Electrochemical equipment for purifying hydrogen in hydrogen-rich gas

Abstract

The invention discloses electrochemical equipment for purifying hydrogen in hydrogen-rich gas, and aims to provide electrochemical equipment capable of reducing CO adsorption capacity of the surface of a catalyst in the electrochemical hydrogen purification equipment so as to improve poisoning resistance of the catalyst, so that CO poisoning of the catalyst is effectively solved; and the electrochemical equipment for purifying the hydrogen in the hydrogen-rich gas is used for solving the problem of failure of the purification equipment. The electrochemical purification device comprises a whole gas inlet and a pure hydrogen outlet, an oil path channel is arranged in the purification device, one end of the oil path channel is an oil path inlet, and the other end of the oil path channel is an oil path outlet; the heat exchanger comprises a whole gas inlet, a whole gas outlet, an oil inlet and an oil outlet, and the whole gas outlet is connected with the whole gas inlet through a connecting pipeline; the oil way pipeline comprises an oil supply pipeline connecting the oil way inlet and the oil liquid outlet and an oil return pipeline connecting the oil way outlet and the oil liquid inlet, and a pump, a heater and a temperature sensor are arranged on the oil way pipeline.

Description

Technical Field

[0001] This invention relates to the field of hydrogen purification technology, and more specifically to an electrochemical device for purifying hydrogen from hydrogen-rich gas. Background Technology

[0002] With the increasing global demand for clean energy, hydrogen energy has gained popularity worldwide. Hydrogen energy has a wide range of sources, currently obtainable through methods such as natural gas production, coal production, chemical by-product hydrogen production, water electrolysis, and biomass production. Considering factors such as cost and maturity, fossil fuel-based hydrogen production remains the primary source, especially reforming, which is the main method of hydrogen production. In steam reforming, the reaction products are typically hydrogen-rich gases containing hydrogen, carbon dioxide, and carbon monoxide. Therefore, for applications requiring high hydrogen purity, hydrogen purification is necessary.

[0003] Currently, hydrogen purification methods mainly include pressure swing adsorption (PSA), cryogenic separation, and membrane separation. Among these, PSA is the most common in industry. PSA purifies hydrogen by utilizing the different adsorption forces of the adsorbent on different gas molecules. However, the equipment is complex, and the hydrogen recovery rate is relatively low. For example, Chinese patent CN119633548A discloses a pressure swing adsorption hydrogen purification device, which is complex, costly, and suitable for large-scale production.

[0004] Electrochemical purification methods can efficiently purify hydrogen-rich gases using the principle of hydrogen pumps, offering advantages such as simple structure, high hydrogen recovery efficiency, and compatibility with miniaturization. However, most current electrochemical purification methods use perfluorosulfonic acid as the proton exchange membrane, which not only requires gas humidification, making the system more complex, but also often suffers from poisoning by impurities such as CO, leading to catalyst poisoning and system failure. For example, Chinese patents CN118976348A and CN115411304A use electrochemical devices for purification, but they employ a low-temperature perfluorosulfonic acid system, which has limited resistance to CO poisoning, typically only on the order of 0.2 ppm. Since reformed gas usually contains 1-5% CO, it easily leads to catalyst CO poisoning, causing system failure. Summary of the Invention

[0005] The purpose of this invention is to provide an electrochemical device for hydrogen purification in hydrogen-rich gas that can reduce the CO adsorption capacity on the catalyst surface in an electrochemical hydrogen purification device, thereby improving the catalyst's resistance to poisoning and effectively solving the problem of CO poisoning of the catalyst causing the purification device to fail.

[0006] The technical solution of this invention is: An electrochemical device for purifying hydrogen from a hydrogen-rich gas, comprising: An electrochemical purification device includes a gas inlet and a pure hydrogen outlet. The purification device is equipped with an oil passage, with one end of the oil passage being the oil inlet and the other end being the oil outlet. The heat exchanger includes a gas inlet and a gas outlet, as well as an oil inlet and an oil outlet. The gas outlet and the gas inlet are connected by a connecting pipe. The oil pipeline includes an oil supply pipeline connecting the oil inlet and the oil outlet, and a return oil pipeline connecting the oil outlet and the oil inlet. The oil pipeline is equipped with a pump, a heater and a temperature sensor. When the oil temperature in the oil pipeline is lower than the set value t, the heater turns on to heat the oil in the oil pipeline; when the oil temperature in the oil pipeline is higher than the set value t, the heater turns off. The specific operation of an electrochemical device for hydrogen purification from hydrogen-rich gas according to this scheme is as follows: The reformed gas is fed into the heat exchanger through the reforming inlet, where it is preheated to increase its temperature. Next, the reformed gas is fed into the electrochemical purification unit through the oil outlet, connecting pipeline and reformed gas inlet, where the reformed gas (hydrogen-rich gas) is efficiently purified, and the purified hydrogen is output from the pure hydrogen outlet. In this process, during the initial operation of the electrochemical equipment, the overall temperature of the equipment is low, which can easily lead to CO poisoning of the catalyst in the electrochemical purification unit. To solve this problem, this application sets up an oil passage within the electrochemical purification unit and forms a temperature control loop through the oil passage pipes, pumps, heaters, and temperature sensors. During the initial operation of the electrochemical equipment, the heater is turned on to heat the oil in the oil passage pipes. The pump drives the oil to circulate within the oil passage and oil passage pipes of the electrochemical purification unit, thereby rapidly heating the ambient temperature inside the electrochemical purification unit. This reduces the CO adsorption capacity on the catalyst surface in the electrochemical purification unit, improves the catalyst's resistance to poisoning, and effectively solves the problem of CO poisoning of the catalyst causing purification equipment failure.

