Fuel cell power generation system and method based on solid ammonia storage and hydrogen production integrated module

Abstract

The invention provides a fuel cell power generation system and method based on a solid-state ammonia storage and hydrogen production integrated module, and the system comprises a solid-state ammonia storage and hydrogen production coupled integrated module and a fuel cell, and the solid-state ammonia storage and hydrogen production coupled integrated module is used for decomposing solid-state ammonia and providing hydrogen for the fuel cell; the solid ammonia storage coupling hydrogen production integrated module comprises an ammonia decomposition hydrogen production module and a solid ammonia storage module, and high-temperature waste gas heat exchange channels are arranged outside and inside the ammonia decomposition hydrogen production module; the solid ammonia storage module is communicated with the ammonia decomposition hydrogen production module through a valve, the high-temperature waste gas heat exchange channel is communicated with a waste gas outlet of the fuel cell, and the ammonia decomposition hydrogen production module is communicated with the fuel cell through a valve; the overall system energy efficiency is effectively improved, the solid-state ammonia storage module and the ammonia hydrogen production module are integrated, the waste gas flow channel is arranged, high-temperature waste gas of the fuel cell is changed into medium-temperature waste gas after passing through the ammonia decomposer, the medium-temperature waste gas is continuously used for ammonia desorption of solid-state ammonia storage, and efficient utilization of waste heat of tail gas of the fuel cell is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen production by ammonia decomposition, and specifically, to a fuel cell power generation system and method based on a solid ammonia storage and hydrogen production integrated module. Background Art

[0002] In recent years, under the background of carbon peaking and carbon neutrality, China has increased its research efforts on the utilization and development of clean energy, especially hydrogen energy, and gradually implemented the popularization of technologies such as hydrogen heavy trucks and hydrogen ships, thus promoting the booming demand for hydrogen energy. How to produce, transport, and store hydrogen greenly, efficiently, and economically has become an important research topic at present. In terms of hydrogen production, the current hydrogen production methods can be divided into hydrolysis hydrogen production, ammonia decomposition hydrogen production, fossil fuel hydrogen production, etc. Fossil fuel hydrogen production is the most mature hydrogen production technology at present, but its disadvantage of high carbon emissions is difficult to meet the "carbon peaking and carbon neutrality" goal. Hydrolysis hydrogen production is the most promising hydrogen production method at present, and a large number of research results have emerged.

[0003] Thermal catalytic ammonia decomposition hydrogen production belongs to one of the ways of thermochemical hydrogen production and is considered an effective hydrogen replenishment method. For example, Patent CN116924327A proposes a technology for decomposing ammonia to produce hydrogen by using the heat energy of hydrogen combustion. In terms of hydrogen transportation and storage, the hydrogen content in the same volume of liquid ammonia is more than 60% higher than that of liquid hydrogen, and the energy consumption of ammonia synthesis is equivalent to that of hydrogen liquefaction, making ammonia an important carrier for storing and transporting hydrogen. For example, Patent CN102782921A proposes a technology for generating hydrogen from ammonia stored in a solid material and integrating the device with a low-temperature fuel cell. This patent CN102782921A can effectively avoid the explosion risk of high-pressure anhydrous liquid ammonia / hydrogen during vehicle transportation in the form of solid ammonia storage. However, the technical form of this patent for producing hydrogen by using the heat energy generated by the catalytic combustion of ammonia to drive ammonia decomposition will inevitably generate polluting gases such as NOX, increasing the investment and operating costs of subsequent NOX gas capture equipment. In addition, at the same operating temperature, as the hydrogen production flow rate increases, the ammonia decomposition rate will rapidly decay, which can rapidly decay from 90% to 10-20%. If no corresponding measures are taken, it will cause unstable hydrogen supply. Summary of the Invention

[0004] Aiming at the defects in the prior art, the purpose of the present invention is to provide a fuel cell power generation system and method based on a solid ammonia storage and hydrogen production integrated module.

[0005] According to the fuel cell power generation system based on the solid ammonia storage and hydrogen production integrated module provided by the present invention, it includes a solid ammonia storage and hydrogen production integrated module and a fuel cell. The solid ammonia storage and hydrogen production integrated module is used to decompose solid ammonia and supply hydrogen to the fuel cell.

[0006] The integrated solid-state ammonia storage and hydrogen production module includes an ammonia decomposition hydrogen production module and a solid-state ammonia storage module arranged in sequence along the radial direction pointing to the axis. High-temperature waste gas heat exchange channels are provided both outside and inside the ammonia decomposition hydrogen production module;

[0007] The gas outlet of the solid-state ammonia storage module is connected to the gas inlet of the ammonia decomposition hydrogen production module through a valve. The high-temperature waste gas heat exchange channel is connected to the waste gas outlet of the fuel cell. The gas outlet of the ammonia decomposition hydrogen production module is connected to the hydrogen inlet of the fuel cell through a valve;

[0008] High-temperature waste gas flows into the high-temperature waste gas heat exchange channel through a valve, providing heat for the solid-state ammonia storage module to complete ammonia desorption, and providing heat for the ammonia decomposition hydrogen production module to decompose ammonia into a mixed gas of ammonia, hydrogen, and nitrogen, where hydrogen flows into the fuel cell.

