plurality of cleaning branch pipes are connected in parallel to the outlet of the cleaning main pipe, the air inlet pipe of each electrolysis module is correspondingly connected with the outlet end of one air inlet side three-way valve, a plurality of carbon dioxide branch pipes are connected with a carbon dioxide gas source in parallel, the carbon dioxide branch pipes and the cleaning branch pipes are in one-to-one correspondence, the two inlet ends of each air inlet side three-way valve are respectively connected with one carbon dioxide branch pipe and one cleaning branch pipe, each liquid outlet pipe is respectively connected with the inlet end of one corresponding air outlet side three-way valve, the two outlet ends of each air outlet side three-way valve are respectively connected with a corresponding gas analysis instrument and a corresponding cleaning liquid recovery pipe, the gas analysis instrument is connected with a gas product output pipe, the cleaning liquid recovery pipe is connected with a cleaning liquid recovery device, the liquid inlet pipe is connected with an electrolyte supply source and is provided with a liquid inlet switch valve, and the liquid outlet pipe is externally output a liquid product and oxygen and is provided with a liquid switch valve.
2. The carbon dioxide electrocatalytic device with self cleaning function of claim 1, wherein: the control module comprises a detection judging unit, a passage switching unit and a cleaning control unit,
the detection judging unit is used for receiving data output by the gas analysis instrument, calculating the concentration ratio of carbon monoxide to carbon dioxide, comparing the concentration ratio with a set threshold value, judging that the corresponding electrolytic module of the corresponding gas analysis instrument needs to be converted into a cleaning state when the concentration ratio is lower than the set ratio, and outputting a judging result;
the passage switching unit is used for changing the air passage structure of the corresponding electrolytic module through the air inlet side three-way valve and the air outlet side three-way valve according to the judging result and the cleaning feedback signal, controlling the on-off of a power supply circuit of the corresponding electrolytic module, and controlling the on-off of the liquid passage structure of the corresponding electrolytic module through the liquid inlet switch valve and the liquid outlet switch valve, so that the corresponding electrolytic module is switched between a working state and a cleaning state;
the cleaning control unit is used for sequentially opening and closing a cleaning liquid valve, a clear water valve and a nitrogen valve after the channel switching is finished, controlling the electric control four-way valve (7) to sequentially select the corresponding inlet end to be opened, realizing the effect of sequentially inputting acid cleaning liquid, clear water and nitrogen into the gas channel structure of the electrolysis module in the cleaning state, and sending a cleaning feedback signal to the channel switching module after the cleaning is finished.
3. The carbon dioxide electrocatalytic device with self cleaning function of claim 1, wherein: the electrolytic module is a bipolar electrolytic tank and comprises a plurality of electrolytic units (11), each electrolytic unit (11) in the same electrolytic module is connected in parallel to the gas path structure and the liquid path structure of the electrolytic module, and each electrolytic unit (11) is connected in series to the power supply circuit of the electrolytic module.
4. The carbon dioxide electrocatalytic device with self cleaning function of claim 1, wherein: the acid cleaning liquid supply source, the clear water supply source and the nitrogen gas source are respectively and correspondingly provided with a cleaning liquid valve, a clear water valve and a nitrogen valve, the cleaning liquid valve, the clear water valve and the nitrogen valve adopt a switch valve and/or a flow regulating valve, and the cleaning liquid valve, the clear water valve and the nitrogen valve are controlled by a control module.
5. The carbon dioxide electrocatalytic device with self cleaning function of claim 1, wherein: the liquid outlet pipes of the two electrolysis modules are connected in parallel to a liquid product main pipe, the liquid product main pipe is connected to the inlet of a gas-liquid separator (10), and the gas path outlet and the liquid path outlet of the gas-liquid separator (10) respectively output oxygen and liquid products outwards.