[0007] After the electrochemical equipment has been operating for a period of time, the reaction within it generates heat, raising the ambient temperature inside the electrochemical purification unit. To prevent the ambient temperature inside the electrochemical purification unit from becoming too high, the heater is turned off when the oil temperature in the oil pipeline exceeds a set value t. The heat generated by the reaction within the electrochemical equipment is then used to maintain the ambient temperature inside the electrochemical purification unit. Conversely, during the operation of the electrochemical equipment, a temperature sensor monitors the oil temperature in the oil pipeline in real time. When the oil temperature in the oil pipeline falls below the set value t, the heater is turned on to heat the oil in the oil pipeline, thereby maintaining the ambient temperature inside the electrochemical purification unit.

[0008] On the other hand, when reformed gas at room temperature, especially at low temperature, enters the electrochemical purification unit, the heat exchange between the reformed gas and the ambient temperature within the unit takes time. This results in CO poisoning of some catalysts within the unit, particularly those near the reformed gas inlet. To address this issue, this design incorporates a heat exchanger. The reformed gas is preheated through the inlet, increasing its temperature and effectively resolving the aforementioned problem.

[0009] As a preferred option, the electrochemical purification device also includes: Two manifolds, The electrochemical purification unit is located between two current collectors and consists of conductive separators and membrane electrodes that are alternately distributed in sequence. The membrane electrodes include a separator, which is a phosphoric acid-doped PBI membrane. Two end plates, two current collectors, and the electrochemical purification unit are located between the two end plates, with an insulating layer between each end plate and current collector. The membrane electrode diaphragm in this design is a phosphoric acid-doped PBI membrane (i.e., high-temperature proton exchange membrane), which can achieve proton conduction at high temperatures (typically 100–200°C) while maintaining the membrane's thermal stability and chemical inertness. This allows the electrochemical purification device to better adapt to high-temperature environments, eliminating the need for gas humidification and simplifying the electrochemical equipment.

[0010] Preferably, the partition is provided with a partition oil supply port and a partition oil return port, and the partition is provided with a partition inner cavity. The partition oil supply port and the partition oil return port are both connected to the partition inner cavity. Sealing rings are provided on the opposite two sides of the partition at the edges of the partition oil supply port and the partition oil return port. The membrane electrode is provided with an oil supply port and an oil return port. The oil supply port of the partition plate on each partition plate and the oil supply port on each membrane electrode are connected in series to form an oil supply channel. One end of the oil supply channel is connected to the oil inlet. Each baffle's return oil port is connected in series with the return oil outlet on each membrane electrode to form a return oil channel, one end of which is connected to the oil outlet. Thus, the baffle's supply oil port, inner cavity, and return oil port within each baffle form a baffle oil channel structure, with these structures distributed in parallel between the supply and return oil channels. During pump operation, oil entering through the oil inlet flows sequentially into the baffle oil channel structure within each baffle through the supply channel, rapidly heating or removing heat from the baffles, and then flows out through the return oil channel and oil outlet. In this way, when the oil temperature in the oil pipeline is lower than the set value t, the baffles can rapidly heat the ambient temperature within the electrochemical purification unit, further reducing the CO adsorption capacity on the catalyst surface and improving the catalyst's resistance to poisoning. When the oil temperature in the oil pipeline is higher than the set value t, the oil can rapidly remove heat from the baffles to maintain the ambient temperature within the electrochemical purification unit.

[0011] Preferably, the partition is provided with a gas-rectifying inlet and a pure hydrogen inlet, and sealing rings are provided on the opposite sides of the partition at the edges of the gas-rectifying inlet and the pure hydrogen inlet. The membrane electrode is provided with an electrode gas rectifier port and an electrode pure hydrogen port; The gas rectifier ports on each partition are connected in series with the gas rectifier ports on each membrane electrode to form a gas rectifier channel, and one end of the gas rectifier channel is connected to the gas rectifier inlet. The pure hydrogen inlets on each partition plate are connected in series with the pure hydrogen inlets on each membrane electrode to form a pure hydrogen flow channel, one end of which is connected to the pure hydrogen outlet. In this way, the reformed gas input through the reforming inlet can be fed into various parts of the electrochemical purification unit through the reforming flow channel, thereby improving the purification efficiency of the electrochemical purification unit; simultaneously, the purified hydrogen from the electrochemical purification unit is output through the pure hydrogen flow channel and the pure hydrogen outlet, ensuring that the reformed gas and pure hydrogen do not interfere with each other.

[0012] Preferably, a flow field is provided in the middle of the partition, and sealing rings are provided on the opposite two sides of the partition at the edge of the flow field. The flow field includes several strip-shaped openings provided on the partition.

[0013] Preferably, the membrane electrode further includes an anode gas diffusion layer and an anode catalyst layer, as well as a cathode catalyst layer and a cathode gas diffusion layer, with the anode gas diffusion layer, anode catalyst layer, membrane, cathode catalyst layer and cathode gas diffusion layer distributed sequentially.

[0014] Preferably, the catalyst in the anode catalyst layer is a Pt / C catalyst, a Pt-Ru / C catalyst, a Pt-Rh / C catalyst, or a Pt-Ir / C catalyst; the catalyst in the cathode catalyst layer is a Pt / C catalyst or a PtM alloy catalyst. Using a Pt / C, Pt-Ru / C, Pt-Rh / C, or Pt-Ir / C catalyst in the anode catalyst layer can improve the catalyst's resistance to poisoning. Similarly, using a Pt / C or PtM alloy catalyst in the cathode catalyst layer can also improve the catalyst's resistance to poisoning.