[0009] Preferably, an external hydrogen purifier is further included. The gas inlet of the external hydrogen purifier is connected to the gas outlet of the ammonia decomposition hydrogen production module through a valve;

[0010] The external gas purifier (12) is used to purify the mixed gas to form two paths of gas. One path is hydrogen, which flows out through the hydrogen outlet of the external gas purifier (12) and then flows into the fuel cell through a valve. The other path is a mixed gas of ammonia and nitrogen, which flows out through the mixed gas outlet of the external gas purifier (12) and then flows into the gas inlet of the ammonia decomposition hydrogen production module through a valve.

[0011] Preferably, a hydrogen purification module is coaxially arranged in the ammonia decomposition hydrogen production module. The hydrogen purification module is used to purify the mixed gas in the ammonia decomposition hydrogen production module and form hydrogen;

[0012] Hydrogen flows into the fuel cell through a valve, and the remaining ammonia and nitrogen in the mixed gas flow into the gas inlet of the ammonia decomposition hydrogen production module through a valve.

[0013] Preferably, a gas storage tank is further included. The gas storage tank is connected to the gas outlet of the ammonia decomposition hydrogen production module through a valve.

[0014] Preferably, a continuous gas component analyzer is further included. The continuous gas component analyzer is connected to the gas outlet of the ammonia decomposition hydrogen production module and is used to detect the residual ammonia concentration in the mixed gas;

[0015] If the ammonia concentration is higher than the preset value, the valve between the gas inlet and the gas outlet of the ammonia decomposition hydrogen production module is controlled to open, and the valve between the gas outlet of the ammonia decomposition hydrogen production module and the gas storage tank is controlled to close, and the mixed gas flows into the inside of the ammonia decomposition hydrogen production module;

[0016] If the ammonia concentration is lower than the preset value, the valve between the gas inlet and the gas outlet of the ammonia decomposition hydrogen production module is closed, and the valve between the gas outlet of the ammonia decomposition hydrogen production module and the gas storage tank is opened, and the mixed gas flows into the gas storage tank.

[0017] Preferably, a buffer is provided between the gas outlet of the ammonia decomposition hydrogen production module and the hydrogen inlet of the fuel cell, and the buffer is communicated with the gas outlet of the ammonia decomposition hydrogen production module through a valve;

[0018] Shunt channels are provided at both the buffer and the gas storage tank for evacuating flammable and explosive gases in the system.

[0019] Preferably, the high-temperature exhaust gas flow channel of the fuel cell is connected to the inlet of the high-temperature exhaust gas heat exchange channel located outside the ammonia decomposition hydrogen production module through a valve;

[0020] The outlet of the high-temperature exhaust gas heat exchange channel located outside the ammonia decomposition hydrogen production module is connected to the inlet of the high-temperature exhaust gas heat exchange channel located inside the ammonia decomposition hydrogen production module, and the outlet of the high-temperature exhaust gas heat exchange channel located inside the ammonia decomposition hydrogen production module is communicated with an external exhaust gas collection device.

[0021] Preferably, it further includes an electric heating component and a backup power source, and the electric heating component is powered and heated by the backup power source;

[0022] The electric heating component is used to heat the gas flow, and the heated gas flow is respectively communicated with the fuel cell and the high-temperature exhaust gas heat exchange channel through valves.

[0023] According to the fuel cell power generation method based on the integrated solid ammonia storage and hydrogen production module provided by the present invention, using the fuel cell power generation system based on the integrated solid ammonia storage and hydrogen production module, the following steps are included:

[0024] Step 1: Start the backup power source to supply power and heat the electric heating component;

[0025] Step 2: Determine whether the gas temperature in the electric heating component is higher than the preset temperature value. If so, open the valve connecting the electric heating component and the fuel cell to preheat the fuel cell. If not, continue heating;

[0026] Step 3: Determine whether the temperature of the fuel cell meets the operating temperature requirement. If so, close the valve connecting the electric heating component and the fuel cell, and open the valve connecting the electric heating component and the integrated solid ammonia storage and hydrogen production connection module. If not, continue heating;

[0027] Step 4: Obtain the hydrogen flow rate requirement of the fuel cell and obtain the current operating temperature of the integrated solid ammonia storage and hydrogen production module;

[0028] Step 5: According to the relationship between the hydrogen production flow rate, the operating temperature of the integrated solid ammonia storage and hydrogen production module, and the ammonia desorption flow rate of the solid ammonia storage module obtained from the experiment, adjust the valve opening at the outlet of the solid ammonia storage module and the valve opening at the outlet of the high-temperature waste gas of the fuel cell to obtain the required ammonia flow rate;

[0029] Step 6: The ammonia flowing out of the solid ammonia storage module is purified through the ammonia decomposition and hydrogen production module (12) and / or the hydrogen purification module to obtain purified hydrogen, which then flows into the buffer;

[0030] Step 7: The hydrogen flows into the fuel cell through the buffer to realize the power generation process;

