A special vehicle and method for hydrogen storage, transportation and dehydrogenation

Abstract

The present application relates to a kind of special vehicle of hydrogen storage, hydrogen transport and dehydrogenation and method, the special vehicle mainly by the box of being equipped with hydrogen storage, hydrogen transport and dehydrogenation equipment, transport vehicle two parts are made of, the box is fixed on transport vehicle chassis and becomes whole, is made of a kind of special vehicle of hydrogen storage, hydrogen transport and dehydrogenation;Using liquid organic hydrogen storage / dehydrogenation technology (LOHC for short), the DL-1 type solid catalyst (Raney-Ni-W-Co / Al2O3) disclosed in the present application can improve the hydrogenation / dehydrogenation catalytic reaction activity of unsaturated liquid organic matter and the efficiency of industrial fixed bed reactor, the special vehicle of the present application can implement a one-stop service of hydrogen storage, hydrogen transport, dehydrogenation and hydrogen supply, solve the problem of complicated process, multiple links, low efficiency and high cost in hydrogen storage and use;With the advantages of high hydrogen storage capacity of transport vehicle, short operation process, less investment, low operating cost, safe and reliable and all-round scientific management, and good industrial practicability.

Description

Technical Field

[0001] This invention relates to the field of hydrogen energy storage technology and equipment, specifically to a special vehicle and method for storing, transporting, and dehydrogenating hydrogen. Background Technology

[0002] Hydrogen energy is a crucial carrier for energy transformation and upgrading, and a significant solution for achieving carbon peaking and carbon neutrality. It is a plentiful, clean, efficient, and widely applicable "green energy" source. Currently, mature industrial hydrogen production methods include hydrogen production from fossil fuels such as natural gas, methanol reforming, pressure swing adsorption (PSA) of coke oven gas, and water electrolysis. Storing hydrogen as an energy carrier is considered the best solution to energy problems. The hydrogen energy system mainly includes four stages: hydrogen production, storage, transportation, and dehydrogenation applications. Hydrogen storage is key and currently the main technological obstacle to hydrogen energy applications. Hydrogen is the lightest of all elements; under standard conditions, its density is 0.0899 g / L, one ten-thousandth the density of water. At -252.7℃, it can be a liquid with a density of 70 g / L, only one-fifteenth the density of water. Therefore, hydrogen can be stored, but high-density storage is difficult. The International Energy Agency stipulates that practical hydrogen storage systems must have a mass hydrogen storage density of 5 wt% and a volumetric hydrogen storage density greater than 40 kg / m³. 3 The U.S. Department of Energy (DOE) proposes that the mass hydrogen storage density and volumetric hydrogen storage density of onboard hydrogen sources be 6.5 wt% and 62 kg / m³, respectively. 3 Currently, the most reported hydrogen storage methods include cryogenic liquid hydrogen storage, high-pressure gaseous hydrogen storage, metal alloy hydrogen storage, carbon material adsorption hydrogen storage, chemical hydride hydrogen storage, and metal-organic framework (MOF) hydrogen storage. These methods have all made some progress, but further consideration is needed regarding mass hydrogen storage density, volumetric hydrogen storage density, energy efficiency, safety, and cost. Therefore, finding efficient, low-cost, and scalable hydrogen storage methods has become crucial. In recent years, liquid organic hydride hydrogen storage technology based on chemical reactions has attracted much attention from many countries due to its advantages such as large hydrogen storage capacity, high energy density, and safe and convenient liquid storage and transportation. This technology is considered an alternative to liquefaction or high-pressure hydrogen storage and is expected to play an important role in future hydrogen energy storage and transportation.

[0003] Hydrogen storage and transportation is a crucial bridge connecting hydrogen production and demand. Low-cost and efficient hydrogen storage and transportation technologies are essential for the large-scale application of hydrogen. Currently, room-temperature high-pressure gaseous hydrogen storage is the most mature hydrogen storage technology in my country. High-pressure gaseous storage is a common and direct storage method, allowing hydrogen to be released directly by adjusting a high-pressure valve. Ordinary high-pressure gaseous hydrogen storage is a widely used, simple, and easy-to-implement hydrogen storage method with low cost, fast filling and discharging speed, and can be carried out at room temperature. However, its disadvantages include the need for heavy pressure-resistant containers, the consumption of significant hydrogen compression work, and the potential for hydrogen leakage and container explosion. Safety concerns include the high requirements for high-pressure hydrogen storage tanks, resulting in high manufacturing costs and potential safety risks associated with high-pressure hydrogen storage; cryogenic liquid hydrogen storage, a physical storage method, involves compressing hydrogen and cryogenically cooling it to below 21K (approximately -253℃) to liquefy it, then storing it in specialized cryogenic insulated liquid hydrogen tanks. Its density can reach 70.78 kg / cm³, approximately 850 times the density of standard hydrogen, offering a large volumetric capacity suitable for large-scale, long-distance hydrogen storage and transportation; however, it requires highly insulating hydrogen storage containers and consumes significant energy during liquefaction and transportation. Solid-state hydrogen storage uses metal hydrides, chemical hydrides, or nanomaterials as hydrogen storage carriers, achieving hydrogen storage through chemical and physical adsorption. It offers advantages such as high hydrogen storage density, low storage pressure, good safety, and high hydrogen purity during dehydrogenation. Disadvantages include high cost and the need for high temperatures for dehydrogenation. The properties of the hydrogen storage agent and carrier are similar to gasoline, making storage, transportation, maintenance, and upkeep safe and convenient. The simplicity of storage facilities is particularly unmatched by traditional hydrogen storage technologies. It can be recycled multiple times and has a long lifespan. The hydrogenation reaction releases a large amount of heat that can be utilized. Considering factors such as hydrogen storage content, energy consumption during the hydrogen storage process, and cost, monocyclic aromatic hydrocarbons like benzene and toluene have a large hydrogen storage capacity, reversible storage processes, and good performance. The cycle system has high thermal efficiency. The hydrogenation process is exothermic, while the dehydrogenation process is endothermic. The heat released during hydrogenation can be recovered and used as heat for the dehydrogenation reaction, effectively reducing heat loss and improving the overall thermal efficiency of the cycle system. Hydrogenated organic hydrides exhibit stable performance and high safety, allowing for storage at ambient temperature and pressure, similar to petroleum. They also boast a high hydrogen storage density, reaching 5.0-7.2% / wt. Due to its unique advantages, reversible organic liquid hydrogen storage / release technology is technically feasible as a large-scale, seasonal hydrogen energy storage method or for in-vehicle hydrogen removal and use as automotive fuel, demonstrating significant development potential and becoming a promising hydrogen storage technology.

[0004] Liquid organic hydrogen storage technology originated in the 1980s. It is a chemical storage method that utilizes organic liquids and hydrogen gas to undergo reversible hydrogenation and dehydrogenation reactions under the action of a catalyst, enabling hydrogen storage and transportation at ambient temperature and pressure. This method offers advantages such as high hydrogen storage density, high safety, and low cost, and is poised to become the dominant approach for large-scale, safe, and widely adopted atmospheric-pressure hydrogen storage and supply. However, it requires specialized hydrogenation, transportation, and dehydrogenation equipment, which is complex, inefficient, and increases the overall cost of hydrogen storage, transportation, and supply. While hydrogen is indispensable in the energy structure transformation, its practical application remains uncertain, primarily due to cost, especially in the storage and transportation stages. Currently, gaseous hydrogen transportation is the main method, with a 49-ton, 12-meter-long hydrogen tubing vehicle carrying approximately 350 kg of hydrogen. Liquid hydrogen transportation is more challenging and costly.

