Liquid organic hydrogen storage and dehydrogenation system and method coupled with solid oxide fuel cell and application

Abstract

The invention provides a liquid organic hydrogen storage and dehydrogenation system and method coupled with a solid oxide fuel cell and application. The system comprises a hydrogen storage unit used for storing a liquid organic hydrogen-rich material; the dehydrogenation unit is used for carrying out dehydrogenation reaction on the liquid organic hydrogen-rich material to obtain hydrogen and an organic hydrogen storage material; the combustion unit comprises a solid oxide fuel cell, and the solid oxide fuel cell carries out combustion by taking the hydrogen generated by the dehydrogenation unit as fuel and generates combustion tail gas; the heat distribution unit comprises a plurality of heat distribution devices, and at least one heat distribution device is used for collecting heat generated after the organic hydrogen storage material obtained through dehydrogenation is cooled and heat of the combustion tail gas and transmitting the heat to the dehydrogenation unit and the solid oxide fuel cell.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen storage for fuel cells, and particularly to a liquid organic hydrogen storage dehydrogenation system, method and application coupled with a solid oxide fuel cell. Background Art

[0002] A solid oxide fuel cell (SOFC) is an energy conversion device that directly converts the chemical energy of fuel into electrical energy, with high energy conversion efficiency, and has advantages such as wide fuel adaptability, clean and pollution-free, all-solid-state structure, and no use of precious metal catalysts. SOFC can efficiently and greenly utilize hydrogen energy. However, the power generation efficiency of solid oxide fuel cells is often about 50%, and the remaining energy is wasted in the form of heat.

[0003] Currently, relatively mature and promising hydrogen storage technologies include high-pressure gaseous hydrogen storage, cryogenic liquid hydrogen storage, solid alloy hydrogen storage, and organic liquid hydrogen storage. High-pressure gaseous hydrogen storage and cryogenic liquid hydrogen storage have disadvantages such as high safety risks, low volumetric hydrogen storage density, and high energy consumption for pressurization or liquefaction. For the solid alloy hydrogen storage technology, the hydrogen storage materials often have a relatively high hydrogen release temperature, high energy consumption, and increased costs. The organic liquid hydrogen storage technology does not require pressure-resistant containers and cryogenic equipment during hydrogen storage and transportation, and hydrogen can be generated and released through a dehydrogenation reaction, which has great advantages in terms of safety, hydrogen storage density, and transportation efficiency. In existing organic liquid hydrogen storage technologies, heat needs to be absorbed during the dehydrogenation reaction to release hydrogen. Therefore, in existing technologies, the dehydrogenation system often requires external auxiliary heating, resulting in high energy consumption. In addition, the heat of the hydrogen-depleted material generated after dehydrogenation usually cannot be effectively utilized, and the energy utilization rate is low. Summary of the Invention

[0004] To solve one of the above technical problems existing in the prior art, the present invention provides a liquid organic hydrogen storage dehydrogenation system coupled with a solid oxide fuel cell, as well as a heat regulation method for the SOFC-coupled organic hydrogen storage dehydrogenation system. The system and method of the present invention can realize the waste heat utilization of solid oxide fuel cells and precise heat management in the SOFC-coupled liquid organic hydrogen storage dehydrogenation system. In addition, the present invention also provides the application of the system, especially in the operation of transportation vehicles.

[0005] The first aspect of the present invention provides a liquid organic hydrogen storage dehydrogenation system coupled with a solid oxide fuel cell, comprising:

[0006] A hydrogen storage unit for storing a liquid organic hydrogen-rich material;

[0007] A dehydrogenation unit for dehydrogenating the liquid organic hydrogen-rich material to obtain hydrogen and an organic hydrogen storage material;

[0008] A combustion unit, which includes a solid oxide fuel cell that burns using the hydrogen gas generated by the dehydrogenation unit as fuel and produces combustion exhaust gas;

[0009] A heat distribution unit, which includes a plurality of heat distribution devices, and at least one heat distribution device is used to collect and distribute the heat generated by cooling the organic hydrogen storage material obtained by the dehydrogenation unit and the heat of the combustion exhaust gas generated by the combustion unit to the dehydrogenation unit and the combustion unit.

[0010] Furthermore, the dehydrogenation unit of the present invention includes a heating device and a dehydrogenation reactor. The heating device is used to heat the liquid organic hydrogen-rich material from the hydrogen storage unit to the dehydrogenation reaction temperature, and the dehydrogenation reactor contains a dehydrogenation catalyst.

[0011] Furthermore, a first regulating device is also connected between the hydrogen storage unit and the heating device of the dehydrogenation unit. The first regulating device is used to regulate the flow rate and / or pressure of the liquid organic hydrogen-rich material entering the dehydrogenation unit from the hydrogen storage unit.

[0012] Furthermore, the system also includes a gas-liquid separation unit. The gas-liquid separation unit includes a gas-liquid separator, a gas storage tank, and a liquid storage tank. The gas-liquid separator is used to separate the hydrogen gas and the organic hydrogen storage material generated by the dehydrogenation unit. The gas storage tank is used to receive the hydrogen gas separated from the gas-liquid separator, and the liquid storage tank is used to receive the cooled organic hydrogen storage material. Further, the gas-liquid separation unit is directly connected to the dehydrogenation reactor in the dehydrogenation reaction unit.