[0031] According to the fuel cell power generation method based on the integrated solid ammonia storage and hydrogen production module provided by the present invention, using the fuel cell power generation system based on the integrated solid ammonia storage and hydrogen production module, the following steps are included:

[0032] Step 1: When the electric heating component is working, determine whether the tail gas temperature of the fuel cell is higher than the preset temperature;

[0033] If yes, close the valve connecting the electric heating component to the integrated solid ammonia storage and hydrogen production module, open the valve connecting the fuel cell to the integrated solid ammonia storage and hydrogen production module, and introduce the high-temperature waste gas into the high-temperature waste gas heat exchange channel. If no, repeat Step 1;

[0034] Step 2: Charge the backup power supply and determine whether the backup power supply is fully charged. If yes, supply power to the electrical components. If no, repeat Step 2;

[0035] Step 3: Detect whether a shutdown instruction is issued. If yes, end. Otherwise, continue to Step 4;

[0036] Step 4: Use a continuous gas component analyzer to sample and analyze the nitrogen and ammonia mixed gas at the outlet of the ammonia decomposition and hydrogen production module;

[0037] Step 5: Determine whether the concentration of ammonia is higher than the set value. If yes, execute Step 6. If no, execute Step 8;

[0038] Step 6: Open the reflux valve of the integrated solid ammonia storage and hydrogen production module to reflux the mixed gas to the inlet of the ammonia decomposition and hydrogen production module;

[0039] Step 7: Determine whether the pressure of the integrated solid ammonia storage and hydrogen production module is lower than the maximum operating pressure. If yes, execute Step 8. If no, execute Step 6;

[0040] Step 8: Open the valve connecting the gas storage tank to the integrated solid ammonia storage and hydrogen production module, and close the reflux valve of the integrated solid ammonia storage and hydrogen production module;

[0041] Step 9: Determine whether the pressure of the gas storage tank is higher than its allowable pressure. If yes, execute Step 10; if no, execute Step 9.

[0042] Step 10: Close the valve connecting the gas storage tank to the integrated ammonia storage and hydrogen production module, open the reflux valve of the solid ammonia storage integrated hydrogen production module, and execute Step 3.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] 1. The present invention effectively improves the overall system energy efficiency. By integrating the solid ammonia storage module and the ammonia gas hydrogen production module into one, and setting an exhaust gas flow path in the module, the high-temperature exhaust gas of the fuel cell becomes medium-temperature exhaust gas after passing through the ammonia decomposer, and the medium-temperature exhaust gas is continuously used for ammonia desorption of solid ammonia storage, realizing the efficient utilization of the waste heat of the fuel cell tail gas.

[0045] 2. The fuel cell power generation system provided by the present invention detects by determining the ammonia concentration in the mixed gas flowing out of the ammonia decomposition hydrogen production module, and is used to determine whether to return the mixed gas with high ammonia concentration to the inlet of the ammonia decomposition hydrogen production module for further decomposition, thereby improving the utilization rate of ammonia. The present invention effectively improves the total energy efficiency of the solid ammonia storage integrated hydrogen production system by means of efficient waste heat utilization and improving the ammonia utilization rate.

[0046] 3. The present invention effectively reduces the occupied space of ammonia storage and hydrogen production. By coupling the solid ammonia storage module, the ammonia gas hydrogen production module, and the hydrogen purification module into an integrated module, the occupied space of ammonia storage and hydrogen production can be effectively reduced, and the energy density per unit volume of the energy storage system is improved.

[0047] 4. The present invention realizes the efficient and reliable supply of hydrogen under different flow rates. Based on the characteristic that the ammonia decomposition hydrogen production efficiency is strongly correlated with the ammonia desorption flow rate, the present invention obtains the relationship between the hydrogen production flow rate - operating temperature - ammonia desorption flow rate of the solid ammonia storage integrated hydrogen production module through experiments, dynamically adjusts the valve opening degree at the outlet of the solid ammonia storage module, and obtains the ammonia desorption flow rate corresponding to the required hydrogen production flow rate, realizing the efficient and reliable supply of hydrogen under different flow rates. Description of the Drawings

[0048] By reading the detailed description of the non-limiting embodiments with reference to the following drawings, other features, objects, and advantages of the present invention will become more apparent:

[0049] Figure 1 It is a schematic diagram of the overall structure of an embodiment of the present invention;

[0050] Figure 2(a) is a schematic structural diagram of a solid ammonia storage coupled hydrogen production integrated module in an embodiment of the present invention;

[0051] Figure 2 (b) is a schematic structural diagram of the solid ammonia storage module in the present invention;

[0052] Figure 3 is a schematic overall structural diagram of another embodiment of the present invention;

[0053] Figure 4 is a schematic structural diagram of a solid ammonia storage coupled hydrogen production integrated module in another embodiment of the present invention;

[0054] Figure 5 is a schematic flow diagram of the control method of the present invention.

[0055] Solid ammonia storage coupled hydrogen production integrated module 1 Pressure gauge 8

[0056] Fuel cell 2 Gas storage tank 9

[0057] Electric heating component 3 External hydrogen purifier 11

[0058] Standby power supply 4 High-temperature waste gas heat exchange channel 101

[0059] Electrical component 5 Ammonia decomposition hydrogen production module 102

[0060] Continuous gas component analyzer 6 Solid ammonia storage module 103

[0061] Buffer 7 Hydrogen purification module 104 Detailed implementation manners

[0062] The present invention will be described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several changes and improvements can still be made. These all belong to the protection scope of the present invention.