[0005] In particular, traditional hydrogenation catalysts such as Raney-Ni, which are porous framework nickel catalysts formed by leaching amorphous nickel-aluminum alloys with sodium hydroxide solution, are widely used in the petrochemical and fine chemical industries due to their simple preparation process, excellent active hydrogen properties, and good resistance to sulfur and arsenic poisoning. However, this catalyst lacks mechanical strength and cannot meet the requirements of fixed bed packing. Therefore, it can only be operated in a paddle bubbling bed or a batch stirred tank. Moreover, due to the extremely poor wear resistance of the catalyst, the catalyst pulverization phenomenon is very prominent during paddle bubbling and batch stirring, which greatly limits the application of traditional Raney-Ni catalysts in industrial large-tonnage fixed bed continuous catalytic hydrogenation equipment.

[0006] In CN114497630A, "An Organic Liquid Material for Hydrogen Storage, a Catalytic Hydrogen Storage System, and a Hydrogen Storage Method," the reaction temperature reaches as high as 300℃, and the reaction system pressure reaches as high as 10MPa. The high-temperature and high-pressure conditions required for the hydrogen storage process are quite harsh, increasing the energy consumption cost of the hydrogenation reaction. The selected hydrogenation catalyst active component is an expensive metal, such as ruthenium, palladium, and platinum, with the total loading of these three metals accounting for 0.3-2.5% of the total mass of the hydrogen storage reaction catalyst. Example 1 uses a ruthenium-containing Ru-Cu / Al2O3 catalyst, and Example 2 uses a platinum-containing ruthenium Pt-Ru-Cu / Al2O3 catalyst. Precious metals are easily "poisoned" by sulfides in the raw materials, increasing the catalyst regeneration cost. In Example 1, Ru(ruthenium)-Cu / Al2O3 catalyst was used. The catalyst contains 2.0 wt% Ru and 10.0 wt% Cu. The catalyst is a fine powder with a mesh size of 20-40. Fine powder catalysts have high resistance in fixed beds and are not suitable for use in fixed beds. Fine powder catalysts are only suitable for use in indirect production in a stirred tank reactor. The catalyst in the fixed bed is 2.0 g. This is a laboratory hydrogenation experiment and does not take into account the fact that the hydrogenation reaction of hydrogen and liquid organic matter in industrial production is an exothermic reaction. The heat of reaction must be removed from the system in time. Otherwise, the heat in the catalytic reactor will accumulate in large quantities, forming a vicious cycle, which will cause the temperature of the hydrogenation reactor or catalytic bed to rise sharply (runaway). At best, it will damage the catalyst and reduce its life. At worst, it may cause serious equipment or pipeline explosion accidents.

[0007] To overcome the shortcomings of cumbersome processes, numerous steps, low efficiency, and high costs associated with hydrogen storage, transportation, and dehydrogenation, this invention provides a "Dedicated Vehicle and Method for Hydrogen Storage, Transportation, and Dehydrogenation." Utilizing this method, liquid organic matter is hydrogenated or loaded with hydrogen at the hydrogen production site. The hydrogen-loaded liquid organic matter is then transported by the "Dedicated Vehicle" to the hydrogen production site. A dehydrogenation device on the "Dedicated Vehicle" releases the hydrogen, which is then supplied to the user using a hydrogen compressor with high-pressure hydrogen. Specifically, the DL-1 type solid catalyst (Raney-Ni-W-Co / Al2O3) of this invention overcomes the shortcomings of traditional Raney-Ni hydrogenation catalysts, which have poor crush resistance and cannot be used in large-scale industrial fixed-bed hydrogenation catalytic reactors. This invention offers advantages such as short operation process, low equipment investment, low operating costs, safety and reliability, and scientific management, enabling a systematic and comprehensive application service for hydrogen storage, transportation, and dehydrogenation.

[0008] Through searching and reviewing a large number of domestic and foreign documents, magazines, books, CDs, patents, etc., no relevant reports on "a special vehicle and method for hydrogen storage, transportation and dehydrogenation" have been found domestically or internationally. Summary of the Invention

[0009] This invention discloses a special vehicle for hydrogen storage, transportation, and dehydrogenation, mainly composed of a cargo box equipped with hydrogen storage, transportation, and dehydrogenation equipment, and a transport vehicle. The cargo box can be a fixed or movable cargo box on the vehicle. The hydrogen storage, transportation, and dehydrogenation equipment includes: valve one, valve two, hydrogen compressor one, pressure gauge one, gas-liquid separator, sampling valve, organic solvent pump, shell-and-tube condenser, hydrogen compressor two, hydrogen buffer tank, heat exchanger one, valve three, pressure gauge two, pressure gauge three, thermometer one, tubular fixed-bed catalytic reactor two, thermometer two, heat exchanger two, tubular fixed-bed catalytic reactor one, gas-liquid mixer, and heating furnace. The hydrogen storage, transportation, and dehydrogenation equipment is configured inside the cargo box, forming a cargo box equipped with hydrogen storage, transportation, and dehydrogenation equipment. The cargo box equipped with hydrogen storage, transportation, and dehydrogenation equipment is fixed to the chassis of the transport vehicle to form a whole, constituting a special vehicle for hydrogen storage, transportation, and dehydrogenation.

[0010] The features are as follows: the hydrogen outlet five on the hydrogen buffer tank is connected to the inlet three of the hydrogen compressor two via a pipe; the outlet four of the hydrogen compressor two is connected to the shell-side inlet of the heat exchanger one via a pipe five; the shell-side outlet of the heat exchanger one is connected to the shell-side inlet of the heat exchanger two via a pipe seven; the shell-side outlet of the heat exchanger two is connected to the inlet ten of the gas-liquid mixer via a pipe eight; the outlet eight of the gas-liquid mixer is connected to the top inlet nine of the tubular fixed-bed catalytic reactor one via a pipe; the bottom outlet seven of the tubular fixed-bed catalytic reactor one is connected to the tube-side inlet of the heat exchanger two via a pipe nine; the tube-side outlet of the heat exchanger two is connected to the top inlet four of the tubular fixed-bed catalytic reactor two via a pipe six; the bottom outlet six of the tubular fixed-bed catalytic reactor two is connected to the tube-side inlet of the heat exchanger one; and the tube-side outlet of the heat exchanger one is connected to the tube-side inlet of the shell-and-tube condenser via a pipe four. The tube outlet of the apparatus is connected to the top inlet 2 of the gas-liquid separator via pipe 1. The top outlet 2 of the gas-liquid separator is connected to the inlet 1 of the hydrogen compressor 1 via pipe. The outlet 1 of the hydrogen compressor 1 is connected to the inlet of valve 1 and the inlet of valve 2 via pipe. The outlet of valve 1 is equipped with a hydrogen outlet pipe. The outlet of valve 2 is connected to the inlet 8 and inlet 7 of the tubular fixed-bed catalytic reactor 1 via cold hydrogen pipe. The outlet of valve 2 is connected to the inlet 5 and inlet 6 of the tubular fixed-bed catalytic reactor 2 via cold hydrogen pipe. The outlet of valve 2 is connected to the inlet 10 of the gas-liquid mixer via the cold hydrogen pipe. The bottom outlet 3 of the gas-liquid separator is connected to the inlet of the organic solvent pump via pipe 11. The outlet of the organic solvent pump is connected to the inlet 11 of the heating furnace via pipe 3. The outlet 9 of the heating tube in the heating furnace is connected to the inlet 10 of the gas-liquid mixer via pipe 10.

