CN216698450U - Impurity purification device of hydrogen for fuel cell - Google Patents
Impurity purification device of hydrogen for fuel cell Download PDFInfo
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- CN216698450U CN216698450U CN202220323379.XU CN202220323379U CN216698450U CN 216698450 U CN216698450 U CN 216698450U CN 202220323379 U CN202220323379 U CN 202220323379U CN 216698450 U CN216698450 U CN 216698450U
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
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Abstract
The utility model provides an impurity purification device of hydrogen for a fuel cell, belongs to the technical field of fuel cells, and solves the problems that the existing purification device is complex in process, various in equipment, not beneficial to portable movement and high in adsorption control difficulty. The device comprises a solid-state electrochemical reactor and a controller, wherein the controller is used for controlling the working temperature of the solid-state electrochemical reactor, the humidity and the pressure of hydrogen to be purified and the anode voltage as the oxidation-reduction potential of impurities; wherein the solid-state electrochemical reactor further comprises an anode electrode layer, an electrolyte layer, a cathode electrode layer, and a reference electrode; the anode electrode layer is provided with a hydrogen inlet to be purified and a purified hydrogen outlet; the cathode electrode layer is provided with an air inlet and an air outlet; the electrolyte layer is arranged between the anode electrode layer and the cathode electrode layer; the reference electrode is arranged in the electrolyte layer; the anode electrode layer and the cathode electrode layer are connected through an external lead. The device utilizes the electrochemical principle to carry out hydrogen on-line purification, and can be applied to a fuel cell system.
Description
Technical Field
The utility model relates to the technical field of fuel cells, in particular to an impurity purification device of hydrogen for a fuel cell.
Background
Fuel cell engines use hydrogen as a fuel to convert chemical energy into electrical energy through an electrochemical reaction. Since the electrode kinetics are slow, it is desirable to accelerate the reaction by a catalyst, such as platinum metal. At present, the source of hydrogen is mainly industrial by-product hydrogen, such as reforming hydrogen production, a gas source often contains CO impurities, and trace CO can cause catalyst poisoning and reduce the performance of a fuel cell engine. The concentration of carbon monoxide should not be higher than 0.2 ppm in the hydrogen purity requirement specified by the international organization for standardization hydrogen energy technology committee.
Among the most widely used existing hydrogen purification methods, the Pressure Swing Adsorption (PSA) method is used. PSA is based on the physical adsorption of the inside surface of the adsorbent to gas molecules, utilize the adsorbent easily to adsorb high boiling point component under the same pressure, be difficult for adsorbing low boiling point component and be increased by the component adsorption capacity of adsorbing under the high pressure, the separation of impurity is realized to the characteristic that the adsorption capacity reduces under the low pressure, the energy consumption is low, the regeneration rate is fast, but its process is more and complicated, equipment is various, the area occupied is big, be unfavorable for portable removal, the absorption relates to a plurality of valves and reaction tower with the desorption process, the accurate control degree of difficulty is great, limited its practical scene.
SUMMERY OF THE UTILITY MODEL
In view of the above analysis, an embodiment of the present invention is directed to provide an impurity purification apparatus for hydrogen gas for a fuel cell, so as to solve the problems of complicated process, various devices, inconvenience for portable movement, and difficulty in adsorption control of the conventional purification apparatus.
In one aspect, an embodiment of the present invention provides an apparatus for purifying impurities in hydrogen for a fuel cell, including a solid-state electrochemical reactor and a controller configured to control an operating temperature of the solid-state electrochemical reactor, a humidity and a pressure of hydrogen to be purified, and an anode voltage as an oxidation-reduction potential of the impurities; wherein the content of the first and second substances,
the solid-state electrochemical reactor further comprises an anode electrode layer (4), an electrolyte layer (6), a cathode electrode layer (5) and a reference electrode (3); the anode electrode layer (4) is provided with a hydrogen inlet to be purified and a purified hydrogen outlet; the cathode electrode layer (5) is provided with an air inlet and an air outlet; the electrolyte layer (6) is arranged between the anode electrode layer (4) and the cathode electrode layer (5); the reference electrode is arranged in the electrolyte layer (6); the anode electrode layer (4) and the cathode electrode layer (5) are connected through an external lead;
the output end of the controller is respectively connected with the anode electrode layer (4) and the hydrogen inlet and the air inlet of the solid-state electrochemical reactor to be purified.