[0015] Preferably, the electrochemical purification device also includes a battery, with the positive electrode of the battery electrically connected to a current collector and the negative electrode of the battery electrically connected to another current collector.

[0016] Preferably, the setpoint t is greater than or equal to 120℃ and less than or equal to 150℃. Maintaining the ambient temperature within the electrochemical purification device between 120-200℃ reduces the CO adsorption capacity on the catalyst surface, improves the catalyst's resistance to poisoning, and simultaneously maintains the thermal stability of the membrane electrochemical purification device. Therefore, this scheme sets the setpoint t to be greater than or equal to 120℃ and less than or equal to 150℃. This allows for two main advantages: firstly, it enables a rapid increase in the ambient temperature within the electrochemical purification device to 120℃ during the initial operation of the electrochemical equipment, thereby reducing the CO adsorption capacity on the catalyst surface and improving the catalyst's resistance to poisoning; secondly, after the electrochemical equipment has been operating for a period of time, the heater can be turned off, and the heat generated by the reaction within the electrochemical equipment can be used to maintain the ambient temperature within the electrochemical purification device.

[0017] Preferably, a radiator is also installed on the oil pipeline. In this way, after the electrochemical equipment has been working for a period of time, the pump can drive the oil to circulate, and the heat of the oil can be quickly dissipated through the radiator, which helps to maintain the ambient temperature inside the electrochemical purification device.

[0018] The beneficial effects of this invention are: Firstly, during the operation of the electrochemical equipment, the temperature sensor monitors the oil temperature in the oil pipeline in real time. When the oil temperature in the oil pipeline is lower than the set value t, the heater is turned on to heat the oil in the oil pipeline, thereby maintaining the ambient temperature in the electrochemical purification device, reducing the CO adsorption capacity on the catalyst surface in the electrochemical purification device, and improving the catalyst's resistance to poisoning.

[0019] Secondly, in the initial stage of operation of the electrochemical equipment, the heater can be turned on to heat the oil in the oil pipeline, thereby rapidly increasing the ambient temperature inside the electrochemical purification device. This reduces the CO adsorption capacity on the catalyst surface in the electrochemical purification device, improves the catalyst's resistance to poisoning, and effectively solves the problem of CO poisoning of the catalyst, which causes the purification equipment to fail.

[0020] After the electrochemical equipment has been working for a period of time, the heat generated by the reaction inside the electrochemical equipment will be used to maintain the ambient temperature inside the electrochemical purification device in order to prevent the ambient temperature inside the electrochemical purification device from becoming too high. When the oil temperature in the oil pipeline is higher than the set value t, the heater is turned off. The heat generated by the reaction inside the electrochemical equipment is used to maintain the ambient temperature inside the electrochemical purification device.

[0021] Third, the reformed gas is fed into the heat exchanger through the reforming gas inlet. The heat exchanger preheats the reformed gas, increasing the temperature of the reformed gas entering the electrochemical purification unit, thereby further improving the catalyst's resistance to poisoning. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of one embodiment of an electrochemical device for purifying hydrogen in a hydrogen-rich gas according to the present invention.

[0023] Figure 2 This is a schematic diagram of another embodiment of an electrochemical device for purifying hydrogen in a hydrogen-rich gas according to the present invention.

[0024] Figure 3 This is a schematic diagram of the structure of an electrochemical purification device for purifying hydrogen in a hydrogen-rich gas according to the present invention.

[0025] Figure 4 This is a schematic diagram of the structure of a partition in an electrochemical device for purifying hydrogen in a hydrogen-rich gas according to the present invention.

[0026] In the picture: Electrochemical purification device 1, gas inlet 1.1, pure hydrogen outlet 1.2, impurity gas outlet 1.3, oil inlet 1.4, oil outlet 1.5, battery 1.6, end plate 1.7, current collector 1.8, electrochemical purification unit 1.9, separator 1.91, separator gas inlet 1.911, separator oil inlet 1.912, flow field 1.913, separator impurity gas inlet 1.914, separator oil return inlet 1.915, separator pure hydrogen inlet 1.916, sealing ring 1.917, membrane electrode 1.92, insulating plate 1.10, fastening device 1.11; Heat exchanger 2, gas inlet 2.1, gas outlet 2.2, oil inlet 2.3, oil outlet 2.4; Oil pipeline 3, oil supply pipeline 3.1, oil return pipeline 3.2; 4 reformer gas storage tanks; 5 pure hydrogen storage tanks; Pump 6; Temperature sensor 7; Heater 8; Radiator 9; Bypass pipe 10. Detailed Implementation

[0027] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments: Specific Implementation Example 1, such as Figure 1 , Figure 3 As shown, an electrochemical device for purifying hydrogen in a hydrogen-rich gas includes an electrochemical purification unit 1, a heat exchanger 2, and an oil pipeline 3.

[0028] The electrochemical purification unit 1 includes a rectified gas inlet 1.1, a pure hydrogen outlet 1.2, and an impurity gas outlet 1.3. The purification unit is equipped with an oil passage. One end of the oil passage is the oil inlet 1.4, and the other end is the oil outlet 1.5.

[0029] Heat exchanger 2 includes a gas purifying inlet 2.1 and a gas purifying outlet 2.2, as well as an oil inlet 2.3 and an oil outlet 2.4. The gas purifying outlet 2.2 of heat exchanger 2 is connected to the gas purifying inlet 1.1 of electrochemical purification device 1 via a connecting pipe.

[0030] The oil pipeline 3 includes an oil supply pipeline 3.1 connecting the oil inlet 1.4 and the oil outlet 2.4, and a return pipeline 3.2 connecting the oil outlet 1.5 and the oil inlet 2.3. The oil pipeline 3 is equipped with a pump 6, a heater 8, and a temperature sensor 7. The heater 8 is used to heat the oil in the oil pipeline 3, and the temperature sensor 7 is used to detect the temperature of the oil in the oil pipeline 3.