[0013] Furthermore, a second regulating device is also connected between the gas-liquid separator of the gas-liquid separation unit and the gas storage tank. The second regulating device is used to prevent the hydrogen gas in the gas storage tank from flowing back into the gas-liquid separator. Preferably, the second regulating device is a one-way regulating device, such as a back pressure valve.

[0014] Furthermore, the gas-liquid separation unit and the heat distribution unit are connected by a pipeline filled with a heat transfer medium. The heat transfer medium exchanges heat with the organic hydrogen storage material generated by dehydrogenation and transfers the heat to the heat distribution unit.

[0015] Furthermore, the combustion unit and the heat distribution unit are connected by a pipeline filled with a heat transfer medium. The heat transfer medium exchanges heat with the combustion exhaust gas generated by the solid oxide fuel cell and transfers the heat to the heat distribution unit.

[0016] Further, the system further includes a preheating unit configured to preheat hydrogen before the hydrogen enters the solid oxide fuel cell. Further, the preheating unit is directly connected to the solid oxide fuel cell. Still further, a third regulating device is connected between the preheating unit and the gas storage tank of the gas-liquid separation unit, and the third regulating device is used to regulate the pressure and / or flow rate of the hydrogen entering the solid oxide fuel cell unit.

[0017] Further, the heat distribution unit includes a first heat distribution device configured to collect and distribute the heat generated by cooling the organic hydrogen storage material produced by the dehydrogenation unit and the heat of the combustion exhaust gas produced by the combustion unit to the dehydrogenation reactor in the dehydrogenation unit and the combustion unit to maintain the operating temperature of the dehydrogenation reactor and the operating temperature of the solid oxide fuel cell.

[0018] Further, the first heat distribution device is connected to the gas-liquid separator and the solid oxide fuel cell through pipes filled with a heat transfer medium. The heat transfer medium exchanges heat with the organic hydrogen storage material and the combustion exhaust gas, and transfers the heat generated by cooling the organic hydrogen storage material and the heat of the combustion exhaust gas to the first heat distribution unit.

[0019] Further, the heat distribution unit further includes a second heat distribution device connected to the first distribution device, and the second heat distribution device is configured to redistribute the heat distributed from the first heat distribution device to the dehydrogenation reactor in the dehydrogenation unit, the heating device in the dehydrogenation unit, and / or the preheating unit.

[0020] Further, the heat distribution unit further includes a third heat distribution device and / or a fourth heat distribution device connected to the second heat distribution device. The third heat distribution device is configured to redistribute the heat distributed from the second heat distribution device to the preheating unit to heat the hydrogen entering the solid oxide fuel cell; the fourth heat distribution device is configured to redistribute the heat distributed from the second heat distribution device to the heating device of the dehydrogenation unit to heat the liquid organic hydrogen-rich material to the dehydrogenation reaction temperature.

[0021] Further, the system further includes a first auxiliary heating device configured to assist the heating device in the dehydrogenation unit to heat the liquid organic hydrogen-rich material when the liquid organic hydrogen-rich material cannot reach the optimal operating temperature of the dehydrogenation unit at the start of the system.

[0022] Further, the system further includes: a second auxiliary heating device configured to heat the dehydrogenation reactor to maintain the required dehydrogenation reaction temperature.

[0023] Further, the system further includes: a third auxiliary heating device configured to assist the preheating unit in heating hydrogen when the hydrogen cannot reach the operating temperature of the solid oxide fuel cell.

[0024] Further, the system further includes: a fourth auxiliary heating device configured to heat the solid oxide fuel cell during cold start to rapidly bring the solid oxide fuel cell to the operating temperature.

[0025] In the present invention, the heating devices, preheating unit, first auxiliary heating device, second auxiliary heating device, third auxiliary heating device, and fourth auxiliary heating device in the dehydrogenation unit may adopt the same or different heating methods. Conventional heating methods in the art may be selected, or new heating methods in the art may be adopted, such as: pulse heating, microwave heating, Joule heating, heat conduction frame heating, electromagnetic heating, etc.

[0026] Further, the heating method adopted by the first auxiliary heating device is microwave heating, the heating method adopted by the second auxiliary heating device is electromagnetic heating, the heating method adopted by the third auxiliary heating device is Joule heating, and the heating method adopted by the fourth auxiliary heating device is pulse heating.

[0027] In a second aspect, the present invention provides a heat regulation method for a SOFC-coupled organic hydrogen storage and dehydrogenation system, including the following steps:

[0028] (1) Subjecting the liquid organic hydrogen-rich material to a dehydrogenation reaction to obtain hydrogen and an organic hydrogen storage material, and cooling the organic hydrogen storage material to generate heat;

[0029] (2) Passing the hydrogen obtained in step (1) into a solid oxide fuel cell for combustion to obtain combustion exhaust gas;

[0030] (3) Collecting the heat generated in step (1) and the heat of the combustion exhaust gas obtained in step (2) and using them to maintain the dehydrogenation reaction temperature of the liquid organic hydrogen-rich material and the operating temperature of the solid oxide fuel cell.