The beneficial effects of the above technical scheme are as follows: provides a novel hydrogen impurity purification device, which utilizes the difference of different gas oxidation-reduction potentials of different components to apply a specific potential to oxidize impurity gas into other components with small influence on a fuel cell, such as CO oxidation into CO2The gas is converted into solid, thereby achieving the purpose of purification. The device has small volume and simple control, and is suitable for removing gas impurities on line by the vehicle fuel cell. After the reference electrode is added, the potential can be accurately controlled.
Based on the further improvement of the device, for CO impurities, the working temperature of the solid electrochemical reactor is 50-80 ℃, the gas temperature of the hydrogen inlet to be purified and the gas temperature of the air inlet are 0-40 ℃, the gas pressure is 100-250 kPa, and the gas humidity is 20-100% RH.
Further, the catalyst of the anode electrode layer (4) is a composite of metal oxide and platinum;
the catalyst of the cathode electrode layer (5) comprises platinum or a platinum alloy.
Further, the controller further includes: the device comprises a potentiostat (1) for controlling the potential of an anode electrode layer (4) at a CO oxidation potential, an environment temperature controller for controlling the working temperature of a solid-state electrochemical reactor at 50-80 ℃, a gas temperature controller for controlling the gas temperature of a hydrogen inlet to be purified and an air inlet at 0-40 ℃, a gas humidity controller for controlling the gas humidity of the hydrogen inlet to be purified and the air inlet at 20-100% RH, and a gas pressure controller for controlling the gas pressure of the hydrogen inlet to be purified and the air inlet at 100-250 kPa.
Further, the impurity purification device also comprises a pressure reducing valve (11); wherein the content of the first and second substances,
the output end of the pressure reducing valve (11) is connected with a hydrogen inlet to be purified of the solid-state electrochemical reactor, and the control end of the pressure reducing valve is connected with the output end of the controller.
Further, the impurity purification device also comprises a current sensor (2); wherein the content of the first and second substances,
the input end of the current sensor (2) is electrically connected with the anode electrode layer (4), and the output end of the current sensor is electrically connected with the cathode electrode layer (5).
Further, the impurity purification device also comprises an air compressor (7); and the number of the first and second electrodes,
the output end of the air compressor (7) is connected with the air inlet of the solid-state electrochemical reactor, and the control end of the air compressor is connected with the output end of the controller.
Further, the impurity purification device also comprises a three-way valve (8); wherein the content of the first and second substances,
the input end of the three-way valve (8) is connected with the output end of the air compressor (7), the first output end of the three-way valve is connected with the air inlet of the solid-state electrochemical reactor, and the second output end of the three-way valve is connected with the air inlet of the external hydrogen fuel cell.
Further, the impurity purification device also comprises a tail discharge valve (9); wherein the content of the first and second substances,
the input end of the tail exhaust valve (9) is connected with the air outlet of the solid-state electrochemical reactor, and the output end of the tail exhaust valve is connected with an air tail exhaust pipeline of an external hydrogen fuel cell.
Compared with the prior art, the utility model can realize at least one of the following beneficial effects:
1. the catalyst can purify trace carbon monoxide in hydrogen, avoid poisoning the fuel cell catalyst, reduce the requirement on the hydrogen purity, enlarge the hydrogen source of the fuel cell, improve the power generation efficiency of the fuel cell and prolong the service life.