[0031] When the oil temperature in oil pipeline 3 is lower than the set value t, heater 8 is turned on to heat the oil in oil pipeline 3. When the oil temperature in oil pipeline 3 is higher than the set value t, heater 8 is turned off. The set value t is greater than or equal to 120℃ and less than or equal to 150℃. For example, the set value t is 120℃, 130℃, 140℃, or 150℃. The ambient temperature inside the electrochemical purification device 1 is between 120-200℃, which can reduce the CO adsorption capacity on the catalyst surface, improve the catalyst's resistance to poisoning, and at the same time maintain the thermal stability of the membrane electrochemical purification device 1. Therefore, in this embodiment, the set value t is greater than or equal to 120°C and less than or equal to 150°C. This allows the ambient temperature inside the electrochemical purification device 1 to be rapidly increased to 120°C during the initial operation of the electrochemical equipment, thereby reducing the CO adsorption capacity on the catalyst surface and improving the catalyst's resistance to poisoning. At the same time, after the electrochemical equipment has been operating for a period of time, the heater 8 can be turned off, and the ambient temperature inside the electrochemical purification device 1 can be maintained by the heat generated by the reaction inside the electrochemical equipment.

[0032] The specific operation of the electrochemical device for hydrogen purification in a hydrogen-rich gas according to this embodiment is as follows: Pump 6 drives the oil to circulate in the oil passage and oil pipeline 3 within the electrochemical purification device 1.

[0033] The reformed gas is fed into heat exchanger 2 through reforming gas inlet 2.1, where it is preheated to increase its temperature. (The reformed gas can be methanol reformed gas, natural gas reformed gas, ammonia reformed gas, etc., and the CO concentration in the reformed gas can be 0~10%). Next, the reformed gas is fed into electrochemical purification unit 1 through oil outlet 2.4 and a connecting pipe to reforming gas inlet 1.1. The reformed gas (hydrogen-rich gas) undergoes efficient purification, and the purified hydrogen is output through pure hydrogen outlet 1.2, while impurity gases are discharged through impurity gas outlet 1.3. During this process, in the initial stage of operation of the electrochemical equipment, the overall temperature of the electrochemical equipment is low, which can easily lead to CO poisoning of the catalyst in the electrochemical purification device 1. To solve this problem, this embodiment sets up an oil passage in the electrochemical purification device 1 and forms a temperature control loop through the oil passage pipe 3, pump 6, heater 8 and temperature sensor 7. In the initial stage of operation of the electrochemical equipment, the heater 8 is turned on to heat the oil in the oil passage pipe 3. The pump 6 drives the oil to circulate in the oil passage and oil passage pipe 3 in the electrochemical purification device 1, thereby quickly heating the ambient temperature in the electrochemical purification device 1, thereby reducing the CO adsorption capacity on the surface of the catalyst in the electrochemical purification device 1, improving the catalyst's resistance to poisoning, and thus effectively solving the problem of CO poisoning of the catalyst, which causes the purification equipment to fail.

[0034] After the electrochemical equipment has been operating for a period of time, the reaction within the equipment generates heat, raising the ambient temperature inside the electrochemical purification device 1. To prevent the ambient temperature inside the electrochemical purification device 1 from becoming too high, when the oil temperature in the oil pipeline 3 exceeds the set value t, the heater 8 is turned off. The heat generated by the reaction within the electrochemical equipment is used to maintain the ambient temperature inside the electrochemical purification device 1. Of course, during the operation of the electrochemical equipment, the temperature sensor 7 monitors the oil temperature in the oil pipeline 3 in real time. When the oil temperature in the oil pipeline 3 falls below the set value t, the heater 8 is turned on to heat the oil in the oil pipeline 3, thereby maintaining the ambient temperature inside the electrochemical purification device 1.

[0035] On the other hand, when reformed gas at room temperature, especially at low temperature, enters the electrochemical purification unit 1, the heat exchange between the reformed gas and the ambient temperature within the unit takes time. This results in CO poisoning of some catalysts within the unit, particularly those near the reformed gas inlet 1.1. To further address this issue, this design incorporates a heat exchanger 2. The reformed gas is input into the heat exchanger 2 through the reformed gas inlet 2.1, where it is preheated, increasing the temperature of the reformed gas entering the electrochemical purification unit 1 and effectively resolving the aforementioned problem.

[0036] Specific embodiment two, such as Figures 1-4 As shown, an electrochemical device for purifying hydrogen in a hydrogen-rich gas includes an electrochemical purification unit 1, a heat exchanger 2, and an oil pipeline 3.

[0037] The electrochemical purification device 1 includes a gas inlet 1.1, a pure hydrogen outlet 1.2, an impurity gas outlet 1.3, a battery 1.6, two end plates 1.7, two current collectors 1.8, and an electrochemical purification unit 1.9. The electrochemical purification unit 1.9 is located between the two current collectors 1.8. The two current collectors 1.8 and the electrochemical purification unit 1.9 are located between the two end plates 1.7. An insulating layer is provided between each end plate 1.7 and the current collector 1.8.

[0038] In one example, the insulating layer is formed by an insulating plate 1.10. The insulating plate 1.10 is disposed between the end plate 1.7 and the current collector 1.8.

[0039] In another example, the current collector 1.8 has an insulating layer on one side facing the end plate 1.7, which constitutes the insulating spacer.