[0031] Further, the liquid organic hydrogen-rich material described in step (1) includes at least one of hydrogenation products of C2-C20 olefins, hydrogenation products of C2-C20 alkynes, hydrogenation products of C6-C20 aromatics, and hydrogenation products of C3-C20 heteroaromatics; preferably, it includes at least one of cyclohexane, methylcyclohexane, cyclohexylbenzene, hydrogenation products of xylene, hydrogenation products of dibenzyltoluene, hydrogenation products of ethylcarbazole, and hydrogenation products of propylcarbazole.

[0032] Further, in step (3), the heat generated in step (1) and the heat of the combustion exhaust gas obtained in step (2) are collected and further used for heating the liquid organic hydrogen-rich material before dehydrogenation reaction.

[0033] Further, in step (3), the heat generated in step (1) and the heat of the combustion exhaust gas obtained in step (2) are collected and further used for preheating hydrogen before entering the solid oxide fuel cell.

[0034] Further, in step (1), the dehydrogenation reaction is carried out in a dehydrogenation reactor, and the cooling of the organic hydrogen storage material is carried out in a gas-liquid separator; in step (3), after the heat is collected, a heat distributor is used to distribute the heat to the dehydrogenation reactor and the solid oxide fuel cell.

[0035] Further, the dehydrogenation reactor is filled with a dehydrogenation catalyst, and the dehydrogenation catalyst includes at least one of nickel-based catalysts, palladium-based catalysts, platinum-based catalysts, ruthenium-based catalysts, and rhodium-based catalysts.

[0036] In a third aspect, the present invention provides an application of the above-mentioned liquid organic hydrogen storage dehydrogenation system coupled with a solid oxide fuel cell in the operation of a vehicle.

[0037] The vehicle of the present invention includes but is not limited to at least one of a bus, a heavy truck, a high-speed train, and a large ship.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] 1. By coupling the solid oxide fuel cell with the liquid organic hydrogen storage dehydrogenation unit, the present invention can use the heat generated in the dehydrogenation process to maintain the operating temperature of the solid oxide fuel cell; it can also use the heat generated by the combustion of the solid oxide fuel cell for the dehydrogenation process of the liquid organic hydrogen storage material, achieving the maximum utilization of heat.

[0040] 2. By using multiple heat distributors, the present invention can also achieve an accurate balance between the dehydrogenation of liquid organic hydrogen storage materials and the heat required for the combustion of solid oxide fuel cells, that is, the heat released after the fuel cell combustion exactly matches the heat of dehydrogenation, and the heat released after the battery combustion just meets the operating temperature of the SOFC, enabling refined control in system heat management.

[0041] 3. The system structure of the present invention is simple and highly operable, and can provide the released heat as the power for the operation of vehicles, having broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 FIG. shows a schematic diagram of a liquid organic hydrogen storage dehydrogenation system coupled with a solid oxide fuel cell according to a specific embodiment of the present invention, where 1: hydrogen storage device, 2: regulating valve; 3: heating device; 4: dehydrogenation reactor; 5: gas-liquid separator, 6: back pressure valve; 7: gas storage tank; 8: regulating valve; 9: preheating device; 10: solid oxide fuel cell; 11: heat distributor; 12: heat distributor; 13: heat distributor; 14: heat distributor; 15: liquid storage tank; 16: microwave heating device; 17: electromagnetic heating device; 18: Joule heating device; 19: pulse heating device. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0043] To make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the embodiments and the drawings. The specific embodiments described herein are only used to explain the present invention and do not constitute any limitation to the present invention.

[0044] The term "solid oxide fuel cell" (abbreviated as SOFC) used herein belongs to the third generation of fuel cells. It uses an oxide ion conductor as the electrolyte, supplies fuel gases such as hydrogen at the anode, supplies air at the cathode, and directly and efficiently converts the chemical energy stored in the fuel and oxidant into electrical energy in an environmentally friendly manner at medium and high temperatures, and is a fuel cell with the highest theoretical energy density.

[0045] The term "organic hydrogen storage material" or "liquid organic hydrogen storage material" used herein refers to some unsaturated liquid organic compounds that can undergo a reversible reaction with hydrogen, store hydrogen through a hydrogenation reaction (chemical bonding), and release hydrogen through a dehydrogenation reaction. Specific types of liquid organic hydrogen storage materials include, for example: olefins, alkynes, aromatic hydrocarbons, heteroaromatic hydrocarbons, etc.

[0046] The term "liquid organic hydrogen-rich material" used herein corresponds to the material obtained after the above-mentioned "organic hydrogen storage material" or "liquid organic hydrogen storage material" stores hydrogen through a hydrogenation reaction.

[0047] As used herein, the term "heat distribution device" refers to any device for distributing thermal energy in the form of heat.

[0048] As a specific embodiment of the present invention, a liquid organic hydrogen storage dehydrogenation system coupled with a solid oxide fuel cell includes:

[0049] A hydrogen storage unit for storing a liquid organic hydrogen-rich material;

[0050] A dehydrogenation unit for dehydrogenating the liquid organic hydrogen-rich material to obtain hydrogen and an organic hydrogen storage material;

[0051] A combustion unit including a solid oxide fuel cell, which burns using the hydrogen generated by the dehydrogenation unit as fuel and generates combustion exhaust gas;

[0052] A heat distribution unit including a plurality of heat distribution devices, wherein at least one heat distribution device is used to collect and distribute the heat generated by cooling the organic hydrogen storage material obtained by the dehydrogenation unit and the heat of the combustion exhaust gas generated by the combustion unit to the dehydrogenation unit and the combustion unit.

