Heat source switching thermal management method and device suitable for dehydrogenation of carbazole hydrogen storage carrier

Abstract

The application provides a heat source switching heat management method suitable for dehydrogenation of a carbazole hydrogen storage carrier, which can balance the starting speed, steady-state efficiency and safety of dehydrogenation. The reactor is connected to a main heat source channel and at least one auxiliary heat source channel, and the main heat source channel and the auxiliary heat source channel are directly or indirectly connected to the inner cavity of the reactor through a heat conduction device. The gas phase outlet end of the reactor is externally connected to an online gas chromatograph or an online mass spectrometer, the hydrogen concentration / flow rate is detected in real time through sampling from the gas phase outlet of the reactor, the instantaneous / cumulative hydrogen release curve is drawn, and the phase transition of dehydrogenation is directly corresponded, so that the starting phase, the steady-state phase, the high-load phase and the low-load standby phase can be distinguished in real time and further quickly. A heat source control system drives the main heat source channel and the auxiliary heat source channel to supply heat to the inner cavity of the reactor according to the corresponding phase of dehydrogenation.

Description

Technical Field

[0001] This invention relates to the technical field of hydrogen storage carrier dehydrogenation, specifically to a heat source switching thermal management method applicable to carbazole-based hydrogen storage carrier dehydrogenation. This invention also provides an apparatus adapted to this heat source switching thermal management method. Background Technology

[0002] Nitrogen-containing organic liquid carbazole is widely used as a hydrogen carrier with high mass hydrogen storage density for hydrogen storage. It is converted into 12H-NEC (hydrogenated state) through catalytic hydrogenation, and hydrogen is released through dehydrogenation reaction of 12H-NEC (hydrogenated state) when hydrogen is needed.

[0003] The dehydrogenation process of carbazole-based hydrogen storage carriers is an endothermic reaction. Therefore, the dehydrogenation of carbazole-based hydrogen storage carriers in the reactor requires heating. Existing heat sources for providing heat to the reactor are all single heat sources. In actual operation, the dehydrogenation system has slow cold start, large thermal inertia, and difficulty in quickly tracking under fluctuating loads. As a result, the single heat source solution cannot simultaneously take into account start-up speed, steady-state efficiency, and safety.

[0004] Therefore, there is an urgent need to develop a heat source switching thermal management method applicable to the dehydrogenation of carbazole-based hydrogen storage carriers, so as to balance start-up speed, steady-state efficiency and dehydrogenation safety. Summary of the Invention

[0005] To address the aforementioned issues, this invention provides a thermal management method for switching heat sources suitable for dehydrogenation of carbazole-based hydrogen storage carriers, which can balance start-up speed, steady-state efficiency, and dehydrogenation safety.

[0006] A heat source switching thermal management method applicable to dehydrogenation of carbazole-based hydrogen storage carriers is characterized by: connecting the reactor to a main heat source channel and at least one auxiliary heat source channel respectively, and connecting the main heat source channel and the auxiliary heat source channel directly or indirectly to the inner cavity of the reactor through heat conduction equipment. Connect an online gas chromatograph or online mass spectrometer to the gas phase outlet of the reactor, sample from the gas phase outlet of the reactor, detect hydrogen concentration / flow rate in real time, and plot instantaneous / cumulative hydrogen release curves to directly correspond to the dehydrogenation stage transitions, thereby judging in real time and quickly distinguishing the start-up stage, steady state stage, high load stage, and low load standby stage. The heat source control system drives the main heat source channel and auxiliary heat source channel to supply heat to the inner cavity of the reactor according to the corresponding stage of dehydrogenation.