[0011] The tubular fixed-bed catalytic reactor is a cylindrical, sealed metal cylinder. An upper perforated plate and a lower perforated plate are arranged in the middle section of the cylinder. An inlet eight is located on the side wall below the upper perforated plate, and an inlet seven is located on the side wall below the lower perforated plate. A solid catalyst is placed between the upper and lower perforated plates. The temperature sensor of a thermometer is inserted into the solid catalyst. An inlet nine is located at the top of the tubular fixed-bed catalytic reactor, and an outlet seven is located at the bottom. The interior of the tubular fixed-bed catalytic reactor is filled with liquid organic matter, and a pressure gauge three is inserted into the liquid organic matter.

[0012] The tubular fixed-bed catalytic reactor II is a cylindrical metal sealed cylinder. An upper perforated plate II and a lower perforated plate II are configured in the middle section of the cylinder. An inlet V is configured on the side wall of the cylinder below the upper perforated plate II, and an inlet VI is configured on the side wall of the cylinder below the lower perforated plate II. A solid catalyst is placed between the upper and lower perforated plates II. The temperature sensing head of thermometer I is inserted into the solid catalyst. An inlet IV is configured at the top of the tubular fixed-bed catalytic reactor II, and an outlet VI is configured at the bottom. The interior of the tubular fixed-bed catalytic reactor II is filled with liquid organic matter, and pressure gauge I is inserted into the liquid organic matter.

[0013] The heating furnace described is a cylindrical tube heating furnace used in petrochemicals, commonly used as a heating furnace for atmospheric and vacuum distillation of crude oil. The heating furnace consists of a radiant chamber, a convection chamber, a waste heat recovery system, a burner, and a ventilation system. A coil is installed inside the heating furnace. The coil is a seamless high-temperature resistant steel pipe, and the liquid organic material flowing inside the seamless high-temperature resistant steel pipe is heated by electric heating, fuel oil, or natural gas combustion, which heats the outer wall of the coil inside the heating chamber and raises the temperature of the liquid organic material flowing inside the seamless high-temperature resistant steel pipe.

[0014] The hydrogen compressors described, namely Hydrogen Compressor 1 and Hydrogen Compressor 2, are common hydrogen compressors, with models including QB, DSR, and FXY, each with different compression ratios and displacements. The QB series is the basic model, the DSR series is the high-pressure model (≥15MPa), and the FXY series is the large-displacement model.

[0015] The gas-liquid separator described herein is a conventional chemical industrial gas-liquid separator, consisting of a sealed tank. The top of the tank is equipped with an inlet for gas and a outlet for liquid materials, and the bottom of the tank is equipped with a bottom outlet. The liquid level inside the tank is located at 2 / 3 to 4 / 5 of the tank height. A sampling valve is installed on the outlet pipe on the side at 1 / 2 of the tank height, and the outlet pipe is inserted into the liquid organic matter.

[0016] The aforementioned gas-liquid mixer is a commonly used industrial gas-liquid two-phase mixing device. Its basic working principle is to utilize a mixing unit fixed inside a pipe to change the flow state of the fluid within the pipe, achieving good dispersion and thorough mixing between different gas and liquid fluids. This widely applicable device is a highly efficient mixing equipment that relies on the special structure of the mixing unit and fluid movement without moving parts to disperse and mix immiscible fluids. Compared to traditional mixing equipment such as agitators, colloid mills, homogenizers, and venturi tubes, the static mixer has advantages such as compact structure, low energy consumption, low investment, high operational flexibility, no maintenance, and excellent mixing performance. It can replace traditional equipment in processes involving liquid-liquid, liquid-gas, liquid-solid, and gas-gas mixing, as well as emulsification, neutralization, absorption, extraction, reaction, and enhanced heat transfer. Therefore, it is widely used in the mixing of substances in petroleum refining, chemical industry, and wastewater treatment.

[0017] The organic solvent pump mentioned above is a commonly used pneumatic diaphragm pump or corrosion-resistant pump in the chemical industry. It is suitable for conveying various corrosive liquids, liquids containing particles, high viscosity, volatile organic compounds, flammable and highly toxic liquids.

[0018] The aforementioned shell-and-tube condenser is a conventional shell-and-tube heat exchanger used in the petrochemical industry. It consists of a shell, heat transfer tube bundles, tube sheets, baffles, and tube boxes. The shell is cylindrical, containing the tube bundles, both ends of which are fixed to the tube sheets. The heat exchange occurs between two fluids: the hot gas-liquid material flows inside the tubes (the tube-side fluid), while the cooling medium, water, flows outside the tubes (the shell-side fluid). To improve the heat transfer coefficient of the external fluid, several baffles are typically installed inside the shell. These baffles increase the shell-side fluid velocity, forcing the fluid to pass laterally through the tube bundle multiple times along a predetermined path, thus enhancing fluid turbulence.

[0019] The heat exchangers 1 and 2 described above are shell-and-tube heat exchangers used in the petrochemical industry, including a tube side and a shell side. The tube side contains flowing high-temperature liquid organic matter, while the shell side contains flowing cold hydrogen. The cold hydrogen is converted into hot hydrogen after heat exchange, and the temperature of the high-temperature liquid organic matter decreases after heat exchange.

[0020] The transport vehicle mainly includes: a cab, engine, generator, clutch, gearbox, power take-off unit (PTO) mounted on the gearbox, chassis, vehicle drive shaft, and wheels; it is a modified vehicle that uses the power output shaft of the PTO connected to the vehicle gearbox to drive the generator to generate electricity, or a vehicle with an external power source to charge the on-board battery; the transport vehicle is a vehicle manufactured by a vehicle manufacturer or a modified diesel, gasoline, or new energy vehicle; the engine power of the transport vehicle is between 80 and 350 horsepower; the transport vehicle is equipped with an external power socket, or an external power source (220V or 380V) to provide electrical or thermal energy to the hydrogen storage and dehydrogenation equipment in the cargo box.