[0053] In some specific embodiments, the liquid organic hydrogen-rich material includes at least one of hydrogenation products of C2-C20 olefins, hydrogenation products of C2-C20 alkynes, hydrogenation products of C6-C20 aromatics, and hydrogenation products of C3-C20 heteroaromatics. In some preferred embodiments, the liquid organic hydrogen-rich material includes at least one of cyclohexane, methylcyclohexane, cyclohexylbenzene, hydrogenation product of toluene, hydrogenation product of dibenzyltoluene, hydrogenation product of ethylcarbazole, and hydrogenation product of propylcarbazole.

[0054] In some specific embodiments, the dehydrogenation unit includes a heating device and a dehydrogenation reactor. The heating device is used to heat the liquid organic hydrogen-rich material from the hydrogen storage unit to the dehydrogenation reaction temperature, and the dehydrogenation reactor contains a dehydrogenation catalyst. In some specific embodiments, the dehydrogenation catalyst includes at least one of a nickel-based catalyst, a palladium-based catalyst, a platinum-based catalyst, a ruthenium-based catalyst, and a rhodium-based catalyst.

[0055] In some specific embodiments, a first regulating device is further connected between the hydrogen storage unit and the heating device of the dehydrogenation unit. The first regulating device is used to regulate the flow rate and / or pressure of the liquid organic hydrogen-rich material entering the dehydrogenation unit from the hydrogen storage unit.

[0056] In some specific embodiments, the system further includes a gas-liquid separation unit, which includes a gas-liquid separator, a gas storage tank, and a liquid storage tank. The gas-liquid separator is used to separate the hydrogen gas and the organic hydrogen storage material generated by the dehydrogenation unit. The gas storage tank is used to receive the hydrogen gas separated by the gas-liquid separator, and the liquid storage tank is used to receive the organic hydrogen storage material separated by the gas-liquid separator. In some specific embodiments, the organic hydrogen storage material is cooled in the gas-liquid separator and then enters the liquid storage tank.

[0057] In some specific embodiments, the gas-liquid separation unit is directly connected to the dehydrogenation reactor in the dehydrogenation reaction unit.

[0058] In some specific embodiments, a second regulating device is further connected between the gas-liquid separator of the gas-liquid separation unit and the gas storage tank. The second regulating device is used to prevent the hydrogen gas in the gas storage tank from flowing back into the gas-liquid separator. In some specific embodiments, the second regulating device is a one-way regulating device, preferably a back pressure valve.

[0059] In some specific embodiments, the gas-liquid separation unit is connected to the heat distribution unit through a pipeline filled with a heat transfer medium. The heat transfer medium exchanges heat with the organic hydrogen storage material and transfers the heat generated by cooling the organic hydrogen storage material to the heat distribution unit.

[0060] In some specific embodiments, the gas-liquid separator of the gas-liquid separation unit is connected to the heat distribution unit through a pipeline filled with a heat transfer medium. The heat transfer medium exchanges heat with the organic hydrogen storage material generated by dehydrogenation and transfers the heat generated by cooling the organic hydrogen storage material to the heat distribution unit.

[0061] In some specific embodiments, the combustion unit is connected to the heat distribution unit through a pipeline filled with a heat transfer medium. The heat transfer medium exchanges heat with the combustion exhaust gas generated by the solid oxide fuel cell and transfers the heat of the combustion exhaust gas to the heat distribution unit.

[0062] In some specific embodiments, the solid oxide fuel cell is connected to the heat distribution unit through a pipeline filled with a heat transfer medium. The heat transfer medium exchanges heat with the combustion exhaust gas generated by the solid oxide fuel cell and transfers the heat of the combustion exhaust gas to the heat distribution unit.

[0063] The heat transfer medium of the present invention includes, but is not limited to: liquid media, gas media, etc.

[0064] In some specific embodiments, the system further includes a preheating unit configured to preheat hydrogen before it enters the solid oxide fuel cell. In some specific embodiments, the preheating unit is directly connected to the solid oxide fuel cell. In some specific embodiments, a third regulating device is connected between the preheating unit and the gas storage tank of the gas-liquid separation unit, and the third regulating device is used to regulate the pressure and / or flow rate of the hydrogen entering the solid oxide fuel cell unit.

[0065] In some specific embodiments, the heat distribution unit includes 2 to 6 (such as 2, 3, 4, 5, 6) heat distribution devices.

[0066] In some specific embodiments, the heat distribution unit includes a first heat distribution device configured to collect and distribute the heat generated by cooling the organic hydrogen storage material produced by the dehydrogenation unit and the heat of the combustion exhaust gas produced by the combustion unit to the dehydrogenation reactor in the dehydrogenation unit and the combustion unit to maintain the operating temperature of the dehydrogenation reactor and the operating temperature of the solid oxide fuel cell.

[0067] In some specific embodiments, the first heat distribution device is connected to the gas-liquid separator through a pipeline filled with a heat transfer medium, and the heat transfer medium exchanges heat with the organic hydrogen storage material and transfers the heat generated by cooling the organic hydrogen storage material to the first heat distribution unit.