[0007] Its further features are: The reactor is also equipped with a temperature sensor, which is connected to a heat source control system. The heat source control system supplies heat to the reactor cavity according to the corresponding stage of dehydrogenation and the real-time temperature and temperature change trend of the reactor cavity. During startup, both the main heat source channel and the auxiliary heat source channel supply heat to the reactor at maximum power, causing the reactor's internal temperature to rise rapidly to 200℃. In the steady-state phase, the auxiliary heat source channel is closed, and the output power of the main heat source channel is dynamically adjusted to ensure the reactor's temperature is dynamically maintained between 180℃ and 220℃. During the high-load phase, initially, the main heat source channel supplies heat at maximum power while the auxiliary heat source channel is opened to heat the reactor, using the temperature rise to accelerate the kinetic response. Once the reactor's temperature reaches 240℃, the auxiliary heat source channel is closed, and the output power of the main heat source channel is dynamically adjusted to ensure the reactor's temperature is maintained between 220℃ and 240℃. During the low-load standby phase, only the main heat source channel is opened, and its output power is dynamically adjusted to ensure the reactor's temperature is maintained between 100℃ and 180℃. The main heat source channel is equipped with an opening adjustment valve. When the opening adjustment valve is fully open, the main heat source channel is in the maximum power output state. When the opening adjustment valve is closed, the main heat source channel is closed. The input end of the main heat source channel is connected to at least two sets of heat sources. All heat sources are turned on at the same time or only one set of heat sources is turned on to supply heat to the main heat source channel. In the design, when one set of heat sources is under maintenance, the heat supply from the other heat sources can ensure the normal heat energy supply of the entire reactor during the dehydrogenation operation. The heat source for the main heat source channel is at least two of the following: electric heating, heat transfer oil, industrial waste heat, combustion flue gas, exhaust gas enthalpy recovery, or waste heat from fuel cells / engines. The auxiliary heat source channel is an electric heating mechanism integrated into the inner wall of the reactor. The combination of the electric heating mechanism and the main heat source channel is used to rapidly increase the temperature rise. In order to enable the main heat source channel to quickly heat the reactor during the start-up, steady-state and high-load phases, a heat storage unit is also integrated on the side of the main heat source channel. The excess heat generated by the heat source is stored in the heat storage unit during the low-load standby phase. When a large amount of heat is required, the heat energy of the heat storage unit is continuously transported to the reactor through the main heat source channel at the maximum output power, which saves heating time. During the low-load standby phase, at least one heat source normally supplies heat to the main heat source channel. By adjusting the opening regulating valve on the main heat source channel, some heat energy is dynamically supplied to the reactor, while the other part of the heat energy is bypassed and stored in the heat storage unit. When the temperature inside the reactor is greater than 175°C, the opening regulating valve is closed or adjusted to a smaller value. When the temperature inside the reactor is less than 105°C, the opening regulating valve is adjusted to a larger value, so that the temperature inside the reactor is maintained between 100°C and 180°C.

[0008] A device for heat source switching and thermal management of dehydrogenation of carbazole-based hydrogen storage carriers is characterized by comprising a heat source control system, a dehydrogenation stage analysis device, a main heat source system, an auxiliary heat source system, and a temperature sensor. The heat source control system is connected to the main heat source system, the auxiliary heat source system, the temperature sensor, and the dehydrogenation stage analysis equipment. The heat source control system is pre-set with the operating parameters of the main heat source system and the auxiliary heat source system under the corresponding temperature environment of the dehydrogenation stage.

[0009] Its further feature is that: the dehydrogenation stage analysis system includes a sampling end and an online gas chromatograph or an online mass spectrometer. The online gas chromatograph or online mass spectrometer samples from the gas phase outlet of the reactor through the sampling end, detects the hydrogen concentration / flow rate in real time, and plots the instantaneous / cumulative hydrogen release curve, which directly corresponds to the dehydrogenation stage broken line, thereby judging in real time and quickly distinguishing the start-up stage, steady state stage, high load stage, and low load standby stage. The temperature sensor is installed in the reactor and transmits the temperature to the heat source control system in real time via wireless or wired signals. The main heat source system includes a main heat source channel, at least two sets of branch heat source pipelines, at least two heat sources, a heat storage unit, and an opening regulating valve. The input end of the main heat source channel is connected to the corresponding heat source through the branch heat source pipeline. The main heat source channel is integrated with an opening regulating valve. A bypass heat storage unit is also provided in the main heat source channel at the position corresponding to the opening regulating valve. The output end of the heat storage unit is also connected to the output end of the main heat source channel through a one-way valve. The auxiliary heat source system is an electric heating mechanism integrated into the inner wall of the reactor.