2. The device has the advantages of small volume, high efficiency and simple device, can be used for on-line purification on a fuel cell automobile and can be applied as a mobile purification device.
3. The equipment is simple, and the adaptation condition is wide in range, utilizes the potentiostat to carry out accurate control to the anode potential, and the purification effect that prevents that the potential deviation from leading to is low, can tolerate temperature and humidity on a relatively large scale, and is lower to the requirement of control.
The following detailed description is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. The summary is not intended to identify key features or essential features of the disclosure, nor is it intended to limit the scope of the disclosure.
Drawings
The foregoing and other objects, features and advantages of the disclosure will be apparent from the following more particular descriptions of exemplary embodiments of the disclosure as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the disclosure.
FIG. 1 is a schematic view showing the composition of an impurity removing device for hydrogen gas for a fuel cell in accordance with example 1;
FIG. 2 is a schematic view showing the structure of an impurity removing device for hydrogen gas for a fuel cell in accordance with example 2;
fig. 3 is a schematic view showing the structure of a hydrogen gas impurity purification apparatus for a fuel cell in accordance with example 2.
Reference numerals:
1-potentiostat; 2-a current sensor; 3-a reference electrode; 4-an anode electrode layer; 5-a cathode electrode layer; 6-an electrolyte layer; 7, an air compressor; 8-three-way valve; 9-tail exhaust valve; 10-hydrogen spraying equipment; 11-pressure reducing valve.
Detailed Description
Embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The term "include" and variations thereof as used herein is meant to be inclusive in an open-ended manner, i.e., "including but not limited to". Unless specifically stated otherwise, the term "or" means "and/or". The term "based on" means "based at least in part on". The terms "one example embodiment" and "one embodiment" mean "at least one example embodiment". The term "another embodiment" means "at least one additional embodiment". The terms "first," "second," and the like may refer to different or the same object. Other explicit and implicit definitions are also possible below.
Example 1
In one embodiment of the present invention, an apparatus for purifying impurities in hydrogen gas for a fuel cell is disclosed, comprising a solid-state electrochemical reactor and a controller.
Wherein, as shown in fig. 1, the solid-state electrochemical reactor further comprises an anode electrode layer 4, an electrolyte layer 6, a cathode electrode layer 5, and a reference electrode 3; the anode electrode layer 4 is provided with a hydrogen inlet to be purified and a purified hydrogen outlet; the cathode electrode layer 5 is provided with an air inlet and an air outlet; the electrolyte layer 6 is arranged between the anode electrode layer 4 and the cathode electrode layer 5; the reference electrode 3 is disposed within the electrolyte layer 6; the anode electrode layer 4 and the cathode electrode layer 5 are connected by an external lead.
The output end of the controller is respectively connected with the anode electrode layer 4, and the hydrogen inlet and the air inlet of the solid-state electrochemical reactor to be purified.
And the controller is used for controlling the working temperature (comprising the ambient temperature and the electrolyte temperature) of the solid-state electrochemical reactor, the electrode voltage (the voltage of the anode electrode layer 4 is the oxidation-reduction potential of impurities, and the voltages of the cathode electrode layer 5 and the reference electrode 3 are not required), the gas humidity and the pressure (an inlet of hydrogen to be purified).
When the method is implemented, the gas impurities in the hydrogen to be purified are oxidized into other gases, liquids or solids with small toxic action by the electrochemical principle. The liquid and the solid can be adsorbed in the solid electrochemical reactor and discharged after use, and the gas has small toxic action on the fuel cell and can be input to the galvanic pile of the fuel cell through the purified hydrogen outlet.
Illustratively, the CO in the purified hydrogen can be oxidized to less toxic CO2The phenomenon of catalyst poisoning of the fuel cell caused by CO is avoided, and the service life of the fuel cell is prolonged. The involved electrochemical principles are as follows:
anode: CO + H2O→CO2+2H++2e-
Cathode: o is2+2H++2e-→H2O
CO impurity loses electrons at the anode to generate CO2And protons, which are transferred to the cathode through the electrolyte, undergo a reduction reaction with oxygen in the air to produce water, and in this process, the potential of the anode electrode layer 4 needs to be controlled to the oxidation potential of CO to prevent the hydrogen gas from reacting.