[0068] In some specific embodiments, the first heat distribution device is connected to the solid oxide fuel cell through a pipeline filled with a heat transfer medium, and the heat transfer medium exchanges heat with the combustion exhaust gas and transfers the heat of the combustion exhaust gas to the first heat distribution unit.

[0069] In some specific embodiments, the heat distribution unit further includes a second heat distribution device connected to the first distribution device, and the second heat distribution device is configured to redistribute the heat distributed from the first heat distribution device to the dehydrogenation reactor in the dehydrogenation unit, the heating device in the dehydrogenation unit, and / or the preheating unit.

[0070] In some specific embodiments, the heat distribution unit further includes a third heat distribution device connected to the second heat distribution device, and the third heat distribution device is configured to redistribute the heat distributed from the second heat distribution device to the preheating unit to heat the hydrogen entering the solid oxide fuel cell.

[0071] In some specific embodiments, the heat distribution unit further includes a fourth heat distribution device connected to the second heat distribution device. The fourth heat distribution device is configured to redistribute the heat distributed from the second heat distribution device to the heating device of the dehydrogenation unit, so as to heat the liquid organic hydrogen-rich material to the dehydrogenation reaction temperature.

[0072] In some specific embodiments, the system further includes: a first auxiliary heating device, which is configured to assist the heating device in the dehydrogenation unit to heat the liquid organic hydrogen-rich material when the liquid organic hydrogen-rich material cannot reach the optimal operating temperature of the dehydrogenation unit at the start of the system.

[0073] In some specific embodiments, the system further includes: a second auxiliary heating device, which is configured to heat the dehydrogenation reactor to maintain the required dehydrogenation reaction temperature.

[0074] In some specific embodiments, the system further includes: a third auxiliary heating device, which is configured to assist the preheating unit to heat hydrogen when the hydrogen cannot reach the operating temperature of the solid oxide fuel cell.

[0075] In some specific embodiments, the system further includes: a fourth auxiliary heating device, which is configured to heat the solid oxide fuel cell during cold start to enable the solid oxide fuel cell to quickly reach the operating temperature.

[0076] In some specific embodiments, the heating devices in the dehydrogenation unit, the preheating unit, the first auxiliary heating device, the second auxiliary heating device, the third auxiliary heating device, and the fourth auxiliary heating device adopt the same heating method.

[0077] In some specific embodiments, the heating devices in the dehydrogenation unit, the preheating unit, the first auxiliary heating device, the second auxiliary heating device, the third auxiliary heating device, and the fourth auxiliary heating device adopt different heating methods.

[0078] In some specific embodiments, the heating methods adopted by the heating devices in the dehydrogenation unit, the preheating unit, the first auxiliary heating device, the second auxiliary heating device, the third auxiliary heating device, and the fourth auxiliary heating device include at least one of pulse heating, microwave heating, Joule heating, heat conduction frame heating, and electromagnetic heating.

[0079] In some specific embodiments, the heating method adopted by the first auxiliary heating device is microwave heating, the heating method adopted by the second auxiliary heating device is electromagnetic heating, the heating method adopted by the third auxiliary heating device is Joule heating, and the heating method adopted by the fourth auxiliary heating device is pulse heating.

[0080] In the present invention, the solid oxide fuel cell in the combustion unit may be composed of multiple stacks, and by setting multi-level regulation, such as adjusting the opening of the electric valve, the radiator power, etc., the operating temperature of each stack can be maintained within the optimal working temperature range.

[0081] In some embodiments, the system further includes a coupling unit, which is used to connect the circulation path of the cooling medium of the solid oxide fuel cell stack with the circulation path of the cooling medium of the hydrogen storage unit. The coupling unit can not only realize the further recycling of heat, but also accelerate the process of the system warming up to the working temperature.

[0082] In the present invention, heat transfer in the dehydrogenation stage can be achieved by setting multi-level hydrogen storage devices in the hydrogen storage unit, so as to be better used for subsequent thermal management.

[0083] As a specific embodiment of the present invention, the heat regulation method of the SOFC-coupled organic hydrogen storage dehydrogenation system includes the following steps:

[0084] (1) Subject the liquid organic hydrogen-rich material to a dehydrogenation reaction to obtain hydrogen and an organic hydrogen storage material, and cool the organic hydrogen storage material to generate heat;

[0085] (2) Pass the hydrogen obtained in step (1) into the solid oxide fuel cell for combustion to obtain combustion exhaust gas;

[0086] (3) Collect the heat generated in step (1) and the heat of the combustion exhaust gas obtained in step (2) and use them to maintain the dehydrogenation reaction temperature of the liquid organic hydrogen-rich material and the working temperature of the solid oxide fuel cell.

[0087] In some embodiments, the liquid organic hydrogen-rich material in step (1) includes but is not limited to: hydrogenation products of C2-C20 olefins, hydrogenation products of C2-C20 alkynes, hydrogenation products of C6-C20 aromatics, hydrogenation products of C3-C20 heteroaromatics, etc. Examples of the liquid organic hydrogen-rich material are: cyclohexane, methylcyclohexane, cyclohexylbenzene, hydrogenation products of xylene, hydrogenation products of dibenzyltoluene, hydrogenation products of ethylcarbazole, and hydrogenation products of propylcarbazole, etc.