[0063] The present invention provides a fuel cell power generation system and method based on a solid ammonia storage coupled hydrogen production integrated module, which can effectively improve the overall system energy efficiency. By integrating the solid ammonia storage module and the ammonia hydrogen production module into one, and setting up an exhaust gas flow channel in the module, the high-temperature exhaust gas of the fuel cell becomes medium-temperature exhaust gas after passing through the ammonia decomposer, and the medium-temperature exhaust gas is continuously used for ammonia desorption of solid ammonia storage, realizing the efficient utilization of the waste heat of the fuel cell exhaust gas.

[0064] According to the fuel cell power generation system based on the solid ammonia storage coupled hydrogen production integrated module provided by the present invention, refer to Figure 1 and Figure 2As shown in the figure, it includes a solid-state ammonia storage and hydrogen production integrated module 1, a fuel cell 2, an electric heating component 3, a backup power supply 4, an electrical component 5, a continuous gas component analyzer 6, a buffer 7, a pressure gauge 8, a gas storage 9, valves and other components.

[0065] The fuel cell power generation system based on the solid-state ammonia storage and hydrogen production integrated module has different working modes according to different operating states, including a low-temperature startup state and a stable operating state.

[0066] When the system is in the low-temperature startup state, the key components in operation are the solid-state ammonia storage and hydrogen production integrated module 1, the fuel cell 2, the electric heating component 3, and the backup power supply 4. The backup power supply 4 supplies power to the electric heating component 3. After the working medium is heated by the electric heating component 3, it then flows into the fuel cell 2 through a valve to preheat it until it reaches the required operating temperature, and then the fuel cell 2 is started. Then, the valve connecting the electric heating component 3 and the fuel cell 2 is closed, and the valve connecting the electric heating component 3 and the solid-state ammonia storage and hydrogen production integrated module 1 is opened to supply sufficient heat to the latter. When the high-temperature exhaust gas of the fuel cell 2 meets the heat demand of the solid-state ammonia storage and hydrogen production integrated module 1, the system enters the stable operating condition. At this time, the electric heating component 3 and the backup power supply 4 stop operating, and the corresponding valves are closed.

[0067] When the system enters the stable operating state, the key components in operation are the solid-state ammonia storage and hydrogen production integrated module 1 and the fuel cell 2. The valve connecting the high-temperature exhaust gas of the fuel cell 2 and the solid-state ammonia storage and hydrogen production integrated module 1 is opened, and the high-temperature exhaust gas of the fuel cell 2 is used to provide sufficient heat to the solid-state ammonia storage and hydrogen production integrated module 1 to produce the hydrogen flow rate required by the fuel cell 2. The hydrogen produced by the solid-state ammonia storage and hydrogen production integrated module 1 flows into the fuel cell 2 through components such as the buffer 7 and valves to complete the power generation process and provide electrical energy for the electrical component 5.

[0068] As Figure 2 As shown in the figure, the solid-state ammonia storage and hydrogen production integrated module 1 includes a high-temperature exhaust gas heat exchange channel 101, an ammonia decomposition and hydrogen production module 102, a solid-state ammonia storage module 103, and a hydrogen purification module 104. It is in the shape of a "toilet paper roll". Along the radial direction pointing to the axis, the high-temperature exhaust gas heat exchange channel 101, the ammonia decomposition and hydrogen production module 102, the hydrogen purification module 104, the ammonia decomposition and hydrogen production module 102, the high-temperature exhaust gas heat exchange channel 101, and the solid-state ammonia storage module 103 are arranged in sequence, which can realize the efficient ammonia desorption, ammonia decomposition, and hydrogen purification coupling process of the solid-state ammonia storage and hydrogen production integrated module 1, and can also effectively reduce the utilization space required for ammonia storage and hydrogen production.

[0069] The integrated solid-state ammonia storage and hydrogen production module 1 needs to be heated by high-temperature waste gas to achieve ammonia desorption and ammonia decomposition. Since the temperature required by the solid-state ammonia storage module 103 is lower than that required by the ammonia decomposition and hydrogen production module 102, the high-temperature waste gas in the high-temperature waste gas heat exchange channel 101 first heats the ammonia decomposition and hydrogen production module 102, and then heats the solid-state ammonia storage module 103.

[0070] The basic hydrogen production process of the integrated solid-state ammonia storage and hydrogen production module 1 is as follows: After the solid-state ammonia storage module 103 is heated, the ammonia desorption process is completed. The desorbed ammonia enters the ammonia decomposition and hydrogen production module 102 and is decomposed into a mixed gas of ammonia, hydrogen, and nitrogen. Then, under the action of concentration difference, hydrogen flows into the hydrogen purification module 104, and under the entrainment of the inert gas stream, hydrogen flows out of the hydrogen purification module 104 and flows into the fuel cell 2 via the buffer 7 and the valve.