[0010] By adopting this invention, different heat source priorities and switching conditions can be set according to the startup stage, steady-state stage, high-load stage, and low-load standby stage of the online gas chromatograph or online mass spectrometer in real time analysis, which can take into account the startup speed, steady-state efficiency, and dehydrogenation safety. Attached Figure Description

[0011] Figure 1 This is a schematic diagram of the device of the present invention; The names corresponding to the serial numbers in the diagram are as follows: Reactor 100; 10. Heat source control system; 20. Dehydrogenation stage analysis equipment; 21. Sampling end; 22. Online gas chromatograph or online mass spectrometer; 30. Main heat source system; 31. Main heat source channel; 32. Branch heat source pipeline; 33. Electric heating equipment; 34. Heat transfer oil equipment; 35. Heat storage unit; 36. Opening degree regulating valve; 37. One-way valve; 40. Auxiliary heat source system; 50. Temperature sensor. Detailed Implementation

[0012] A heat source switching thermal management method applicable to dehydrogenation of carbazole-based hydrogen storage carriers: The reactor is connected to a main heat source channel and at least one auxiliary heat source channel, and the main heat source channel and the auxiliary heat source channel are directly or indirectly connected to the inner cavity of the reactor through heat conduction equipment. Connect an online gas chromatograph or online mass spectrometer to the gas phase outlet of the reactor, sample from the gas phase outlet of the reactor, detect hydrogen concentration / flow rate in real time, and plot instantaneous / cumulative hydrogen release curves to directly correspond to the dehydrogenation stage transitions, thereby judging in real time and quickly distinguishing the start-up stage, steady state stage, high load stage, and low load standby stage. The heat source control system drives the main heat source channel and auxiliary heat source channel to supply heat to the inner cavity of the reactor according to the corresponding stage of dehydrogenation.

[0013] In practice, the reactor is also equipped with a temperature sensor, which is connected to the heat source control system. The heat source control system supplies heat to the reactor cavity according to the corresponding stage of dehydrogenation and the real-time temperature and temperature change trend of the reactor cavity. During startup, both the main heat source channel and the auxiliary heat source channel supply heat to the reactor at maximum power, causing the reactor's internal temperature to rise rapidly to 200℃. In the steady-state phase, the auxiliary heat source channel is closed, and the output power of the main heat source channel is dynamically adjusted to ensure the reactor's temperature is dynamically maintained between 180℃ and 220℃. During the high-load phase, initially, the main heat source channel supplies heat at maximum power while the auxiliary heat source channel is opened to heat the reactor, using the temperature rise to accelerate the kinetic response. Once the reactor's temperature reaches 240℃, the auxiliary heat source channel is closed, and the output power of the main heat source channel is dynamically adjusted to ensure the reactor's temperature is maintained between 220℃ and 240℃. During the low-load standby phase, only the main heat source channel is opened, and its output power is dynamically adjusted to ensure the reactor's temperature is maintained between 100℃ and 180℃. An opening regulating valve is installed on the main heat source channel. When the opening regulating valve is fully open, the main heat source channel is in the maximum power output state. When the opening regulating valve is closed, the main heat source channel is closed. At least two sets of heat sources are connected to the input end of the main heat source channel. All heat sources are turned on at the same time or only one set of heat sources is turned on to supply heat to the main heat source channel. During the design, when one set of heat sources is under maintenance, the heat supply from the other heat sources can ensure the normal heat energy supply of the entire reactor during the dehydrogenation operation. The heat source for the main heat source channel is at least two of the following: electric heating, heat transfer oil, industrial waste heat, combustion flue gas, exhaust gas enthalpy recovery, or waste heat from fuel cells / engines. The auxiliary heat source channel is an electric heating mechanism integrated into the inner wall of the reactor. The combination of the electric heating mechanism and the main heat source channel is used to rapidly increase the temperature rise. In order to enable the main heat source channel to quickly heat the reactor during the start-up, steady-state and high-load phases, a heat storage unit is also integrated on the side of the main heat source channel. The excess heat generated by the heat source is stored in the heat storage unit during the low-load standby phase. When a large amount of heat is required, the heat energy of the heat storage unit is continuously transported to the reactor through the main heat source channel at the maximum output power, which saves heating time. During the low-load standby phase, at least one heat source normally supplies heat to the main heat source channel. By adjusting the opening regulating valve on the main heat source channel, some heat energy is dynamically supplied to the reactor, while the other part of the heat energy is bypassed and stored in the heat storage unit. When the temperature inside the reactor is greater than 175°C, the opening regulating valve is closed or adjusted to a smaller value. When the temperature inside the reactor is less than 105°C, the opening regulating valve is adjusted to a larger value, so that the temperature inside the reactor is maintained between 100°C and 180°C.