[0088] In some embodiments, in step (3), the heat generated in step (1) and the heat of the combustion exhaust gas obtained in step (2) are collected and also used for heating the liquid organic hydrogen-rich material before the dehydrogenation reaction.

[0089] In some embodiments, in step (3), the heat generated in step (1) and the heat of the combustion exhaust gas obtained in step (2) are collected and also used for preheating the hydrogen before it enters the solid oxide fuel cell.

[0090] In some embodiments, in step (1), the dehydrogenation reaction is carried out in a dehydrogenation reactor, and the cooling of the organic hydrogen storage material is carried out in a gas-liquid separator; in step (3), after the heat is collected, a heat distributor is used to distribute the heat to the dehydrogenation reactor and the solid oxide fuel cell.

[0091] In some embodiments, the dehydrogenation reactor is filled with a dehydrogenation catalyst, and the dehydrogenation catalyst includes at least one of a nickel-based catalyst, a palladium-based catalyst, a platinum-based catalyst, a ruthenium-based catalyst, and a rhodium-based catalyst.

[0092] As Figure 1 shown, according to a specific embodiment of the present invention, a liquid organic hydrogen storage dehydrogenation system coupled with a solid oxide fuel cell includes: a hydrogen storage device 1, a heating device 3, a dehydrogenation reactor 4, a gas-liquid separator 5, a gas storage tank 7, a preheating device 9, a solid oxide fuel cell 10, a heat distributor 11, a heat distributor 12, a heat distributor 13, and a heat distributor 14, which are connected in sequence; wherein, a regulating valve 2 is connected between the hydrogen storage device 1 and the heating device 3 to regulate the flow rate and pressure of the liquid organic hydrogen-rich material entering the heating device 3; a back pressure valve 6 is connected between the gas-liquid separator 5 and the gas storage tank 7 to prevent the hydrogen in the gas storage tank 7 from flowing back to the gas-liquid separator 5; a regulating valve 8 is connected between the gas storage tank 7 and the preheating device to regulate the flow rate and pressure of the hydrogen entering the preheating device 9; a liquid storage tank 15 is connected to the gas-liquid separator 5 to receive the separated liquid; one port of the heat distributor 11 is connected to the solid oxide fuel cell 10, and one port is connected to the heat distributor 13; one port of the heat distributor 13 is connected to the dehydrogenation reactor 4, one port is connected to the heat distributor 14, and one port is connected to the heat distributor 12; one port of the heat distributor 12 is connected to the preheating device 9; one port of the heat distributor 14 is connected to the heating device 3.

[0093] Figure 1 In, "→" represents the gas flow direction, represents the material flow direction, represents the heat flow direction represents a valve, represents a safety valve, represents a pump.

[0094] In the above system, liquid organic hydrogen-rich materials such as xylene hydrogenation products, dibenzyltoluene hydrogenation products, ethylcarbazole hydrogenation products, and propylcarbazole hydrogenation products are stored in the hydrogen storage device 1 and enter the heating device 3 at a certain flow rate and pressure under the action of the regulating valve 2 to be heated to the dehydrogenation reaction temperature; the dehydrogenation reactor 4 is filled with dehydrogenation catalysts such as nickel-based catalysts, palladium-based catalysts, platinum-based catalysts, ruthenium-based catalysts, or rhodium-based catalysts. The liquid organic hydrogen-rich material heated to the reaction temperature by the heating device 3 undergoes a dehydrogenation reaction under the action of the catalyst in the dehydrogenation reactor 4 to obtain hydrogen and organic hydrogen storage materials (i.e., "liquid organic hydrogen-rich materials after dehydrogenation"); the hydrogen and organic hydrogen storage materials enter the gas-liquid separator 5 for gas-liquid separation. The separated hydrogen enters the gas storage tank 7, and a backpressure valve 6 is provided to prevent the hydrogen from flowing back to the gas-liquid separator 5. The separated organic hydrogen storage materials enter the liquid storage tank 15 after being cooled; the hydrogen in the gas storage tank first enters the preheating device 9 at a certain flow rate and pressure for preheating treatment, and after reaching the preset temperature, it enters the solid oxide fuel cell 10 for combustion, releasing heat and generating combustion exhaust gas; both between the gas-liquid separator 5 and the heat distributor 11 and between the solid oxide fuel cell 10 and the heat distributor 11 are connected by pipes filled with a heat transfer medium. The heat transfer medium exchanges heat with the organic hydrogen storage materials separated from the gas-liquid separator 5 and transfers the heat to the heat distributor 11. The organic hydrogen storage materials enter the liquid storage tank 15 after being cooled; the heat transfer medium exchanges heat with the combustion exhaust gas discharged from the solid oxide fuel cell 10 and transfers the heat to the heat distributor 11. The heat distributor 11 distributes a part of the heat to the dehydrogenation reactor 4 to maintain the optimal working temperature of the dehydrogenation reaction; at the same time, it distributes a part of the heat to the solid oxide fuel cell 10 to maintain the optimal working temperature of the solid oxide fuel cell. In addition, the heat distribution device 13 can also redistribute the heat distributed from the heat distributor 11, that is: distribute a part of the heat to the dehydrogenation reactor 4 to maintain the optimal working temperature of the dehydrogenation reaction, a part of the heat to the heat distributor 14 to cooperate with the heating device 3 to heat the liquid organic hydrogen-rich materials entering the dehydrogenation reactor; a part of the heat to the heat distributor 12 to cooperate with the preheating device 9 to heat the hydrogen entering the solid oxide fuel cell. In this way, the heat generated by cooling the dehydrogenated liquid organic hydrogen storage materials and the heat of the combustion exhaust gas generated by the combustion of the solid oxide fuel cell can be collected and transmitted back to other components in the system that require heat consumption, realizing the recycling of heat and maximizing the energy utilization. In addition, by adjusting the parameters of each heat distribution device, fine management and utilization of heat in the system can be achieved. For example, the heat released by the combustion of the solid oxide fuel cell 10 is just matched with the heat generated by the dehydrogenation reaction, and the heat released by the combustion of the battery just meets the working temperature of the solid oxide fuel cell 10.