[0040] The electrochemical purification unit 1.9 consists of conductive separators 1.91 and membrane electrodes 1.92 arranged alternately. In this embodiment, each membrane electrode 1.92 has separators 1.91 on both sides. The membrane electrode 1.92 includes a membrane, which is a phosphoric acid-doped PBI membrane (i.e., high-temperature proton exchange). The phosphoric acid-doped PBI membrane can achieve proton conduction at high temperatures (typically 100–200°C) while maintaining the membrane's thermal stability and chemical inertness.

[0041] The purification device is equipped with an oil passage. In this embodiment, the oil passage is located within the electrochemical purification unit 1.9. One end of the oil passage is an oil inlet 1.4, and the other end is an oil outlet 1.5.

[0042] The positive terminal of battery 1.6 is electrically connected to a current collector 1.8, and the negative terminal of battery 1.6 is electrically connected to another current collector 1.8.

[0043] Heat exchanger 2 includes a gas purifying inlet 2.1 and a gas purifying outlet 2.2, as well as an oil inlet 2.3 and an oil outlet 2.4. The gas purifying outlet 2.2 of heat exchanger 2 is connected to the gas purifying inlet 1.1 of electrochemical purification device 1 via a connecting pipe.

[0044] The oil pipeline 3 includes an oil supply pipeline 3.1 connecting the oil inlet 1.4 and the oil outlet 2.4, and a return pipeline 3.2 connecting the oil outlet 1.5 and the oil inlet 2.3. The oil pipeline 3 is equipped with a pump 6, a heater 8, and a temperature sensor 7. The heater 8 is used to heat the oil in the oil pipeline 3; in this embodiment, the heater 8 is an electric heater. The temperature sensor 7 is used to detect the temperature of the oil in the oil pipeline 3.

[0045] When the oil temperature in oil pipeline 3 is lower than the set value t, heater 8 is turned on to heat the oil in oil pipeline 3. When the oil temperature in oil pipeline 3 is higher than the set value t, heater 8 is turned off. The set value t is greater than or equal to 120℃ and less than or equal to 150℃. For example, the set value t is 120℃, 130℃, 140℃, or 150℃. The ambient temperature inside the electrochemical purification device 1 is between 120-200℃, which can reduce the CO adsorption capacity on the catalyst surface, improve the catalyst's resistance to poisoning, and at the same time maintain the thermal stability of the membrane electrochemical purification device 1. Therefore, in this embodiment, the set value t is greater than or equal to 120°C and less than or equal to 150°C. This allows the ambient temperature inside the electrochemical purification device 1 to be rapidly increased to 120°C during the initial operation of the electrochemical equipment, thereby reducing the CO adsorption capacity on the catalyst surface and improving the catalyst's resistance to poisoning. At the same time, after the electrochemical equipment has been operating for a period of time, the heater 8 can be turned off, and the ambient temperature inside the electrochemical purification device 1 can be maintained by the heat generated by the reaction inside the electrochemical equipment.

[0046] The specific operation of the electrochemical device for hydrogen purification in a hydrogen-rich gas according to this embodiment is as follows: Pump 6 drives the oil to circulate in the oil passage and oil pipeline 3 within the electrochemical purification device 1.

[0047] The reformed gas is supplied via a reformed gas storage tank 4 or a reformed gas pipeline. The reformed gas enters the heat exchanger 2 through the reformed gas inlet 2.1, where it is preheated to increase its temperature (the reformed gas can be methanol reformed gas, natural gas reformed gas, ammonia reformed gas, etc., with a CO concentration of 0-10%). Next, the reformed gas enters the electrochemical purification unit 1 through the oil outlet 2.4 and a connecting pipeline to the reformed gas inlet 1.1. The reformed gas (hydrogen-rich gas) undergoes efficient purification, and the purified hydrogen is output through the pure hydrogen outlet 1.2, while impurities are discharged through the impurity gas outlet 1.3. During this process, in the initial stage of operation of the electrochemical equipment, the overall temperature of the electrochemical equipment is low, which can easily lead to CO poisoning of the catalyst in the electrochemical purification device 1. To solve this problem, this embodiment sets up an oil passage in the electrochemical purification device 1 and forms a temperature control loop through the oil passage pipe 3, pump 6, heater 8 and temperature sensor 7. In the initial stage of operation of the electrochemical equipment, the heater 8 is turned on to heat the oil in the oil passage pipe 3. The pump 6 drives the oil to circulate in the oil passage and oil passage pipe 3 in the electrochemical purification device 1, thereby quickly heating the ambient temperature in the electrochemical purification device 1, thereby reducing the CO adsorption capacity on the surface of the catalyst in the electrochemical purification device 1, improving the catalyst's resistance to poisoning, and thus effectively solving the problem of CO poisoning of the catalyst, which causes the purification equipment to fail.

[0048] After the electrochemical equipment has been operating for a period of time, the reaction inside the equipment generates heat, raising the ambient temperature inside the electrochemical purification device 1. To prevent the ambient temperature inside the electrochemical purification device 1 from becoming too high, when the oil temperature in the oil pipeline 3 exceeds the set value t, the heater 8 is turned off, and the ambient temperature inside the electrochemical purification device 1 is maintained solely by the heat generated by the reaction inside the electrochemical equipment. Of course, during the operation of the electrochemical equipment, the temperature sensor 7 monitors the oil temperature in the oil pipeline 3 in real time. When the oil temperature in the oil pipeline 3 falls below the set value t, the heater 8 is turned on to heat the oil in the oil pipeline 3, thereby maintaining the ambient temperature inside the electrochemical purification device 1.