[0014] For devices suitable for heat source switching thermal management of dehydrogenation of carbazole-based hydrogen storage carriers, see [link to relevant documentation]. Figure 1 It includes a heat source control system 10, a dehydrogenation stage analysis device 20, a main heat source system 30, an auxiliary heat source system 40, and a temperature sensor 50; The heat source control system 10 is connected to the main heat source system 30, the auxiliary heat source system 40, the temperature sensor 50, and the dehydrogenation stage analysis device 20. The heat source control system 10 is pre-set with the operating parameters of the main heat source system 30 and the auxiliary heat source system 40 under the corresponding temperature environment of the dehydrogenation stage.

[0015] In specific implementation, the dehydrogenation stage analysis system 20 includes a sampling end 21 and an online gas chromatograph or online mass spectrometer 22. The online gas chromatograph or online mass spectrometer 22 samples from the gas phase outlet of the reactor 100 through the sampling end 21, detects hydrogen concentration / flow rate in real time, plots instantaneous / cumulative hydrogen release curves, directly corresponding to the dehydrogenation stage broken line, thereby judging in real time and quickly distinguishing the start-up stage, steady state stage, high load stage, and low load standby stage. Temperature sensor 50 is installed in reactor 100 and transmits the temperature to heat source control system 10 in real time via wireless or wired signal; The main heat source system 30 includes a main heat source channel 31, two sets of branch heat source pipelines 32, an electric heating device 33, a heat transfer oil device 34, a heat storage unit 35, and an opening regulating valve 36. The input end of the main heat source channel 31 is connected to the corresponding electric heating device 33 and heat transfer oil device 34 through the branch heat source pipelines 32. The main heat source channel 31 is integrated with the opening regulating valve 36. A bypass heat storage unit 35 is also provided in the main heat source channel 31 at the position corresponding to the opening regulating valve 36. The output end of the heat storage unit 35 is also connected to the output end of the main heat source channel 31 through a one-way valve 37. The auxiliary heat source system 40 is an electric heating mechanism integrated into the inner wall of the reactor.