[0095] Furthermore, the above system further includes four auxiliary heating devices (see the Figure 1 dashed-line box in): a microwave heating device 16, an electromagnetic heating device 17, a Joule heating device 18, and a pulse heating device 19. Among them, the microwave heating device 16 is used to heat the liquid organic hydrogen-rich material by the auxiliary heating device 3 when the liquid organic hydrogen-rich material cannot reach the optimal working temperature of the dehydrogenation reactor 4 at the start of the system; the electromagnetic heating device 17 is used to heat the dehydrogenation reactor 4 to maintain the required dehydrogenation reaction temperature; the Joule heating device 18 is used to assist the preheating device 9 to heat hydrogen when the hydrogen cannot reach the working temperature of the solid oxide fuel cell 10; the pulse heating device 19 is used to heat the solid oxide fuel cell 10 to maintain the required working temperature.

[0096] The technical solution of the present invention is not limited to the limitations of the above specific embodiments. Any technical deformation made according to the technical solution of the present invention falls within the protection scope of the present invention.

Claims

1. A liquid organic hydrogen storage dehydrogenation system coupled with a solid oxide fuel cell, comprising: A hydrogen storage unit for storing liquid organic hydrogen-rich materials; A dehydrogenation unit for dehydrogenating the liquid organic hydrogen-rich materials to obtain hydrogen and organic hydrogen storage materials; A combustion unit including a solid oxide fuel cell, which burns using the hydrogen generated by the dehydrogenation unit as fuel and generates combustion exhaust gas; A heat distribution unit including a plurality of heat distribution devices, wherein at least one heat distribution device is used to collect and distribute the heat generated by cooling the organic hydrogen storage materials obtained by the dehydrogenation unit and the heat of the combustion exhaust gas generated by the combustion unit to the dehydrogenation unit and the combustion unit.

2. The system according to claim 1, wherein The dehydrogenation unit includes a heating device and a dehydrogenation reactor. The heating device is used to heat the liquid organic hydrogen-rich materials from the hydrogen storage unit to the dehydrogenation reaction temperature, and the dehydrogenation reactor contains a dehydrogenation catalyst; Preferably, a first adjustment device is connected between the hydrogen storage unit and the heating device. The first adjustment device is used to adjust the flow rate and / or pressure of the liquid organic hydrogen-rich materials entering the dehydrogenation unit from the hydrogen storage unit.

3. The system according to claim 1 or 2, characterized in that, The system further includes: A gas-liquid separation unit connected to the dehydrogenation reactor. The gas-liquid separation unit includes a gas-liquid separator, a gas storage tank, and a liquid storage tank. The gas-liquid separator is used to separate the hydrogen and organic hydrogen storage materials generated by the dehydrogenation unit. The gas storage tank is used to receive the hydrogen separated from the gas-liquid separator, and the liquid storage tank is used to receive the cooled organic hydrogen storage materials; Preferably, a second adjustment device is connected between the gas-liquid separator and the gas storage tank. The second adjustment device is used to prevent the hydrogen in the gas storage tank from flowing back into the gas-liquid separator; more preferably, the second adjustment device is a back pressure valve; Preferably, the gas-liquid separation unit and the heat distribution unit are connected by a pipeline filled with a heat transfer medium. The heat transfer medium exchanges heat with the organic hydrogen storage materials generated by dehydrogenation and transfers the heat to the heat distribution unit; Preferably, the combustion unit and the heat distribution unit are connected by a pipeline filled with a heat transfer medium. The heat transfer medium exchanges heat with the combustion exhaust gas generated by the solid oxide fuel cell and transfers the heat to the heat distribution unit.

4. The system according to any one of claims 1-3, characterized in that, The system further includes: A preheating unit connected to the solid oxide fuel cell, which is configured to preheat the hydrogen before the hydrogen enters the solid oxide fuel cell; Preferably, a third adjustment device is connected between the preheating unit and the gas storage tank of the gas-liquid separation unit. The third adjustment device is used to adjust the pressure and / or flow rate of the hydrogen entering the solid oxide fuel cell unit.