[0071] In order to achieve efficient and stable hydrogen production of the integrated solid-state ammonia storage and hydrogen production module 1, there are also components such as a reflux channel connected to the inlet and outlet of the ammonia decomposition and hydrogen production module 102 through a valve, a continuous gas component analyzer 6 connected to the reflux channel, a pressure gauge 8 for measuring the operating pressure of the integrated solid-state hydrogen storage and hydrogen production module 1, a gas storage tank 9, and valves. Based on the relationship between the hydrogen production flow rate - operating temperature - ammonia desorption flow rate of the solid-state ammonia storage module obtained through experiments, the valve opening degree at the outlet of the solid-state ammonia storage module 103 and the valve opening degree at the high-temperature tail gas outlet of the fuel cell 2 are adjusted to ensure that the hydrogen production flow rate of the integrated solid-state ammonia storage and hydrogen production module 1 meets the requirements of the fuel cell 2. The continuous gas component analyzer 6 is used to detect the ammonia concentration in the mixed gas at the outlet of the ammonia decomposition and hydrogen production module 102. If the value is relatively high, it is refluxed to the inlet of the ammonia decomposition and hydrogen production module 102 for further decomposition to improve the utilization rate of ammonia. Otherwise, it is introduced into the gas storage tank 9. Returning the incompletely decomposed mixed gas to the integrated solid-state hydrogen storage and hydrogen production module 1 will increase its operating pressure. To ensure the safe operation of the integrated solid-state hydrogen storage and hydrogen production module 1, a pressure gauge 8 is provided. When the operating pressure of the integrated solid-state hydrogen storage and hydrogen production module 1 is higher than its maximum operating pressure, the connection valve between the integrated solid-state hydrogen storage and hydrogen production module 1 and the gas storage tank 9 is opened to discharge the gas into the gas storage tank 9 to reduce the operating pressure inside the integrated solid-state hydrogen storage and hydrogen production module 1. When the pressure of the gas storage tank 9 is also higher than its allowable pressure, the connection valve between the integrated solid-state hydrogen storage and hydrogen production module 1 and the gas storage tank 9 is closed, and the connection valve between the integrated solid-state hydrogen storage and hydrogen production module 1 and the ammonia treatment is opened.

[0072] The high-temperature waste gas heat exchange channel 101 is composed of multiple channels, which respectively provide heat for the ammonia decomposition hydrogen production module 102 and the solid ammonia storage module 103. The ammonia decomposition hydrogen production module 102 is embedded with a hydrogen purification module 104. Hydrogen in the mixed gas such as hydrogen, ammonia, and nitrogen generated after ammonia decomposition enters the hydrogen purification module under the action of hydrogen concentration difference, and then flows into the buffer 7 driven by an inert gas stream.

[0073] A plurality of ammonia gas flow channels are designed in the solid ammonia storage module 103, which are evenly distributed along the radial direction pointing to the axis, and the diameters of the channels along this direction increase in sequence, as Figure 2 shown, d1 < d2 < d3. The advantage of this design is that it can achieve uniform ammonia desorption of the solid ammonia storage metal amino complex material in the solid ammonia storage module 103 and improve the heat exchange effect. The reason is that the heat of the high-temperature waste gas heat exchange channel 101 is transmitted along the radial direction pointing to the axis of the solid ammonia storage module 103. Due to the existence of the thermal resistance of the solid ammonia storage metal amino complex material and the thermal resistance of the ammonia gas flow channel, the temperature of the outer wall surface of the solid ammonia storage module 103 is higher than that at the axis, so that the ammonia desorption rate of the outer wall surface is higher than that at the axis. By setting the diameters of the ammonia gas channels to increase in sequence along the radial direction pointing to the axis, it is possible to avoid the phenomenon that the ammonia of the solid ammonia storage metal amino complex material near the outer wall surface is completely desorbed while the solid ammonia storage metal amino complex material at the axis has not been completely desorbed. In addition, since the thermal resistance of the solid ammonia storage metal amino complex material is smaller than the thermal resistance of the ammonia gas flow channel, by reducing the diameter of the ammonia gas flow channel near the outer wall surface of the solid ammonia storage module 103, the thermal resistance of heat transfer can be effectively reduced, and efficient heat exchange can be achieved on the premise of ensuring the ammonia desorption rate.

[0074] The cross-sectional shape of the ammonia gas flow channel in the solid ammonia storage module 103 can be diamond-shaped, circular, elliptical, rectangular, water droplet-shaped or other shapes, and the cross-sectional shape of the ammonia gas flow channel does not significantly affect its beneficial effect.

[0075] The fuel cell is a fuel cell that can provide high-temperature tail gas, such as a solid oxide fuel cell, a high-temperature proton exchange membrane fuel cell, and an alkaline fuel cell, etc.

[0076] See Figure 3 and Figure 4 Describe another embodiment of the present invention, a fuel cell power generation system based on a solid ammonia storage coupled hydrogen production integrated module, including a solid ammonia storage coupled hydrogen production integrated module 1, a fuel cell 2, an electric heating component 3, a backup power supply 4, an electrical component 5, a continuous gas component analyzer 6, a buffer 7, a pressure gauge 8, a gas storage 9, valves, an external hydrogen purifier 11 and other components.