[0021] The cargo box described is the one configured on the transport vehicle at the factory, modified as follows: the top of the cargo box consists of two parallel, reciprocating sliding front and rear top panels, along with several sets of pulleys supporting the sliding plate; any one of the top panels can be moved parallel to the other, creating an opening of approximately half of the cargo box top area to facilitate the operation, maintenance, replacement, or hoisting of equipment inside; the movement of the front and rear top panels is operated electrically or manually; when the front and rear top panels return to their respective positions, the top of the cargo box will be completely sealed, and the top of the cargo box, combined with the side panels, forms a three-dimensional cargo box; the front and rear top panels can be... The cargo box of the transport vehicle is secured with locks. The left and right side doors can be divided into upper and lower sections. Each side door can extend upwards or downwards at any angle within the range of 0-90 degrees. The extended side doors are controlled and secured by a hydraulic device. When all the extended side doors are closed and the top of the cargo box is sealed, the upper, lower, front, back, left, and right side panels of the cargo box are combined to form a complete cargo box. Each side door, front top panel, and rear top panel is secured with latches. The left and right side doors of the cargo box adopt the double-door structure of a postal express vehicle, which is locked on the center line of the two doors. The two doors can be opened to the left and right. The two side doors and the rear door of the cargo box adopt the traditional box truck structure.

[0022] The liquid organic matter mentioned above belongs to unsaturated liquid organic matter such as alkenes, alkynes or aromatic hydrocarbons (or hereinafter referred to as oil). Industrially used hydrogen storage liquid organic matter includes dibenzyltoluene, decahydronaphthalene, carbazole, N-ethylcarbazole, dimethylindole, benzene and toluene. In 1975, O. Sultan and M. Shaw first proposed the idea of ​​using recyclable liquid chemical hydrogen carriers for hydrogen storage, thus opening up the research field of this new hydrogen storage technology. Liquid organic hydrogen storage (LOHC) technology works by using catalysts and certain unsaturated liquid organic compounds such as alkenes, alkynes, or aromatic hydrocarbons to react with hydrogen gas in a reversible process. Hydrogen is stored through hydrogenation (chemical bonding) and released through dehydrogenation. In LOHC, hydrogen chemically bonds to organic hydrocarbon carrier molecules under the action of a catalyst (hydrogenation) and can be released in the reverse process (dehydrogenation). It has a hydrogen storage density of 5%-10%, a large storage capacity, and uses liquid organic materials, allowing for convenient and safe transport at ambient temperature and pressure. In principle, each unsaturated organic compound (organic molecule with carbon-carbon double or triple bonds) can absorb hydrogen during hydrogenation. During hydrogenation and dehydrogenation, the catalyst not only lowers the reaction temperature but also improves the reaction rate of the chemical hydrogen storage technology.

[0023] Cyclohexane utilizes the reversible chemical reaction of benzene-hydrogen-cyclohexane to store hydrogen, exhibiting high hydrogen storage capacity. It is liquid at room temperature, and the dehydrogenation product, benzene, is also liquid at room temperature and pressure, facilitating transportation. Methylcyclohexane dehydrogenates to produce hydrogen and toluene, and both methylcyclohexane and toluene are liquids at room temperature and pressure; therefore, methylcyclohexane is also a relatively ideal hydrogen storage carrier. (See attached image) Figure 6 ;

[0024] Benzene and toluene have large hydrogen storage capacities, with theoretical hydrogen storage capacities of 7.19% and 6.18% respectively, which are much larger than those of traditional metal hydrides (which typically have hydrogen storage capacities of 1.5% to 3.0%). Decahydronaphthalene has strong hydrogen storage capacity and is a liquid at room temperature, but continuous loss of raw materials may occur during hydrogenation, dehydrogenation, and transportation. These three media belong to traditional organic liquid hydrogen storage materials, and they share a common drawback: high dehydrogenation temperatures. For example, the dehydrogenation temperature of cyclohexane is above 270℃; the dehydrogenation temperature of methylcyclohexane is at least 230℃, and can reach up to 400℃, depending on the conditions; the dehydrogenation temperature of decahydronaphthalene is also above 240℃; carbazole can be hydrogenated at 250℃ and dehydrogenated at 220℃; ethylcarbazole is a colorless, flaky crystal at room temperature and pressure, and can be rapidly hydrogenated at 150℃ to 190℃ and dehydrogenated at 170℃ to 210℃, making it a relatively ideal hydrogen storage medium.

[0025] Furthermore, the method for storing, transporting, and removing hydrogen used in the operation of the special-purpose vehicle includes the following steps:

[0026] (i) 99.99% hydrogen produced by electrolysis of water, natural gas, methanol reforming or coke oven gas is added to hydrogen buffer tank (23) through valve three (27) for later use;

[0027] (ii) Hydrogen storage: The room temperature hydrogen (or cold hydrogen) in the hydrogen buffer tank (23) is first transported to the shell side of heat exchanger one (26) for heat exchange using compressor two (21), and then to the shell side of heat exchanger two (44) for heat exchange. After the room temperature hydrogen (or cold hydrogen) is heated and transformed into hot hydrogen, it is transported to the gas-liquid mixer (53). At the same time, the liquid organic matter (11) (hereinafter referred to as "oil") in the gas-liquid separator (13) is transported by organic solvent pump (15). The liquid organic matter (11) is indirectly heated in the heating tube (56) of the heating furnace (58). After heating, the liquid organic matter (11) is transported to the gas-liquid mixer (53). In the gas-liquid mixer (53), hydrogen and liquid organic matter (11) are mixed to form a gas-liquid homogeneous material. The gas-liquid homogeneous material continuously enters the tubular fixed-bed catalytic reactor (48) from the top inlet nine (51) of the tubular fixed-bed catalytic reactor (48). The mixed material comes into direct contact with the solid catalyst (36) in the tubular fixed-bed catalytic reactor (48) to undergo a hydrogenation catalytic reaction. In the tubular fixed-bed catalytic reactor (48), the catalytic reaction pressure is controlled at 1.5-8.0 MPa and the temperature is controlled at 130-210℃. The material after the hydrogenation catalytic reaction is continuously discharged from the bottom outlet seven (47) of the tubular fixed-bed catalytic reactor (48). After passing through the tube side of the heat exchanger two (44) for heat exchange and cooling (i.e., the cold hydrogen flowing in the shell side absorbs heat and cools down), the material enters the tubular fixed-bed catalytic reactor two (39) through the pipe six (42) and the top inlet four (31) of the tubular fixed-bed catalytic reactor two (39), and comes into direct contact with the solid catalyst (36) in the tubular fixed-bed catalytic reactor two (39) to undergo a hydrogenation catalytic reaction. In the tubular fixed-bed catalytic reactor two (39), the catalytic reaction pressure is controlled at 1.5-8.0 MPa.At 0 MPa, the temperature is controlled at 130-210℃. The material after the hydrogenation catalytic reaction is continuously discharged from the bottom outlet six (41) of the tubular fixed-bed catalytic reactor two (39). After heat exchange in the tube side of heat exchanger one (26) (i.e., the cold hydrogen flowing in the shell side absorbs heat and cools down), the material discharged from heat exchanger one (26) enters the shell-and-tube condenser (18) through pipe four (19) and is cooled to room temperature with water, so that the discharged hot material becomes room temperature material. The room temperature material is then transported to the gas-liquid separator (13) through pipe one (7) and the top inlet two (8) of the gas-liquid separator (13). In the gas-liquid separator (13), the tubular fixed-bed catalytic reactor one (48) and the tubular fixed-bed catalytic reactor (13) are cooled to room temperature. The unabsorbed greenhouse hydrogen (or cold hydrogen) in the second tubular fixed-bed catalytic reactor (39) separates from the liquid organic matter, allowing the cold hydrogen to be continuously recycled. The cold hydrogen absorbs the heat released during the hydrogenation reaction in the first tubular fixed-bed catalytic reactor (48) and the second tubular fixed-bed catalytic reactor (39), maintaining the hydrogen absorption catalytic reaction temperature in the range of 130-210℃. The cold hydrogen overflows from the top outlet (9) of the gas-liquid separator (13) and enters the inlet (5) of the hydrogen compressor (4). Using the hydrogen compressor (4) and the cold hydrogen pipeline (29), the cold hydrogen is circulated to the inlet (50) and inlet (49) of the first tubular fixed-bed catalytic reactor (48), providing... The exothermic hydrogenation catalytic reaction is cooled down, or cold hydrogen is transported to inlet five (34) and inlet six (38) of tubular fixed-bed catalytic reactor two (39) using hydrogen compressor one (4) and cold hydrogen pipeline (29) to cool down the exothermic hydrogenation catalytic reaction and maintain the hydrogen absorption catalytic reaction temperature in the range of 130-210℃, or cold hydrogen is continuously transported to inlet ten (54) of gas-liquid mixer (53) using hydrogen compressor one (4) and cold hydrogen pipeline (29) to replenish the hydrogen feedstock in the hydrogenation catalytic reaction in tubular fixed-bed catalytic reactor one (48); the liquid organic matter (11) in gas-liquid separator (13) is extracted from outlet three (12) using organic solvent pump (15) and passed through After passing through pipe three (17) and inlet eleven (59) of heating furnace (58), the liquid organic matter (11) is transported to heating furnace (58) for heating and temperature rise. Then, it is fed into inlet ten (54) of gas-liquid mixer (53) through outlet nine (57). In gas-liquid mixer (53), the heated liquid organic matter (11) is mixed evenly with the heat-exchanged hydrogen to form a gas-liquid mixed material. The material first enters tubular fixed bed catalytic reactor one (48) and then enters tubular fixed bed catalytic reactor two (39) for hydrogenation catalytic reaction. After catalytic reaction, hydrogen is absorbed by liquid organic matter (11) or hydrogen is stored in liquid organic matter (11). The hydrogenation catalytic reaction pressure is controlled at 1.5-8.0 MPa, temperature controlled at 130-210℃; in the exothermic hydrogenation catalytic reaction, the cold hydrogen generated by the gas-liquid separator (13) is transported through the cold hydrogen pipeline (29) to the inlet eight (50) and inlet seven (49) of the tubular fixed-bed catalytic reactor (48), or the cold hydrogen generated by the gas-liquid separator (13) is transported through the cold hydrogen pipeline (29) to the inlet five (34) and inlet six (38) of the tubular fixed-bed catalytic reactor (39), using the cold hydrogen to cool the hydrogenation catalytic reaction in the catalytic reactor, and controlling and adjusting to maintain the appropriate temperature required for the catalytic reaction;