[0016] In specific implementation, during the start-up phase, no hydrogen flow is out. The heat source control system 10 drives the opening adjustment valve 36 of the main heat source channel 31 to open to the maximum. At the same time, the auxiliary heat source channel supplies heat to the reactor 100 at the maximum power, driving the electric heating equipment 33, the heat transfer oil equipment 34, and the heat storage unit 35 to perform heating operations, so that the temperature inside the reactor cavity rises rapidly to 200°C. In the steady state stage, after the temperature reaches 200℃, the hydrogen release gradually increases. The auxiliary heat source channel is closed, and the output power of the main heat source channel is dynamically adjusted by driving the opening degree regulating valve 36. Only one of the electric heating equipment 33 or the heat transfer oil equipment 34 is turned on to provide heat, ensuring that the temperature inside the reactor is dynamically maintained at 180~220℃. During the high-load phase, the hydrogen release reaches its peak and begins to rise. Initially, the heat source control system 10 drives the main heat source channel 31's opening regulating valve 36 to its maximum, while the auxiliary heat source channel supplies heat to the reactor 100 at maximum power, driving the electric heating device 33, the thermal oil device 34, and the heat storage unit 35 to perform heating operations. This temperature rise accelerates the kinetic response. When the temperature inside the reactor 100 reaches 240°C, the auxiliary heat source channel is closed. The output power of the main heat source channel is dynamically adjusted by driving the opening and closing degree of the opening regulating valve 36, so that only one of the electric heating device 33 or the thermal oil device 34 is turned on for heating, ensuring that the temperature inside the reactor is maintained at 220°C. 240℃; Low-load standby stage, at this time the hydrogen production is low, the carrier dehydrogenation is completed, the carrier is removed, and then only the main heat source channel 31 is opened, and only one of the electric heating equipment 33 or the heat transfer oil equipment 34 is turned on for heating. By adjusting the opening regulating valve 36 on the main heat source channel 31, part of the heat energy is dynamically supplied to the reactor, and the other part of the heat energy is bypassed and stored in the heat storage unit 35. When the temperature inside the reactor 100 is greater than 175℃, the opening regulating valve 36 is closed or adjusted to a smaller degree. When the temperature inside the reactor 100 is less than 105℃, the opening regulating valve 36 is adjusted to a larger degree, so that the temperature inside the reactor 100 is maintained between 100℃ and 180℃.

[0017] It sets different heat source priorities and switching conditions based on the real-time analysis of the online gas chromatograph or online mass spectrometer, which is in the start-up stage, steady-state stage, high-load stage, and low-load standby stage. It can take into account the start-up speed, steady-state efficiency, and dehydrogenation safety.

[0018] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0019] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A thermal management method for switching heat sources in the dehydrogenation of carbazole-based hydrogen storage carriers, characterized in that: The reactor is connected to a main heat source channel and at least one auxiliary heat source channel, and the main heat source channel and the auxiliary heat source channel are connected directly or indirectly to the inner cavity of the reactor through heat conduction equipment. Connect an online gas chromatograph or online mass spectrometer to the gas phase outlet of the reactor, sample from the gas phase outlet of the reactor, detect hydrogen concentration / flow rate in real time, and plot instantaneous / cumulative hydrogen release curves to directly correspond to the dehydrogenation stage transitions, thereby judging in real time and quickly distinguishing the start-up stage, steady state stage, high load stage, and low load standby stage. The heat source control system drives the main heat source channel and auxiliary heat source channel to supply heat to the inner cavity of the reactor according to the corresponding stage of dehydrogenation.

2. The thermal management method for switching heat sources for dehydrogenation of carbazole-based hydrogen storage carriers according to claim 1, characterized in that: The reactor is also equipped with a temperature sensor, which is connected to a heat source control system. The heat source control system supplies heat to the reactor cavity according to the corresponding stage of dehydrogenation and the real-time temperature and temperature change trend of the reactor cavity.