[0077] With Figure 1 and Figure 2Compared with the implementation mode, Figure 3 and Figure 4 Another implementation mode is different in that the hydrogen purification module 104 built in the integrated module 1 for solid-state ammonia storage and hydrogen production by coupling is changed to an external hydrogen purifier 11, and the rest of the solutions remain unchanged.

[0078] Specifically, as Figure 5 shown, the control method for a fuel cell power generation system based on the integrated module for solid-state ammonia storage and hydrogen production by coupling is described, which specifically includes the following steps:

[0079] Step 1: Start.

[0080] Step 2: Start the standby power supply 4, supply power to the electric heating component 5 for heating, and continue to Step 3.

[0081] Step 3: Determine whether the gas temperature in the electric heating component 5 is higher than the set temperature value. If it is, continue to Step 4; otherwise, continue to Step 3.

[0082] Step 4: Open the valve connecting the electric heating component 5 to the fuel cell 2 to preheat the latter, and continue to Step 5.

[0083] Step 5: Determine whether the temperature of the fuel cell 2 meets the operating temperature requirements. If it is, continue to Step 6; otherwise, continue to Step 5.

[0084] Step 6: Close the valve connecting the electric heating component 5 to the fuel cell 2, open the valve connecting the electric heating component 5 to the integrated connection module 1 for solid-state ammonia storage and hydrogen production by coupling, and continue to Step 7.

[0085] Step 7: Obtain the hydrogen flow rate requirement of the fuel cell 2, obtain the current operating temperature of the integrated module 1 for solid-state ammonia storage and hydrogen production by coupling, and continue to Step 8.

[0086] Step 8: According to the relationship of hydrogen production flow rate - operating temperature - ammonia desorption flow rate of the solid-state ammonia module obtained through experiments for the integrated module 1 for solid-state ammonia storage and hydrogen production by coupling, adjust the valve opening degrees of the outlet of the solid-state ammonia module 103 and the outlet of the high-temperature waste gas of the fuel cell 2 to obtain the required ammonia flow rate, and continue to Step 9 and Step 17.

[0087] Step 9: The ammonia flowing out of the solid-state ammonia module 103 obtains purified hydrogen through the ammonia decomposition and hydrogen production module 102 and the hydrogen purification module 104, and flows into the buffer 7, and continue to Step 10.

[0088] Step 10: The hydrogen flows into the fuel cell 2 through the buffer 7 to realize the power generation process, and continue to Step 11 and Step 13 respectively.

[0089] Step 11: Determine whether the exhaust gas temperature of the fuel cell 2 is higher than the set temperature. If so, proceed to Step 12; otherwise, return to Step 11.

[0090] Step 12: Close the valve connecting the electric heating component 3 to the integrated solid ammonia storage and hydrogen production module 1, open the valve connecting the fuel cell 2 to the integrated solid ammonia storage and hydrogen production module 1, and introduce the high-temperature exhaust gas into the high-temperature exhaust gas heat exchange channel 101. Then proceed to Step 16.

[0091] Step 13: Charge the backup power supply 4, and then proceed to Step 14.

[0092] Step 14: Determine whether the backup power supply 4 is fully charged. If so, proceed to Step 15; otherwise, return to Step 14.

[0093] Step 15: Supply power to the electrical component 5, and then proceed to Step 16.

[0094] Step 16: Check whether a shutdown command has been issued. If so, proceed to Step 24; otherwise, return to Step 16.

[0095] Step 17: Use the continuous gas component analyzer 6 to sample and analyze the nitrogen and ammonia mixed gas at the outlet of the ammonia decomposition and hydrogen production module 102, and then proceed to Step 18.

[0096] Step 18: Determine whether the concentration of ammonia is higher than the set value. If so, proceed to Step 19; otherwise, proceed to Step 21.

[0097] Step 19: Open the reflux valve of the integrated solid ammonia storage and hydrogen production module 1, and return the mixed gas to the inlet of the ammonia decomposition and hydrogen production module 102. Then proceed to Step 20.

[0098] Step 20: Determine whether the pressure of the integrated solid ammonia storage and hydrogen production module 1 is lower than the maximum operating pressure. If so, proceed to Step 21; otherwise, return to Step 19.

[0099] Step 21: Open the valve connecting the gas storage tank 9 to the integrated solid ammonia storage and hydrogen production module 1, and close the valve connecting to the ammonia treatment. Then proceed to Step 22.

[0100] Step 22: Determine whether the pressure of the gas storage tank 9 is higher than its allowable pressure. If so, proceed to Step 23; otherwise, return to Step 22.

[0101] Step 23: Close the valve connecting the gas storage tank 9 to the integrated ammonia storage and hydrogen production module 1, open the valve connecting the ammonia treatment to the integrated ammonia storage and hydrogen production module 1, and then proceed to Step 16.

[0102] Step 24: End.