[0028] Open valve (14) to take a sample and test the hydrogenation reaction of liquid organic matter. When the hydrogen storage content in the liquid organic matter is higher than 6 wt% and the hydrogen storage density is higher than 60 kg / m³, the hydrogen storage reaction is tested. 3 When the hydrogen storage operation is completed, the hydrogen storage capacity is greater than 6 wt% and the hydrogen storage density is greater than 60 kg / m³. 3 The liquid organic matter (hereinafter referred to as "hydrogen oil") is buffered in the gas-liquid separator (13), the tubular fixed-bed catalytic reactor one (48) and the tubular fixed-bed catalytic reactor two (39) for later use. The operation of hydrogen compressor one (4) and hydrogen compressor two (21) is stopped, the operation of organic solvent pump (15) is stopped, and valve one (1) is closed at the same time.

[0029] In this invention, in order to configure industrial-scale high-yield hydrogen storage / dehydrogenation equipment in the narrow and height-restricted cargo box of a vehicle, multiple sets of tubular fixed-bed catalytic reactors lower than the height of the cargo box are selected for combined use to increase the hydrogen storage or dehydrogenation capacity per unit time, such as tubular fixed-bed catalytic reactor one, tubular fixed-bed catalytic reactor two, tubular fixed-bed catalytic reactor three, ...;

[0030] In this invention, the volume ratio (V / V) of liquid organic matter to hydrogen is 50–300:1; in the hydrogenation catalytic reaction of this invention, the volume hourly space velocity (VHSV) of the liquid organic matter is 2.0–5.0 h⁻¹. -1 ;

[0031] (III) Hydrogen transportation: A special vehicle for storing, transporting, and dehydrogenating hydrogen, after storing hydrogen as described in (II), is driven to places where hydrogen is needed (such as hydrogen vehicle refueling stations, hydrogen metal smelting plants, hydrogen fuel cell manufacturing plants, hydrogenated grease hardening plants, hydrogen welding and metal cutting, hydrogen balloon refueling, hydrogen airship refueling, hydrogen for petrochemical use, etc.) to deliver the hydrogen stored in the special vehicle for storing, transporting, and dehydrogenating hydrogen to enterprises that use hydrogen.

[0032] (iv) Dehydrogenation (or hydrogen release): Close valve two (2), close valve three (27), close hydrogen compressor two (21), open valve one (1), and connect the hydrogen outlet pipe (81) to the hydrogen storage tank of the hydrogen-using enterprise; then, start hydrogen compressor one (4) and start organic solvent pump (15) to transport the hydrogenated liquid organic matter (hereinafter referred to as "hydrogen oil") in gas-liquid separator (13) to the heating furnace (58) for heating to the required temperature for dehydrogenation catalytic reaction. The heated "hydrogen oil" is passed through a gas-liquid mixer (53) and then sequentially enters the tubular fixed-bed catalytic reactor one (48) and the tubular fixed-bed catalytic reactor two (39). The "hydrogen oil" undergoes a dehydrogenation catalytic reaction with the solid catalyst (36) in the tubular fixed-bed catalytic reactor one (48) and the tubular fixed-bed catalytic reactor two (39). The temperature of the dehydrogenation catalytic reaction is controlled at 150-260℃, the pressure is maintained at atmospheric pressure, and the space velocity of the solid catalyst is 2-5 h⁻¹. -1 After being heated and catalytically reacted, the "hydrogen oil" decomposes into hydrogen and liquid organic matter. The mixture formed by the hydrogen and liquid organic matter enters the shell-and-tube condenser (18) through pipe four (19) and is condensed to room temperature. The mixture at room temperature is then transported to the gas-liquid separator (13) for gas-liquid separation. In the gas-liquid separator (13), hydrogen (cold hydrogen) overflows from the gas-liquid separator (13) outlet two (9), is extracted by the hydrogen compressor one (4), and is transported to the hydrogen buffer tank of the hydrogen-using enterprise for later use through valve one (1) and hydrogen outlet pipe (81). The separated liquid organic matter is stored at the liquid level line (10) of the gas-liquid separator (13). Using the organic solvent pump (15), the liquid organic matter stored in the gas-liquid separator (13) is continuously extracted and transported to the heating furnace (58) for heating and temperature rise, and the above dehydrogenation catalytic reaction process is carried out in a cycle.