3. The thermal management method for switching heat sources for dehydrogenation of carbazole-based hydrogen storage carriers according to claim 2, characterized in that: During the start-up phase, both the main heat source channel and the auxiliary heat source channel supply heat to the reactor at maximum power, causing the reactor cavity temperature to rise rapidly to 200℃. During the steady-state phase, the auxiliary heat source channel is closed, and the output power of the main heat source channel is dynamically adjusted to ensure that the temperature inside the reactor is dynamically maintained between 180℃ and 220℃. During the high-load phase, the main heat source channel initially supplies heat at maximum power, while the auxiliary heat source channel is opened to supply heat to the reactor, using the temperature rise to accelerate the kinetic response. When the temperature inside the reactor reaches 240℃, the auxiliary heat source channel is closed, and the output power of the main heat source channel is dynamically adjusted to ensure that the temperature inside the reactor is maintained between 220℃ and 240℃. During the low-load standby phase, only the main heat source channel is turned on, and the output power of the main heat source channel is dynamically adjusted to ensure that the temperature inside the reactor is maintained between 100℃ and 180℃.

4. The thermal management method for switching heat sources for dehydrogenation of carbazole-based hydrogen storage carriers according to claim 2, characterized in that: The main heat source channel is equipped with an opening regulating valve. When the opening regulating valve is fully open, the main heat source channel is in the maximum power output state. When the opening regulating valve is closed, the main heat source channel is closed.

5. The thermal management method for switching heat sources for dehydrogenation of carbazole-based hydrogen storage carriers according to claim 2, characterized in that: The input end of the main heat source channel is connected to at least two sets of heat sources. All heat sources can be turned on at the same time or only one set of heat sources can be turned on to supply heat to the main heat source channel. In the design, when one set of heat sources is under maintenance, the heat supply from the other heat sources can ensure the normal heat energy supply of the entire reactor during the dehydrogenation operation.

6. The thermal management method for switching heat sources for dehydrogenation of carbazole-based hydrogen storage carriers according to claim 5, characterized in that: The heat source for the main heat source channel is at least two of the following: electric heating, heat transfer oil, industrial waste heat, combustion flue gas, exhaust gas enthalpy recovery, or waste heat from fuel cells / engines.

7. The thermal management method for switching heat sources for dehydrogenation of carbazole-based hydrogen storage carriers according to claim 2, characterized in that: The auxiliary heat source channel is an electric heating mechanism integrated into the inner wall of the reactor. The combination of the electric heating mechanism and the main heat source channel is used to rapidly increase the temperature rise.

8. The thermal management method for switching heat sources for dehydrogenation of carbazole-based hydrogen storage carriers according to claim 2, characterized in that: In order to enable the main heat source channel to quickly heat the reactor during the start-up, steady-state, and high-load phases, a heat storage unit is also integrated on the side of the main heat source channel. The excess heat generated by the heat source is stored in the heat storage unit during the low-load standby phase. When a large amount of heat is required, the heat energy of the heat storage unit is continuously transported to the reactor through the main heat source channel at the maximum output power.

9. An apparatus for heat source switching thermal management of dehydrogenation of carbazole-based hydrogen storage carriers, wherein the apparatus is applied to the heat source switching thermal management method for dehydrogenation of carbazole-based hydrogen storage carriers as described in any one of claims 1-8, characterized in that: It includes a heat source control system, dehydrogenation stage analysis equipment, main heat source system, auxiliary heat source system, and temperature sensors; The heat source control system is connected to the main heat source system, the auxiliary heat source system, the temperature sensor, and the dehydrogenation stage analysis equipment. The heat source control system is pre-set with the operating parameters of the main heat source system and the auxiliary heat source system under the corresponding temperature environment of the dehydrogenation stage.

10. The device for heat source switching thermal management of dehydrogenation of carbazole-based hydrogen storage carriers according to claim 9, characterized in that: The main heat source system includes a main heat source channel, at least two sets of branch heat source pipelines, at least two heat sources, a heat storage unit, and an opening regulating valve. The input end of the main heat source channel is connected to the corresponding heat source through the branch heat source pipeline. The main heat source channel is integrated with an opening regulating valve. A bypass heat storage unit is also provided in the main heat source channel at the position corresponding to the opening regulating valve. The output end of the heat storage unit is also connected to the output end of the main heat source channel through a one-way valve.

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