[0103] Based on this, the present invention provides a fuel cell power generation system and its control method based on a solid-state ammonia storage coupled hydrogen production integrated module. By cascading the waste heat of the fuel cell exhaust gas, an efficient ammonia desorption, ammonia decomposition, and hydrogen purification process of the novel solid-state ammonia storage coupled hydrogen production integrated module is realized, and an efficient, stable, and safe supply of hydrogen fuel with different flow rates is achieved.

[0104] In the description of the present application, it should be understood that the orientation or positional relationship indicated by the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. is based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as a limitation to the present application.

[0105] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various changes or modifications within the scope of the claims, which do not affect the essence of the present invention. Without conflict, the embodiments of the present application and the features in the embodiments can be arbitrarily combined with each other.

Claims

1. A fuel cell power generation system based on an integrated module of solid-state ammonia storage and hydrogen production, characterized in that, It includes a solid-state ammonia storage and hydrogen production integrated module (1) and a fuel cell (3). The solid-state ammonia storage and hydrogen production integrated module (1) is used to decompose solid ammonia and supply hydrogen to the fuel cell (3). The solid-state ammonia storage and hydrogen production integrated module (1) includes an ammonia decomposition and hydrogen production module (102) and a solid-state ammonia storage module (103) arranged in sequence along the radial direction pointing to the axis. High-temperature waste gas heat exchange channels (101) are arranged both outside and inside the ammonia decomposition and hydrogen production module (102). The gas outlet of the solid-state ammonia storage module (103) is connected to the gas inlet of the ammonia decomposition and hydrogen production module (102) through a valve. The high-temperature waste gas heat exchange channel (101) is connected to the waste gas outlet of the fuel cell (3). The gas outlet of the ammonia decomposition and hydrogen production module (102) is connected to the hydrogen inlet of the fuel cell (3) through a valve. High-temperature waste gas flows into the high-temperature waste gas heat exchange channel (101) through a valve, which is used to provide heat for the solid-state ammonia storage module (103) to complete ammonia desorption, and is used to provide heat for the ammonia decomposition and hydrogen production module (102) to decompose ammonia into a mixed gas of ammonia, hydrogen, and nitrogen, and the hydrogen flows into the fuel cell (3).

2. The fuel cell power generation system based on the integrated module of solid-state ammonia storage and hydrogen production according to claim 1, wherein It also includes an external hydrogen purifier (11). The gas inlet of the external hydrogen purifier (11) is connected to the gas outlet of the ammonia decomposition and hydrogen production module (102) through a valve. The external gas purifier (12) is used to purify the mixed gas to form two paths of gas. One path is hydrogen, which flows out through the hydrogen outlet of the external gas purifier (12) and then flows into the fuel cell (3) through a valve. The other path is a mixed gas of ammonia and nitrogen, which flows out through the mixed gas outlet of the external gas purifier (12) and then flows into the gas inlet of the ammonia decomposition and hydrogen production module (102) through a valve.

3. The fuel cell power generation system based on the integrated module of solid-state ammonia storage and hydrogen production according to claim 1, characterized in that, A hydrogen purification module (104) is coaxially arranged in the ammonia decomposition and hydrogen production module (102). The hydrogen purification module (104) is used to purify the mixed gas in the ammonia decomposition and hydrogen production module (102) and form hydrogen. Hydrogen flows into the fuel cell (3) through a valve, and the remaining ammonia and nitrogen in the mixed gas flow into the gas inlet of the ammonia decomposition and hydrogen production module (102) through a valve.

4. The fuel cell power generation system based on the integrated module of solid-state ammonia storage and hydrogen production according to claim 2 or 3, characterized in that It also includes a gas storage tank (9). The gas storage tank (9) is connected to the gas outlet of the ammonia decomposition and hydrogen production module (102) through a valve.

5. The fuel cell power generation system based on the integrated module of solid-state ammonia storage and hydrogen production according to claim 4, wherein It also includes a continuous gas component analyzer (6). The continuous gas component analyzer (6) is connected to the gas outlet of the ammonia decomposition and hydrogen production module (102) and is used to detect the residual ammonia concentration in the mixed gas. If the ammonia concentration is higher than the preset value, the valve between the gas inlet and the gas outlet of the ammonia decomposition and hydrogen production module (102) is controlled to open, and the valve between the gas outlet of the ammonia decomposition and hydrogen production module (102) and the gas storage tank (9) is controlled to close, and the mixed gas flows to the inside of the ammonia decomposition and hydrogen production module (102). If the ammonia concentration is lower than the preset value, close the valve between the gas inlet and the gas outlet of the ammonia decomposition hydrogen production module (102), and open the valve between the gas outlet of the ammonia decomposition hydrogen production module (102) and the gas storage tank (9), so that the mixed gas flows into the gas storage tank (9).

6. The fuel cell power generation system based on the integrated module of solid-state ammonia storage and hydrogen production according to claim 4, wherein, A buffer (7) is provided between the gas outlet of the ammonia decomposition hydrogen production module (102) and the hydrogen inlet of the fuel cell (3), and the buffer (7) is communicated with the gas outlet of the ammonia decomposition hydrogen production module (102) through a valve; Shunt channels are provided at both the buffer (7) and the gas storage tank (9) for evacuating flammable and explosive gases in the system.