[0049] On the other hand, when reformed gas at room temperature, especially at low temperature, enters the electrochemical purification unit 1, the heat exchange between the reformed gas and the ambient temperature within the unit takes time. This results in CO poisoning of some catalysts within the unit, particularly those near the reformed gas inlet 1.1. To further address this issue, this design incorporates a heat exchanger 2. The reformed gas is input into the heat exchanger 2 through the reformed gas inlet 2.1, where it is preheated, increasing the temperature of the reformed gas entering the electrochemical purification unit 1 and effectively resolving the aforementioned problem.

[0050] Furthermore, the membrane of the membrane electrode 1.92 in this embodiment is a phosphoric acid-doped PBI membrane, which can achieve proton conduction at high temperatures (typically 100–200°C) while maintaining the thermal stability and chemical inertness of the membrane; thus, the electrochemical purification device 1 is better adapted to working in high-temperature environments, eliminating the need for gas humidification and simplifying the electrochemical equipment.

[0051] Specifically, such as Figure 1 As shown, an electrochemical device for purifying hydrogen from a hydrogen-rich gas includes a pure hydrogen storage tank 5 and an impurity gas storage tank. A pure hydrogen outlet 1.2 is connected to the pure hydrogen storage tank via a pure hydrogen pipeline. The pure hydrogen output from the pure hydrogen outlet 1.2 is stored in the pure hydrogen storage tank. An impurity gas outlet 1.3 is connected to the impurity gas storage tank via an impurity gas pipeline. The impurity gas discharged from the impurity gas outlet 1.3 is stored in the impurity gas storage tank.

[0052] Furthermore, such as Figure 3 As shown, the electrochemical purification device 1 also includes a fastening device 1.11, which includes a fastening screw. The fastening screw connects the two end plates 1.7 and is located outside the electrochemical purification unit 1.9. By tightening the nut on the fastening screw, the two end plates 1.7 clamp the current collector 1.8 between the two end plates 1.7 and the electrochemical purification unit 1.9.

[0053] Furthermore, such as Figure 1 , Figure 3 As shown, the gas inlet 1.1 is located on one end plate 1.7, and the pure hydrogen outlet 1.2 is located on the other end plate 1.7.

[0054] Each partition 1.91 is provided with a partition gas rectifier port 1.911 and a partition pure hydrogen port 1.916. On the opposite sides of the partition 1.91, at the edge of the gas rectifier port and the pure hydrogen port, a sealing ring 1.917 is provided, which is sealed to the adjacent membrane electrode 1.92.

[0055] The membrane electrode 1.92 is provided with an electrode gas rectifier port and an electrode pure hydrogen port. The electrode gas rectifier port and the separator gas rectifier port 1.911 are directly opposite each other, and the electrode pure hydrogen port and the separator pure hydrogen port 1.916 are directly opposite each other.

[0056] Each partition 1.91 has a rectified gas inlet 1.911 connected in series with the electrode rectified gas inlet 1.92 of each membrane electrode to form a rectified gas channel. One end of the rectified gas channel is connected to the rectified gas inlet 1.1, and the other end is closed. Specifically, a collector plate 1.8 adjacent to the partition 1.91 where the rectified gas inlet 1.1 is located is provided with a collector plate rectified gas inlet, and one end of the rectified gas channel is connected to the rectified gas inlet 1.1 through the collector plate rectified gas inlet. In this way, the reformed gas input through the rectified gas inlet 1.1 can be input to various parts of the electrochemical purification device 1 through the rectified gas channel, thereby improving the purification efficiency of the electrochemical purification device 1.

[0057] The pure hydrogen inlet 1.916 on each partition 1.91 is connected in series with the electrode pure hydrogen inlet on each membrane electrode 1.92 to form a pure hydrogen flow channel. One end of the pure hydrogen flow channel is connected to the pure hydrogen outlet 1.2, and the other end is closed. Specifically, a collector plate 1.8 adjacent to the partition 1.91 where the pure hydrogen outlet 1.2 is located is provided with a collector plate 1.8 pure hydrogen inlet, and one end of the pure hydrogen flow channel is connected to the pure hydrogen outlet 1.2 through the collector plate 1.8 pure hydrogen inlet. In this way, the purified hydrogen gas from the electrochemical purification device 1 is output through the pure hydrogen flow channel and the pure hydrogen outlet 1.2, and the reformed gas and pure hydrogen do not interfere with each other.

[0058] Furthermore, such as Figure 3 As shown, a flow field 1.913 is provided in the middle of the partition 1.91. Sealing rings 1.917 are provided on both opposite sides of the partition 1.91 at the edges of the flow field 1.913, and these sealing rings 1.917 are sealed to the adjacent membrane electrodes 1.92. The flow field 1.913 includes several strip-shaped openings on the partition 1.91. The partition gas rectifying port 1.911 and the partition pure hydrogen port 1.916 are distributed on the outer side of the flow field 1.913.

[0059] Furthermore, such as Figure 3 As shown, the baffle 1.91 is provided with a baffle oil supply port 1.912 and a baffle oil return port 1.915. The baffle oil supply port 1.912 and the baffle oil return port 1.915 are located on the outer side of the flow field 1.913. The baffle 1.91 has an inner cavity. In this embodiment, the baffle 1.91 is a hollow structure, and the hollow cavity of the baffle 1.91 constitutes the inner cavity of the baffle 1.91. Both the baffle oil supply port 1.912 and the baffle oil return port 1.915 are connected to the inner cavity of the baffle 1.91. The various strip ports of the flow field 1.913, the baffle gas straightening port 1.911, and the baffle pure hydrogen port 1.916 are not connected to the inner cavity of the baffle 1.91. On the opposite sides of the partition 1.91, sealing rings 1.917 are provided at the edges of the partition oil supply port 1.912 and the partition oil return port 1.915. The sealing rings 1.917 are sealed to the adjacent membrane electrodes 1.92.