6. A carbon dioxide electrocatalytic device with self cleaning function according to claim 3, wherein: the cleaning method of the carbon dioxide electrocatalytic device in the operation process comprises the following steps:
firstly, collecting detection data, detecting and obtaining concentration data of carbon monoxide and carbon dioxide in a gas product output by a corresponding electrolysis module by a gas analysis instrument, and conveying the concentration data to a detection judging unit;
judging whether each electrolysis module needs to be cleaned or not, respectively calculating the concentration ratio of carbon monoxide to carbon dioxide output by each electrolysis module according to the concentration data received by the detection judging unit, judging that the corresponding electrolysis module needs to be cleaned when the concentration ratio of carbon monoxide to carbon dioxide is lower than a set threshold value, and collecting the results into a final judging result after the judgment of all the electrolysis modules is completed and outputting the final judging result to the channel switching unit;
step three, switching the control passage to switch the corresponding electrolytic module from the working state to the cleaning state, determining the electrolytic module to be switched to the cleaning state by the passage switching unit according to the determination result, opening the passages of the corresponding electrolytic module connected to the cleaning module and the cleaning liquid recovery device, closing the passages from the corresponding electrolytic module to a carbon dioxide gas source and a gas analysis instrument, closing the corresponding power supply circuit, a liquid inlet switch valve and a liquid outlet switch valve, stopping the operation of the corresponding electrolytic module, and outputting a signal to the cleaning control unit;
step four, cleaning the cathode region of the corresponding electrolytic module, after receiving the signals of the passage switching unit, the cleaning control unit sequentially opens and correspondingly switches the communication object at the inlet end of the electric control four-way valve (7) according to the sequence from the acid electrolyte supply source and the clean water supply source to the nitrogen gas source, sequentially inputs acid cleaning liquid, clean water and nitrogen gas into the electrolytic module to be cleaned to complete the cleaning step, and then sends a cleaning feedback signal to the passage switching unit;
step five, switching control channels to convert the corresponding electrolytic modules from a cleaning state to a working state; the passage switching unit is used for closing the passages of the cleaning module and the cleaning liquid recovery device according to the cleaning feedback signal, opening the passages from the corresponding electrolytic module to the carbon dioxide gas source and the gas analysis instrument, and simultaneously opening the corresponding power supply circuit, the corresponding liquid inlet switch valve and the corresponding liquid outlet switch valve, so that the flow is ended.
7. The carbon dioxide electrocatalytic device with self cleaning function of claim 6, wherein: and the second judging step is also included, after judging whether each electrolytic module needs to be cleaned or not, judging whether the number of the electrolytic modules needing to be cleaned is equal to the number of all the electrolytic modules, if yes, selecting the electrolytic module with the highest concentration ratio to be temporarily not converted into a cleaning state, otherwise, converting all the electrolytic modules needing to be cleaned into the cleaning state, and outputting a final judging result according to the judging result.
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| CN110420926A (en) * | 2019-08-16 | 2019-11-08 | 蒋书印 | A kind of multifunctional circulation cleaning system |
| CN112593258A (en) * | 2019-09-17 | 2021-04-02 | 株式会社东芝 | Carbon dioxide electrolysis device and carbon dioxide electrolysis method |
| CN213570777U (en) * | 2020-11-02 | 2021-06-29 | 绍兴橙氧科技有限公司 | Automatic cleaning and purging system for electrolytic cell complete equipment |
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| CN110420926A (en) * | 2019-08-16 | 2019-11-08 | 蒋书印 | A kind of multifunctional circulation cleaning system |
| CN112593258A (en) * | 2019-09-17 | 2021-04-02 | 株式会社东芝 | Carbon dioxide electrolysis device and carbon dioxide electrolysis method |
| CN213570777U (en) * | 2020-11-02 | 2021-06-29 | 绍兴橙氧科技有限公司 | Automatic cleaning and purging system for electrolytic cell complete equipment |
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Effective date of registration: 20230920 Address after: 241000 Floor 16-18, Building 5, Science and Technology Industrial Park, Hi-tech Industrial Development Zone, Yijiang District, Wuhu City, Anhui Province Patentee after: Three Carbon (Anhui) Science and Technology Research Institute Co.,Ltd. Patentee after: NANKAI University Address before: 241000 Floor 16-18, Building 5, Science and Technology Industrial Park, Hi-tech Industrial Development Zone, Yijiang District, Wuhu City, Anhui Province Patentee before: Three Carbon (Anhui) Science and Technology Research Institute Co.,Ltd. |