7. The fuel cell power generation system based on the integrated module of solid-state ammonia storage and hydrogen production according to claim 1, wherein, The high-temperature waste gas flow channel of the fuel cell (2) is connected to the inlet of the high-temperature waste gas heat exchange channel (101) located outside the ammonia decomposition hydrogen production module (102) through a valve; The outlet of the high-temperature waste gas heat exchange channel (101) located outside the ammonia decomposition hydrogen production module (102) is connected to the inlet of the high-temperature waste gas heat exchange channel (101) located inside the ammonia decomposition hydrogen production module (102), and the outlet of the high-temperature waste gas heat exchange channel (101) located inside the ammonia decomposition hydrogen production module (102) is communicated with an external waste gas collection device.

8. The fuel cell power generation system based on the integrated module of solid-state ammonia storage and hydrogen production according to claim 1, wherein It also includes an electric heating component (3) and a standby power supply (4), and the electric heating component (3) is powered for heating by the standby power supply (4); The electric heating component (3) is used to heat the air flow, and the heated air flow is respectively communicated with the fuel cell (2) and the high-temperature waste gas heat exchange channel (101) through valves.

9. A fuel cell power generation method based on an integrated module of solid-state ammonia storage and hydrogen production, characterized in that, Using the fuel cell power generation system based on the integrated solid ammonia storage and hydrogen production module according to any one of claims 1-8, the following steps are included: Step 1: Start the standby power supply (4) to supply power to the electric heating component (3) for heating; Step 2: Determine whether the gas temperature in the electric heating component (3) is higher than the preset temperature value. If so, open the valve connecting the electric heating component (3) and the fuel cell (2) to preheat the fuel cell (2). If not, continue heating; Step 3: Determine whether the temperature of the fuel cell (2) meets the operating temperature requirements. If so, close the valve connecting the electric heating component (3) and the fuel cell (2), and open the valve connecting the electric heating component (3) and the integrated solid ammonia storage and hydrogen production connection module (1). If not, continue heating; Step 4: Obtain the hydrogen flow demand of the fuel cell (2) and obtain the current operating temperature of the integrated solid ammonia storage and hydrogen production module (1); Step 5: According to the relationship between the hydrogen production flow rate, the operating temperature of the integrated solid ammonia storage and hydrogen production module (1) and the ammonia desorption flow rate of the solid ammonia storage module (103) obtained through experiments, adjust the valve opening degree at the outlet of the solid ammonia storage module (103) and the valve opening degree at the high-temperature waste gas outlet of the fuel cell (2) to obtain the required ammonia flow rate; Step 6: The ammonia flowing out of the solid ammonia storage module (103) obtains purified hydrogen through the ammonia decomposition hydrogen production module (12) and / or the hydrogen purification module (104) and flows into the buffer (7); Step 7: Hydrogen flows into the fuel cell (2) via the buffer (7) to achieve the power generation process; 10. A fuel cell power generation method based on an integrated module of solid-state ammonia storage and hydrogen production, characterized in that, The fuel cell power generation system based on the integrated module for solid-state ammonia storage and hydrogen production according to any one of claims 1-8 includes the following steps: Step 1: When the electric heating component (3) is working, determine whether the tail gas temperature of the fuel cell (2) is higher than the preset temperature; If yes, close the valve connecting the electric heating component (3) and the integrated module for solid-state ammonia storage and hydrogen production by coupling (1), open the valve connecting the fuel cell (2) and the integrated module for solid-state ammonia storage and hydrogen production by coupling (1), and introduce the high-temperature waste gas into the high-temperature waste gas heat exchange channel (101); if no, repeat Step 1; Step 2: Charge the backup power supply (4), determine whether the backup power supply (4) is fully charged, if yes, supply power to the electrical component (5), if no, repeat Step 2; Step 3: Detect whether a shutdown instruction is issued, if yes, end, otherwise continue to Step 4; Step 4: Use the continuous gas component analyzer (6) to sample and analyze the nitrogen and ammonia mixed gas at the outlet of the ammonia decomposition hydrogen production module (102); Step 5: Determine whether the concentration of ammonia is higher than the set value, if yes, execute Step 6, if no, execute Step 8; Step 6: Open the reflux valve of the integrated module for solid-state ammonia storage and hydrogen production by coupling (1), and reflux the mixed gas to the inlet of the ammonia decomposition hydrogen production module (102); Step 7: Determine whether the pressure of the integrated module for solid-state ammonia storage and hydrogen production by coupling (1) is lower than the maximum operating pressure, if yes, execute Step 8, if no, execute Step 6; Step 8: Open the valve connecting the gas storage tank (9) and the integrated module for solid-state ammonia storage and hydrogen production by coupling (1), and close the reflux valve of the integrated module for solid-state ammonia storage and hydrogen production by coupling (1); Step 9: Determine whether the pressure of the gas storage tank (9) is higher than its allowable pressure, if yes, execute Step 10, if no, execute Step 9; Step 10: Close the valve connecting the gas storage tank (9) and the integrated module for ammonia storage and hydrogen production by coupling (1), open the reflux valve of the integrated module for solid-state ammonia storage and hydrogen production by coupling (1), and execute Step 3.

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