[0060] The membrane electrode 1.92 is provided with an oil supply port and an oil return port. The oil supply port 1.912 on each diaphragm 1.91 is connected in series with the oil supply port on each membrane electrode 1.92 to form an oil supply channel. One end of the oil supply channel is connected to the oil inlet 1.4, and the other end of the oil supply channel is closed. The oil return port 1.915 on each diaphragm 1.91 is connected in series with the oil return port on each membrane electrode 1.92 to form a oil return channel. One end of the oil return channel is connected to the oil outlet 1.5, and the other end of the oil return channel is closed. In this way, the oil supply port 1.912, the inner cavity of the diaphragm 1.91, and the oil return port 1.915 in each diaphragm 1.91 will form a diaphragm 1.91 oil passage structure, and the diaphragm 1.91 oil passage structures of each diaphragm 1.91 are distributed in parallel between the oil supply channel and the oil return channel. During the operation of pump 6, the oil entering through oil inlet 1.4 flows sequentially into the oil passage structure of each baffle 1.91 through the oil supply channel, rapidly heating or removing heat from the baffles 1.91, and then flowing out through the return channel and oil outlet 1.5. Thus, when the oil temperature in oil passage 3 is lower than the set value t, the baffles 1.91 can rapidly heat the ambient temperature inside the electrochemical purification device 1, further reducing the CO adsorption capacity on the catalyst surface and improving the catalyst's resistance to poisoning. When the oil temperature in oil passage 3 is higher than the set value t, the oil can rapidly remove heat from each baffle 1.91 to maintain the ambient temperature inside the electrochemical purification device 1.

[0061] In this embodiment, both the oil inlet 1.4 and the oil outlet 1.5 are located on the end plate 1.7.

[0062] In one example, such as Figure 1 As shown, the oil inlet 1.4 and oil outlet 1.5 are located on the same end plate 1.7. In this example, a manifold 1.8 adjacent to the partition 1.91 where the oil inlet 1.4 is located is provided with a manifold 1.8 supply port and a manifold 1.8 return port. One end of the oil supply channel is connected to the oil inlet 1.4 through the manifold 1.8 supply port. One end of the oil return channel is connected to the oil outlet 1.5 through the manifold 1.8 return port.

[0063] In another example, Figure 2 As shown, the oil inlet 1.4 is located on one end plate 1.7, and the oil outlet 1.5 is located on the other end plate 1.7. In this example, a manifold 1.8 adjacent to the partition 1.91 where the oil inlet 1.4 is located has a manifold 1.8 supply port, and one end of the oil supply channel is connected to the oil inlet 1.4 through the manifold 1.8 supply port. A manifold 1.8 adjacent to the partition 1.91 where the oil outlet 1.5 is located has a manifold 1.8 return port, and one end of the return channel is connected to the oil outlet 1.5 through the manifold 1.8 return port.

[0064] Furthermore, such as Figure 3 As shown, each partition 1.91 is provided with a partition gas passage 1.914. On the opposite two sides of the partition 1.91, at the edge of the partition gas passage 1.914, a sealing ring 1.917 is provided, which is sealed to the adjacent distributed membrane electrode 1.92.

[0065] The membrane electrode 1.92 is provided with an electrode impurity port. The electrode impurity port and the separator impurity port 1.914 are directly opposite each other.

[0066] The impurity gas inlet 1.914 on each partition 1.91 is connected in series with the electrode impurity gas inlet on each membrane electrode 1.92 to form an impurity gas channel. One end of the impurity gas channel is connected to the impurity gas outlet 1.3, and the other end of the impurity gas channel is closed. Specifically, a collector plate 1.8 adjacent to the partition 1.91 where the impurity gas outlet 1.3 is located is provided with a collector plate impurity gas inlet, and one end of the impurity gas channel is connected to the impurity gas outlet 1.3 through the collector plate impurity gas inlet.

[0067] Furthermore, the membrane electrode 1.92 employs a gas diffusion electrode on the anode side and a nanoarray electrode on the cathode side. Specifically, The membrane electrode 1.92 also includes an anode gas diffusion layer and an anode catalyst layer, as well as a cathode catalyst layer and a cathode gas diffusion layer. The anode gas diffusion layer, anode catalyst layer, membrane, cathode catalyst layer, and cathode gas diffusion layer are sequentially distributed. The membrane thickness is 10~100 μm. The catalyst in the anode catalyst layer is a Pt / C catalyst, a Pt-Ru / C catalyst, a Pt-Rh / C catalyst, or a Pt-Ir / C catalyst. This anode catalyst can help improve the catalyst's resistance to poisoning. The catalyst loading in the anode catalyst layer is 0.1~1.0 mg / cm². The catalyst in the cathode catalyst layer is a Pt / C catalyst or a PtM alloy catalyst. This cathode catalyst can help improve the catalyst's resistance to poisoning. The catalyst loading in the cathode catalyst layer is 0.1~1.0 mg / cm².

[0068] Furthermore, such as Figure 1 , Figure 2 As shown, a radiator 9, such as a finned radiator, is also provided on the oil pipeline 3. In this way, during the long-term operation of the electrochemical equipment, the oil can be circulated by the pump 6, and the heat in the oil can be quickly dissipated through the radiator 9, which helps to maintain the ambient temperature inside the electrochemical purification device 1 and avoid the ambient temperature inside the electrochemical purification device 1 from becoming too high.

[0069] Furthermore, such as Figure 1 , Figure 2As shown, an electrochemical device for purifying hydrogen from a hydrogen-rich gas also includes a bypass pipe 10, on which a bypass switch valve is installed. An oil circuit switch valve is also installed on the oil circuit pipe 3 near the radiator 9. The oil circuit switch valve and the radiator 9 are connected in series and then connected in parallel with the bypass pipe 10.