5. The system according to any one of claims 1-4, characterized in that, The heat distribution unit includes a first heat distribution device, which is used to collect and distribute the heat generated by cooling the organic hydrogen storage material obtained by the dehydrogenation unit and the heat of the combustion exhaust gas generated by the combustion unit to the dehydrogenation reactor and the combustion unit in the dehydrogenation unit, so as to maintain the working temperature of the dehydrogenation reactor and the working temperature of the solid oxide fuel cell; Preferably, the first heat distribution device is connected to the gas-liquid separator and the solid oxide fuel cell through pipes filled with a heat transfer medium. The heat transfer medium exchanges heat with the organic hydrogen storage material and the combustion exhaust gas, and transfers the heat generated by cooling the organic hydrogen storage material and the heat of the combustion exhaust gas to the first heat distribution unit; Preferably, the heat distribution unit further includes a second heat distribution device connected to the first distribution device. The second heat distribution device is used to redistribute the heat distributed from the first heat distribution device to the dehydrogenation reactor in the dehydrogenation unit, the heating device in the dehydrogenation unit and / or the preheating unit; Preferably, the heat distribution unit further includes a third heat distribution device and / or a fourth heat distribution device connected to the second heat distribution device. The third heat distribution device is used to redistribute the heat distributed from the second heat distribution device to the preheating unit to heat the hydrogen entering the solid oxide fuel cell; the fourth heat distribution device is used to redistribute the heat distributed from the second heat distribution device to the heating device of the dehydrogenation unit to heat the liquid organic hydrogen-rich material to the dehydrogenation reaction temperature.

6. The system according to any one of claims 1-5, characterized in that, The system further includes: a first auxiliary heating device, which is used to assist the heating device of the dehydrogenation unit to heat the liquid organic hydrogen-rich material when the liquid organic hydrogen-rich material cannot reach the optimal working temperature of the dehydrogenation unit at the start-up of the system; and / or, The system further includes: a second auxiliary heating device, which is used to heat the dehydrogenation reactor to maintain the required dehydrogenation reaction temperature; and / or, The system further includes: a third auxiliary heating device, which is configured to assist the preheating unit to heat hydrogen when the hydrogen cannot reach the working temperature of the solid oxide fuel cell; and / or, The system further includes: a fourth auxiliary heating device, which is used to heat the solid oxide fuel cell during cold start-up to enable the solid oxide fuel cell to quickly reach the working temperature; Preferably, the heating methods adopted by the heating device, the preheating unit, the first auxiliary heating device, the second auxiliary heating device, the third auxiliary heating device and the fourth auxiliary heating device in the dehydrogenation unit are independently selected from at least one of pulse heating, microwave heating, Joule heating, heat conduction frame heating, and electromagnetic heating; Preferably, the heating method adopted by the first auxiliary heating device is microwave heating, the heating method adopted by the second auxiliary heating device is electromagnetic heating, the heating method adopted by the third auxiliary heating device is Joule heating, and the heating method adopted by the fourth auxiliary heating device is pulse heating.

7. A heat regulation method for a SOFC-coupled organic hydrogen storage and dehydrogenation system, comprising the following steps: (1) Subjecting a liquid organic hydrogen-rich material to a dehydrogenation reaction to obtain hydrogen and an organic hydrogen storage material, and cooling the organic hydrogen storage material to generate heat; (2) Passing the hydrogen obtained in step (1) into a solid oxide fuel cell for combustion to obtain combustion exhaust gas; (3) Collecting the heat generated in step (1) and the heat of the combustion exhaust gas obtained in step (2) and using them to maintain the dehydrogenation reaction temperature of the liquid organic hydrogen-rich material and the operating temperature of the solid oxide fuel cell.

8. The method according to claim 7, wherein In step (1), the liquid organic hydrogen-rich material includes at least one of hydrogenation products of C2-C20 olefins, hydrogenation products of C2-C20 alkynes, hydrogenation products of C6-C20 aromatics, and hydrogenation products of C3-C20 heteroaromatics; preferably includes at least one of cyclohexane, methylcyclohexane, cyclohexylbenzene, hydrogenation products of xylene, hydrogenation products of dibenzyltoluene, hydrogenation products of ethylcarbazole, and hydrogenation products of propylcarbazole; and / or, In step (3), after collecting the heat generated in step (1) and the heat of the combustion exhaust gas obtained in step (2), it is also used for heating the liquid organic hydrogen-rich material before the dehydrogenation reaction; and / or, In step (3), after collecting the heat generated in step (1) and the heat of the combustion exhaust gas obtained in step (2), it is also used for preheating the hydrogen before entering the solid oxide fuel cell.

9. The method according to claim 7 or 8, characterized in that In step (1), the dehydrogenation reaction is carried out in a dehydrogenation reactor, and the cooling of the organic hydrogen storage material is carried out in a gas-liquid separator; and / or, in step (3), after the heat is collected, a heat distributor is used to distribute the collected heat to the dehydrogenation reactor and the solid oxide fuel cell; Preferably, a dehydrogenation catalyst is installed in the dehydrogenation reactor, and the dehydrogenation catalyst includes at least one of a nickel-based catalyst, a palladium-based catalyst, a platinum-based catalyst, a ruthenium-based catalyst, and a rhodium-based catalyst.

10. Application of the liquid organic hydrogen storage and dehydrogenation system coupled with a solid oxide fuel cell in the operation of a vehicle; Preferably, the vehicle includes at least one of a bus, a heavy truck, a high-speed train, and a large ship.

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