If a two-electrode system is adopted, the anode potential cannot be accurately measured due to the polarization phenomenon in the reaction process, so that the potential can be accurately controlled by adopting a three-electrode system and adding a reference electrode. Experiments prove that the CO impurities with the concentration within 100ppm can be removed by controlling the anode potential (the potential of the anode electrode layer 4) to be 0.85V.
Compared with the prior art, this embodiment provides a novel hydrogen impurity purification device, through the electrochemistry principle, utilizes the different difference of the gas redox potential of different compositions, exerts specific potential and oxidizes impurity gas to other compositions that have little influence on fuel cell, for example CO oxidizes to CO2The gas is converted into liquid or solid, so that the purpose of purification is achieved. The device has small volume and simple control, and is suitable for removing gas impurities on line by the vehicle fuel cell. After the reference electrode is added, the potential can be accurately controlled.
Example 2
The method is improved on the basis of the embodiment 1, for CO impurities, the working temperature of the solid-state electrochemical reactor is 50-80 ℃, the gas temperature of a hydrogen inlet to be purified and the gas temperature of an air inlet are 0-40 ℃, the gas pressure is 100-250 kPa, and the gas humidity is 20-100% RH.
Preferably, the anode electrode layer 4 and the cathode electrode layer 5 both adopt a porous carbon structure with a catalyst distributed on the surface. Specifically, a porous electrode capable of transporting gas and protons is constructed using porous carbon having a catalyst distributed on the surface thereof as a base material, a proton-conductive ionomer as a binder, and carbon fibers as a skeleton.
Preferably, the catalyst of the anode electrode layer 4 is a composite of metal oxide and platinum, which can improve the selectivity of the catalyst to CO. Illustratively, the metal oxide may employ titanium oxide (TiO).
Preferably, the catalyst of the cathode electrode layer 5 is platinum or a platinum alloy or the like.
Preferably, the controller further comprises: the device comprises a potentiostat 1 for controlling the potential of an anode electrode layer 4 at a CO oxidation potential (about 0.85V), an environment temperature controller for controlling the working temperature of a solid-state electrochemical reactor at 50-80 ℃, a gas temperature controller for controlling the gas temperature of a hydrogen inlet to be purified and an air inlet at 0-40 ℃, a gas humidity controller for controlling the gas humidity of the hydrogen inlet to be purified and the air inlet at 20-100% RH, and a gas pressure controller for controlling the gas pressure of the hydrogen inlet to be purified and the air inlet at 100-250 kPa.
Preferably, the impurity purification apparatus further includes a pressure reducing valve 11. Wherein, the output end of the pressure reducing valve 11 is connected with the hydrogen inlet to be purified of the solid-state electrochemical reactor, and the control end is connected with the output end of the controller.
Preferably, the impurity purification apparatus further includes a current sensor, as shown in fig. 2. The input end of the current sensor is electrically connected with the anode electrode layer 4, and the output end of the current sensor is electrically connected with the cathode electrode layer 5. A current sensor can be used to monitor the CO concentration, with the higher the CO concentration, the greater the current developed.
Preferably, the impurity purification apparatus further includes an air compressor 7. Wherein, the output of air compressor 7 is connected with the air inlet of solid-state electrochemical reactor, and the control end is connected with the output of controller.
Preferably, the impurity purification apparatus further includes a three-way valve 8. Wherein, the input end of the three-way valve 8 is connected with the output end of the air compressor 7, the first output end thereof is connected with the air inlet of the solid-state electrochemical reactor, and the second output end thereof is connected with the air inlet of the external hydrogen fuel cell.