[0070] When the oil temperature in oil pipeline 3 is lower than the set value t, the oil circuit switch valve closes and the bypass switch valve opens. In this way, pump 6 drives the oil to circulate through bypass pipeline 10, and the oil does not pass through radiator 9; this is beneficial for the heater 8 to quickly heat the ambient temperature inside the electrochemical purification device 1 when it is working.

[0071] When the oil temperature in the oil pipeline 3 is higher than the set value t, the oil circuit switch valve opens and the bypass switch valve closes. In this way, when the pump 6 drives the oil through circulation, the oil passes through the radiator 9, and the heat in the oil is quickly dissipated by the radiator 9, which helps to maintain the ambient temperature inside the electrochemical purification device 1 and avoids the ambient temperature inside the electrochemical purification device 1 from becoming too high.

[0072] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, alterations, and equivalent transformations made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. An electrochemical device for purifying hydrogen from a hydrogen-rich gas, characterized in that, include: An electrochemical purification device includes a gas inlet and a pure hydrogen outlet. The purification device is equipped with an oil passage, with one end of the oil passage being the oil inlet and the other end being the oil outlet. The heat exchanger includes a gas inlet and a gas outlet, as well as an oil inlet and an oil outlet. The gas outlet and the gas inlet are connected by a connecting pipe. The oil pipeline includes an oil supply pipeline connecting the oil inlet and the oil outlet, and a return oil pipeline connecting the oil outlet and the oil inlet. The oil pipeline is equipped with a pump, a heater and a temperature sensor. When the oil temperature in the oil pipeline is lower than the set value t, the heater turns on to heat the oil in the oil pipeline; when the oil temperature in the oil pipeline is higher than the set value t, the heater turns off.

2. The electrochemical device for hydrogen purification in hydrogen-rich gas according to claim 1, characterized in that, The electrochemical purification device also includes: Two manifolds, The electrochemical purification unit is located between two current collectors and consists of conductive separators and membrane electrodes that are alternately distributed in sequence. The membrane electrodes include a separator, which is a phosphoric acid-doped PBI membrane. Two end plates, two current collectors and an electrochemical purification unit are located between the two end plates, and an insulating layer is provided between the end plates and the current collectors.

3. The electrochemical device for purifying hydrogen in a hydrogen-rich gas according to claim 2, characterized in that, The partition plate is provided with a partition plate oil supply port and a partition plate oil return port. The partition plate is provided with a partition plate inner cavity. The partition plate oil supply port and the partition plate oil return port are both connected to the partition plate inner cavity. Sealing rings are provided on the opposite two sides of the partition plate at the edges of the partition plate oil supply port and the partition plate oil return port. The membrane electrode is provided with an oil supply port and an oil return port. The oil supply port of the partition plate on each partition plate and the oil supply port on each membrane electrode are connected in series to form an oil supply channel. One end of the oil supply channel is connected to the oil inlet. The oil return ports on each diaphragm are connected in series with the oil return ports on each membrane electrode to form an oil return channel, and one end of the oil return channel is connected to the oil outlet.

4. An electrochemical device for purifying hydrogen from a hydrogen-rich gas according to claim 2 or 3, characterized in that, The partition plate is provided with a gas-rectifying inlet and a pure hydrogen inlet. Sealing rings are provided on the opposite sides of the partition plate at the edges of the gas-rectifying inlet and the pure hydrogen inlet. The membrane electrode is provided with an electrode gas rectifier port and an electrode pure hydrogen port; The gas rectifier ports on each partition are connected in series with the gas rectifier ports on each membrane electrode to form a gas rectifier channel, and one end of the gas rectifier channel is connected to the gas rectifier inlet. The pure hydrogen inlet on each separator is connected in series with the pure hydrogen inlet on each membrane electrode to form a pure hydrogen flow channel, and one end of the pure hydrogen flow channel is connected to the pure hydrogen outlet.

5. An electrochemical device for purifying hydrogen from a hydrogen-rich gas according to claim 2 or 3, characterized in that, The partition has a flow field in the middle, and sealing rings are provided on the opposite two sides of the partition at the edge of the flow field. The flow field includes several strip-shaped openings on the partition.

6. An electrochemical device for purifying hydrogen from a hydrogen-rich gas according to claim 2 or 3, characterized in that, The membrane electrode further includes an anode gas diffusion layer and an anode catalyst layer, as well as a cathode catalyst layer and a cathode gas diffusion layer, which are distributed sequentially.

7. The electrochemical device for hydrogen purification in hydrogen-rich gas according to claim 6, characterized in that, The catalyst in the anode catalyst layer is a Pt / C catalyst, a Pt-Ru / C catalyst, a Pt-Rh / C catalyst, or a Pt-Ir / C catalyst; the catalyst in the cathode catalyst layer is a Pt / C catalyst or a PtM alloy catalyst.

8. An electrochemical device for purifying hydrogen from a hydrogen-rich gas according to claim 2 or 3, characterized in that, The electrochemical purification device also includes a battery, with the positive electrode of the battery electrically connected to a current collector and the negative electrode of the battery electrically connected to another current collector.

9. An electrochemical device for purifying hydrogen from a hydrogen-rich gas according to claim 1, 2, or 3, characterized in that, The set value t is greater than or equal to 120°C and less than or equal to 150°C.

10. An electrochemical device for purifying hydrogen from a hydrogen-rich gas according to claim 1, 2, or 3, characterized in that, The oil pipeline is also equipped with a radiator.

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