[0033] Open valve (14) to take a sample and detect the dehydrogenation catalytic reaction of liquid organic matter. When the amount of hydrogen stored in the liquid organic matter is less than 0.1-0.5wt%, the dehydrogenation or hydrogen release ends: that is, turn off the operation of hydrogen compressor one (4), stop the operation of organic solvent pump (15), stop the operation of heating furnace (58), and close valve one (1) at the same time.

[0034] In the hydrogen storage and dehydrogenation process of this invention:

[0035] (i) After the hydrogen source continuously enters the hydrogen buffer tank (23), the hydrogen (cold hydrogen) is pressurized by the second hydrogen compressor (21) (pressure controlled at 3-6 MPa). The hydrogen (cold hydrogen) passes through the first heat exchanger (26) and the second heat exchanger (44) in sequence and absorbs the heat released by the hydrogenation reaction, which raises the temperature of the cold hydrogen raw material and improves the thermal efficiency of the hydrogenation catalytic reaction. This is one of the features of the present invention.

[0036] (ii) The hydrogenation reaction of hydrogen with liquid organic matter is an exothermic reaction. The heat of reaction must be removed from the system in a timely manner. Otherwise, the heat in the catalytic reactor will accumulate in large quantities, forming a vicious cycle and causing the temperature of the catalytic bed to rise sharply (runaway). At best, the catalyst will be damaged and its lifespan will be reduced. At worst, it may cause serious equipment or pipeline explosion accidents. Therefore, in the hydrogenation catalytic reactor of the present invention, the catalyst (36) is packed in multiple layers or multiple assemblies. For example, the catalytic reactor can be divided into a tubular fixed bed catalytic reactor one (48) and a tubular fixed bed catalytic reactor two (39) for use in series, or they can be used in parallel. The tubular fixed bed catalytic reactor one (48) A certain amount of cold hydrogen is injected into the first tubular fixed-bed catalytic reactor (48) and the second tubular fixed-bed catalytic reactor (39) to control the catalytic reaction temperature, so as to extend the catalyst life and achieve the optimal operation. Increasing or decreasing the reaction temperature has a decisive influence on the hydrogen conversion rate. In this invention, the hydrogen gas (cold hydrogen) separated in the gas-liquid separator (13) is continuously extracted by the hydrogen compressor (4) and sent into the first tubular fixed-bed catalytic reactor (48) and the second tubular fixed-bed catalytic reactor (39) respectively. The circulating cold hydrogen is used to cool the hydrogen reaction and control and adjust to maintain the appropriate temperature required for the catalytic reaction. This is one of the features of this invention.

[0037] (III) The hydrogen-to-oil ratio (V / V) of the liquid organic matter (hereinafter referred to as oil) to the working hydrogen in this invention is 50-300:1. The working hydrogen is composed of fresh hydrogen and recycled hydrogen. Hydrogenation is a volume reduction reaction. Increasing the partial pressure of hydrogen or the hydrogen-to-oil ratio is beneficial to the hydrogenation reaction. High-pressure hydrogenation can inhibit the occurrence of carbon deposits, prevent catalyst deactivation, extend the catalyst life, and facilitate the reaction. It also improves the degree of coking of liquid organic matter on the catalyst surface. The presence of a large amount of recycled hydrogen in this invention can also timely remove the heat of catalytic reaction from the system, making the temperature of the entire catalytic bed stable and easy to control. The key to high-pressure hydrogenation is the use of a high-pressure-resistant tubular fixed-bed catalytic reactor. This invention employs a tubular fixed-bed catalytic reactor, which is resistant to high pressure and suitable for hydrogenation reactions under high hydrogen partial pressure. This allows for the selection of a high hydrogen-to-oil ratio for rapid hydrogen storage, increasing the hydrogen storage capacity per unit time. The hydrogenation or dehydrogenation of this invention takes place within the same tubular fixed-bed catalytic reactor, ensuring safe production, simple structure, and convenient operation, thus enabling the industrial-scale hydrogenation of liquid organic matter. In particular, hydrogen and liquid organic matter are continuously circulating during the hydrogenation reaction; this is one of the key features of this invention.

[0038] (iv) In order to configure high-yield hydrogen storage / dehydrogenation equipment in the narrow and height-restricted cargo box of a vehicle, the present invention configures multiple sets of height-restricted tubular fixed-bed catalytic reactors to carry out hydrogenation or dehydrogenation reactions. This is one of the features of the present invention.

[0039] (v) The present invention utilizes the engine and power take-off unit on the transport vehicle to generate electricity, which supplies the electrical energy required for the hydrogen storage or dehydrogenation process, thus overcoming the defect that the special vehicle cannot store or supply hydrogen in an environment without power supply; this is one of the features of the present invention.

[0040] (vi) The top of the cargo box of the present invention is equipped with an openable sliding plate, and the left and right side panels of the cargo box can be opened, which is not only convenient for personnel to operate hydrogen storage or dehydrogenation, but also facilitates the dissipation of hydrogen that may be leaked during production, thus ensuring safe production; this is one of the features of the present invention.

[0041] The solid catalyst (36) of this invention belongs to the DL-1 type solid catalyst, which is either strip-shaped or granular. The production method of the DL-1 type solid catalyst is as follows:

[0042] 3% (wt%) tungsten trioxide powder (WO3), 7% (wt%) cobalt tetroxide powder (Co3O4), 45% (wt%) nickel-aluminum alloy powder (nickel / aluminum ratio 1:1) and 45% (wt%) boehmite (Al) were mixed. 13 O4(OH) 24 (H2O) 12 The powders are mixed uniformly by weight ratio. The active component for hydrogenation is Ni, while Co and W act as active co-catalysts and stabilizers, improving the active surface area and thermal stability of the catalyst and preventing surface deformation at operating temperatures. Al2O3, converted from boehmite after high-temperature calcination, serves as a carrier for the active component Ni and the co-catalysts Co and W. A certain amount of 6% nitric acid solution is added for bonding, and the mixture is extruded into strips with a diameter of 4 mm. It is dried at 120℃ for 5-8 hours, then calcined in a muffle furnace at 758-1050℃ for 5 hours and cooled to room temperature to obtain the shaped DL-1 alloy semi-finished product. The shaped DL-1 alloy semi-finished product (i.e., alloy-Ni-W-Co / Al2O3) is then activated by leaching with a 5-6 mol / L NaOH solution at 70-90℃, resulting in the following chemical reaction:

[0043] 2Al+2NaOH+6H2O=2Na[Al(OH)4]+3H2

[0044] The hydrogen generated in this process is collected and measured by a DN3-DN150 gas mass flow meter (Dalian Xindongxing Instrument Co., Ltd.). After being activated by leaching with the above-mentioned NaOH solution, the DL-1 type solid catalyst is obtained. It is rinsed with distilled water or deionized water until neutral to remove any residual sodium aluminate. It is then sealed in a vacuum bag for later use to prevent oxidation from exposure to air.

[0045] The aforementioned nickel-aluminum alloy powder, model RTH-2010, has a particle size distribution of 50μm, contains 48-50% (wt%) nickel, and the remainder is aluminum; it is produced by Yixing Chenfeng Alloy Materials Co., Ltd., Jiangsu Province.