Preferably, the impurity purification apparatus further includes a tail gate valve 9. Wherein, the input end of the tail valve 9 is connected with the air outlet of the solid-state electrochemical reactor, and the output end thereof is connected with the air tail pipe of the external hydrogen fuel cell.
In operation, as shown in FIG. 2, hydrogen containing CO impurity enters into anode electrode layer 4 of impurity purification device, air enters into cathode electrode layer 5 of impurity purification device, anode potential is controlled at 0.85V by potentiostat 1, and CO is oxidized into CO in anode electrode layer 42And H+And generates electrons, which are transferred to the cathode electrode layer 5, H, through an external circuit and the current sensor 2+The electrolyte is transferred to the cathode electrode layer 5, and reacts with oxygen in the air in the cathode electrode layer 5 to generate water. After the reaction, CO in the hydrogen gas is oxidized into CO at the anode electrode layer 42The purified hydrogen is discharged from the outlet (anode outlet), and the trace amount of CO2 has no influence on the performance of the hydrogen fuel cell and can be directly used as fuel.
The structure is shown in figure 3, hydrogen containing CO impurities enters an anode electrode layer 4 of the impurity purification device through a pressure reducing valve 11, air passes through an air compressor 7 and is subjected to flow distribution through a three-way valve 8, most of the air enters a hydrogen fuel cell stack, a small part of the air is separated to enter a cathode electrode layer 5 of the impurity purification device, the anode potential is controlled to be 0.85V through a potentiostat 1, and CO is oxidized into CO in the anode electrode layer 42And H+And generates electrons, which are transferred to the cathode electrode layer 5, H, through an external circuit and the current sensor 2+The electrolyte is transferred to the cathode electrode layer 5, and reacts with oxygen in the air in the cathode electrode layer 5 to generate water. After the reaction, CO in the hydrogen gas is oxidized into CO at the anode electrode layer 42The hydrogen gas from which CO is removed enters the hydrogen injection device 10 of the fuel cell system, and the trace amount of CO2 has no influence on the performance of the hydrogen fuel cell and can be directly used as fuel.
Compared with embodiment 1, the impurity purification device provided by the embodiment has the following effects:
1. the catalyst can purify trace carbon monoxide in hydrogen, avoid poisoning the fuel cell catalyst, reduce the requirement on the hydrogen purity, enlarge the hydrogen source of the fuel cell, improve the power generation efficiency of the fuel cell and prolong the service life.
2. The device has the advantages of small volume, high efficiency and simple device, can be used for on-line purification on a fuel cell automobile and can be applied as a mobile purification device.
3. The equipment is simple, and the adaptation condition is wide in range, utilizes the potentiostat to carry out accurate control to the anode potential, and the purification effect that prevents that the potential deviation from leading to is low, can tolerate temperature and humidity on a relatively large scale, and is lower to the requirement of control.
The foregoing description of the embodiments of the present disclosure has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles of the embodiments, the practical application, or improvements made to the prior art, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. An impurity purification device of hydrogen for a fuel cell is characterized by comprising a solid-state electrochemical reactor and a controller, wherein the controller is used for controlling the working temperature of the solid-state electrochemical reactor, the humidity and the pressure of hydrogen to be purified and the anode voltage to be the oxidation-reduction potential of impurities; wherein the content of the first and second substances,
the solid-state electrochemical reactor further comprises an anode electrode layer (4), an electrolyte layer (6), a cathode electrode layer (5) and a reference electrode (3); the anode electrode layer (4) is provided with a hydrogen inlet to be purified and a purified hydrogen outlet; the cathode electrode layer (5) is provided with an air inlet and an air outlet; the electrolyte layer (6) is arranged between the anode electrode layer (4) and the cathode electrode layer (5); the reference electrode (3) is arranged in the electrolyte layer (6); the anode electrode layer (4) and the cathode electrode layer (5) are connected through an external lead;
the output end of the controller is respectively connected with the anode electrode layer (4) and the hydrogen inlet and the air inlet of the solid-state electrochemical reactor to be purified.
2. The impurity purification device of hydrogen for a fuel cell according to claim 1, wherein for CO impurities, the operating temperature of the solid-state electrochemical reactor is 50 to 80 ℃, the gas temperature of the inlet of hydrogen to be purified and the gas temperature of the air inlet are 0 to 40 ℃, the gas pressure is 100 to 250 kPa, and the gas humidity is 20 to 100% RH.
3. The apparatus for purifying impurities in hydrogen gas for a fuel cell according to claim 1 or 2, wherein the anode electrode layer (4) and the cathode electrode layer (5) each have a porous carbon structure with a catalyst distributed on the surface thereof.
4. An impurity removal device for hydrogen gas for a fuel cell according to claim 3, wherein the catalyst of the anode electrode layer (4) is a composite of a metal oxide and platinum;
the catalyst of the cathode electrode layer (5) comprises platinum or a platinum alloy.
5. An impurity purification apparatus of hydrogen gas for a fuel cell according to claim 4, wherein said controller further comprises: the device comprises a potentiostat (1) for controlling the potential of an anode electrode layer (4) at a CO oxidation potential, an environment temperature controller for controlling the working temperature of a solid-state electrochemical reactor at 50-80 ℃, a gas temperature controller for controlling the gas temperature of a hydrogen inlet to be purified and an air inlet at 0-40 ℃, a gas humidity controller for controlling the gas humidity of the hydrogen inlet to be purified and the air inlet at 20-100% RH, and a gas pressure controller for controlling the gas pressure of the hydrogen inlet to be purified and the air inlet at 100-250 kPa.
6. An impurity purification apparatus of hydrogen gas for a fuel cell according to claim 5, further comprising a pressure reducing valve (11); wherein the content of the first and second substances,
the output end of the pressure reducing valve (11) is connected with a hydrogen inlet to be purified of the solid-state electrochemical reactor, and the control end of the pressure reducing valve is connected with the output end of the controller.
7. An impurity purification apparatus of hydrogen gas for fuel cells according to any one of claims 1 to 2 and 4 to 6, further comprising a current sensor (2); wherein the content of the first and second substances,
the input end of the current sensor (2) is electrically connected with the anode electrode layer (4), and the output end of the current sensor is electrically connected with the cathode electrode layer (5).
8. An impurity purifying device for hydrogen gas for a fuel cell according to any one of claims 1 to 2 and 4 to 6, further comprising an air compressor (7); and the number of the first and second electrodes,
the output end of the air compressor (7) is connected with the air inlet of the solid-state electrochemical reactor, and the control end of the air compressor is connected with the output end of the controller.
9. An impurity purification apparatus of hydrogen gas for a fuel cell according to claim 8, further comprising a three-way valve (8); wherein the content of the first and second substances,
the input end of the three-way valve (8) is connected with the output end of the air compressor (7), the first output end of the three-way valve is connected with the air inlet of the solid-state electrochemical reactor, and the second output end of the three-way valve is connected with the air inlet of the external hydrogen fuel cell.
10. An impurity purifying device for hydrogen gas for a fuel cell according to any one of claims 1 to 2, 4 to 6, and 9, further comprising a tail valve (9); wherein the content of the first and second substances,
the input end of the tail exhaust valve (9) is connected with the air outlet of the solid-state electrochemical reactor, and the output end of the tail exhaust valve is connected with an air tail exhaust pipeline of an external hydrogen fuel cell.
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| CN114464851A (en) * | 2022-02-17 | 2022-05-10 | 北京亿华通科技股份有限公司 | Hydrogen purification device for fuel cell engine |
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| CN114464851A (en) * | 2022-02-17 | 2022-05-10 | 北京亿华通科技股份有限公司 | Hydrogen purification device for fuel cell engine |
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