[0046] The aforementioned pseudoboehmite powder, brand BR-P-DF-1 (macroporous pseudoboehmite), contains 0.2% SiO2, 0.1% Na2O, and 0.04% Fe2O3, and is produced by Shandong Bairui Chemical Co., Ltd.

[0047] The calcination temperature of the DL-1 alloy semi-finished product (i.e., alloy-Ni-W-Co / Al2O3) directly affects the compressive strength of the DL-1 solid strip-shaped catalyst after leaching and activation. The suitable calcination temperature is 848℃, which not only improves the hydrogenation activity and stability of the catalyst, but also oxidizes the dissolved metallic aluminum to form a high-strength "-Al2O3" phase, resulting in a compressive strength of 162 N·cm for the prepared DL-1 solid strip-shaped catalyst hydrogenation catalyst. -1 This meets the requirements for loading industrial fixed beds;

[0048] The table below shows the effect of calcination temperature on the crushing strength (N / cm) of the DL-1 solid catalyst. Sixty-five DL-1 alloy semi-finished products (i.e., alloy-Ni-W-Co / Al2O3) (4 mm in length) were first tested and calcined in a muffle furnace at different temperatures for 5 hours. After natural cooling to room temperature, they were activated by leaching with a 5.5 mol / L NaOH solution to obtain the DL-1 solid catalyst. The crushing strength was then tested, and the crushing strength data are shown in the table below.

[0049] <![CDATA[Catalyst strong N·cm -1 > 151 162 172 191

[0050] The table above shows that as the calcination temperature increases, the crush resistance of the catalyst continuously increases.

[0051] This invention compares and tests the hydrogenation catalytic activity of the DL-1 solid catalyst obtained at different temperatures:

[0052] The hydrogenation catalytic activity of the DL-1 solid catalyst at different calcination temperatures was tested by using benzene (hereinafter referred to as oil) to hydrogenate cyclohexane.

[0053] according to Figure 3 The method for hydrogen storage, transport, and dehydrogenation described in this invention was tested using the hydrogenation of benzene (hereinafter referred to as oil) to produce cyclohexane, at a reaction pressure of 4.5 MPa, a catalytic reaction temperature of 150-160 °C, and a benzene (oil) mass hourly space velocity of 1.8 h⁻¹. -1Under a hydrogen-to-oil ratio (V / V) of 50:1, the hydrogenation catalytic activity of the DL-1 solid catalyst calcined at different temperatures was tested. The apparent density of the DL-1 solid catalyst was approximately 2.7 g / cm³. 3 With an average diameter of 4 mm, under the action of the catalyst, one molecule of cyclohexane undergoes a decomposition reaction after absorbing 205.9 kJ / mol of heat, releasing three hydrogen molecules and one benzene molecule. The reversible reaction is that one benzene molecule absorbs three hydrogen molecules to become one cyclohexane molecule, releasing 205.9 kJ / mol of heat. The chemical equation is as follows, and the principle of hydrogenation is as follows:

[0054]

[0055] Hydrogenation conversion rate (%) 72.3 79.2 71.5 69.3

[0056] The data in the table above show that the catalyst with the highest hydrogenation catalytic activity (79.2%) was achieved at a calcination temperature of 849℃. As the calcination temperature increased, the hydrogenation activity of the catalyst gradually decreased. The conversion rate of benzene to cyclohexane reached 79.2% within the 72-hour period under investigation, indicating that the catalyst with a calcination temperature of 848℃ has ideal hydrogenation catalytic activity and meets the crushing strength requirements of industrial fixed-bed packing.

[0057] The "Liquid Organic Hydrogen Storage" (LOHC) technology described in this invention is a method for storing, transporting, and dehydrogenating hydrogen. It utilizes organic hydrides to undergo hydrogenation / dehydrogenation reactions with a catalyst under increased temperature, changed pressure, and the presence of a catalyst. The chemical principle of liquid organic hydrogen storage is a pair of reversible reactions between unsaturated liquid organic matter and hydrogen under the action of a solid catalyst. This is achieved through reversible catalytic hydrogenation and dehydrogenation reactions. The hydrogenation reaction achieves hydrogen storage (chemical bonding), and the dehydrogenation reaction achieves hydrogen release.

[0058] During hydrogenation, the catalytic reaction of benzene (such as liquid organic matter) to produce cyclohexane is an addition reaction. The overall heat balance of the addition reaction is exothermic. Continuously removing the heat generated in the addition reaction favors the reversible reaction to proceed in the direction of hydrogen storage and cyclohexane production. Conversely, during dehydrogenation, the decomposition of cyclohexane into benzene (such as liquid organic matter) and hydrogen is an endothermic reaction. Continuously heating cyclohexane, under the action of a catalyst, favors the reversible reaction to proceed in the reverse direction to produce benzene (such as liquid organic matter) and hydrogen products. This invention uses diesel fuel from a vehicle's fuel tank as fuel, which is burned in a heating furnace to heat the circulating liquid organic matter or provide the heat required for the dehydrogenation reaction. Room temperature air is used as a cooling medium to cool the hydrogenation reaction and absorb the heat released during hydrogen storage or the hydrogenation reaction.

[0059] The key to organic liquid hydrogen storage lies in selecting a suitable hydrogen storage medium. Key performance indicators to consider when selecting an organic hydrogen storage medium include: 1) high mass and volumetric hydrogen storage capacity; 2) suitable melting point, ensuring a stable liquid state at room temperature; 3) stable composition, high boiling point, and low volatility; 4) high ring chain stability during dehydrogenation, preventing hydrogen contamination, high hydrogen release purity, and easy dehydrogenation; 5) cost of the storage medium itself; 6) high recyclability; and 7) low or non-toxicity.

[0060] Unsaturated organic liquids such as alkenes, alkynes, and aromatics can all be used as hydrogen storage materials, with aromatics being the best. Commonly used liquid organic hydrogen storage materials include benzene, toluene, carbazole, and naphthalene, with hydrogen storage capacities exceeding 6 wt% and hydrogen storage densities exceeding 50 kg / m³. 3 In principle, every unsaturated compound (an organic molecule with carbon-carbon double or triple bonds) can absorb hydrogen during hydrogenation. Liquid organic hydrogen storage technology utilizes hydrogen storage agents such as certain alkenes, alkynes, or aromatic hydrocarbons to achieve hydrogenation and dehydrogenation through reversible reactions with hydrogen gas. In LOHC, hydrogen chemically bonds to the organic hydrocarbon support molecule (hydrogenation) and can be released through a reverse process (dehydrogenation).

[0061] The advantages of this invention are:

[0062] 1. The special vehicle described in this invention can scientifically and energy-efficiently implement a one-stop service for hydrogen storage, transportation, and dehydrogenation high-pressure hydrogen supply, solving the problems of cumbersome processes, multiple steps, low efficiency, and high costs associated with hydrogen storage, transportation, and dehydrogenation supply; it has the advantages of high hydrogen storage capacity, short operation process, low equipment investment, low operating cost, safety and reliability, and comprehensive scientific management.

[0063] 2. The hydrogen transport and dehydrogenation of this invention are carried out at atmospheric pressure. Atmospheric pressure transport of hydrogen is safe and reliable, overcoming the safety hazards that may occur during the transport of hydrogen stored in high-pressure cylinders. In particular, it overcomes the need for heavy pressure-resistant containers for high-pressure hydrogen storage and operation, which consumes a large amount of hydrogen compression work. It also overcomes the safety hazards such as easy hydrogen leakage and container explosion, and overcomes the high material requirements, high manufacturing cost, and safety risks of high-pressure hydrogen storage tanks.

[0064] 3. The DL-1 type solid catalyst used in the hydrogenation / dehydrogenation catalytic reaction of this invention has a hydrogenation catalytic reaction temperature of 130-210℃ and a dehydrogenation temperature of 150-260℃. It has the advantages of high crushing strength, good hydrogenation / dehydrogenation efficiency, no precious metal materials, and low cost.

[0065] 4. The cargo box top plate of the transport vehicle described in this invention can slide parallel or open, which facilitates the upward dissipation of trace amounts of hydrogen gas leaking from the cargo box and prevents the generation of hydrogen gas "explosion gas" in the cargo box. The left and right side panels of the cargo box can extend upward or downward at will within the range of 0-90 degrees, which is convenient for workers to operate.

[0066] 5. The present invention uses multiple sets of tubular catalytic reactors for hydrogenation / dehydrogenation with limited cargo box height, which can be connected in series or in parallel, greatly improving the output of hydrogen storage and dehydrogenation applications in vehicle cargo boxes;

[0067] 6. This invention uses a tubular fixed-bed catalytic reactor, which is resistant to high pressure and safe to operate;

[0068] 7. The present invention converts the heat released by the cold hydrogen absorption hydrogenation catalytic reaction into hot hydrogen, thereby improving the thermal efficiency of the hydrogenation reaction;

[0069] 8. This invention utilizes room temperature hydrogen (or cold hydrogen) to cool the hydrogen reaction, thereby controlling and regulating the appropriate temperature required to maintain the catalytic reaction;

[0070] 9. This invention employs a pressure-resistant tubular fixed-bed catalytic reactor. The tubular equipment can withstand high pressure, and a high hydrogen-to-oil ratio or increased hydrogen partial pressure can promptly remove the heat of the catalytic reaction from the system, making the temperature of the entire catalytic bed stable and easy to control. Using a high hydrogen-to-oil ratio and increasing the hydrogen partial pressure improves the hydrogenation reaction rate and the hydrogen storage capacity per unit time.

[0071] 10. This invention utilizes the engine and power take-off unit on the transport vehicle to generate electricity, which supplies the electrical energy required for the hydrogen storage or dehydrogenation process, overcoming the defect that the aforementioned special vehicle cannot store or supply hydrogen in an environment without power supply.

[0072] 11. This invention performs hydrogenation or dehydrogenation within the same tubular fixed-bed catalytic reactor, which greatly saves equipment investment and reduces production energy consumption; Attached Figure Description

[0073] Figure 1 A schematic diagram of a special vehicle structure for hydrogen storage, transportation, and dehydrogenation according to the present invention;

[0074] Figure 2 This invention provides a schematic diagram of a cargo box structure for a hydrogen storage, transportation, and dehydrogenation device.

[0075] Figure 3 A schematic diagram of the structure of a hydrogen storage, transportation and dehydrogenation device according to the present invention;

[0076] Figure 4 A rear view structural schematic diagram of the cargo box of a hydrogen storage, transportation and dehydrogenation device according to the present invention;

[0077] Figure 5 Schematic diagram of the generator configuration structure of the special vehicle of this invention:

[0078] Figure 6 A schematic diagram illustrating the reversible chemical reaction of "methylcyclohexane-hydrogen-toluene" described in the method of this invention, involving hydrogenation and hydrogen release;

[0079] exist Figure 1 , Figure 2 , Figure 3 , Figure 4 and Figure 5 In the diagram, 1-Valve One, 2-Valve Two, 3-Outlet One, 4-Hydrogen Compressor One, 5-Inlet One, 6-Pressure Gauge One, 7-Pipe One, 8-Inlet Two, 9-Outlet Two, 10-Liquid Level Line, 11-Liquid Organic Matter, 12-Bottom Outlet Three, 13-Gas-Liquid Separator, 14-Sampling Valve, 15-Organic Solvent Pump, 16-Vehicle Fuel Tank, 17-Pipe Three, 18-Shell-and-Tube Condenser, 19-Pipe Four, 20-Inlet Three, 21-Hydrogen Compressor Two, 22-Outlet... 23-Hydrogen buffer tank, 24-Outlet 5, 25-Pipeline 5, 26-Heat exchanger 1, 27-Valve 3, 28-Pressure gauge 2, 29-Cold hydrogen pipeline, 30-Pressure gauge 3, 31-Inlet 4, 32-Rear door of cargo box, 33-Upper sieve plate 2, 34-Inlet 5, 35-Thermometer 1, 36-Solid catalyst, 37-Lower sieve plate 2, 38-Inlet 6, 39-Tubular fixed bed catalytic reactor 2, 40-Thermometer 2, 41-Outlet 6, 42-Pipeline 6 43-Pipe 7, 44-Heat Exchanger 2, 45-Pipe 8, 46-Pipe 9, 47-Outlet 7, 48-Tubular Fixed Bed Catalytic Reactor 1, 49-Inlet 7, 50-Inlet 8, 51-Inlet 9, 52-Outlet 8, 53-Gas-Liquid Mixer, 54-Inlet 10, 55-Pipe 10, 56-Heating Tube, 57-Outlet 9, 58-Heating Furnace, 59-Inlet 11, 60-Cargo Box, 61-Pulley, 62-Front Top Plate of Cargo Box, 63-Rear Top of Cargo Box Top plate, 64-Vehicle engine, 65-Power take-off, 66-Generator, 67-Pulley, 68-Vehicle clutch, 69-Vehicle gearbox, 70-Cargo box side door panel, 71-Latch, 72-Hydraulic device for opening or closing the cargo box side door panel, 73-Transport vehicle, 74-Vehicle drive shaft, 75-Generator, 76-Transport vehicle chassis, 77-Wheel, 78-Upper screen plate one, 79-Lower screen plate one, 80-Pipe eleven, 81-Hydrogen outlet pipe; Detailed Implementation

[0080] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments are not limited thereto.

[0081] A special vehicle for hydrogen storage, transportation, and dehydrogenation mainly consists of two parts: a cargo box (60) equipped with hydrogen storage, transportation, and dehydrogenation equipment, and a transport vehicle (73). The cargo box (60) can be a fixed or movable cargo box on the vehicle. The hydrogen storage, transportation, and dehydrogenation equipment includes: valve one (1), valve two (2), hydrogen compressor one (4), pressure gauge one (6), gas-liquid separator (13), sampling valve (14), organic solvent pump (15), shell-and-tube condenser (18), hydrogen compressor two (21), hydrogen buffer tank (23), heat exchanger one (26), valve three (27), and pressure gauge one (73). Force gauge 2 (28), pressure gauge 3 (30), thermometer 1 (35), tubular fixed-bed catalytic reactor 2 (39), thermometer 2 (40), heat exchanger 2 (44), tubular fixed-bed catalytic reactor 1 (48), gas-liquid mixer (53) and heater (58); the aforementioned hydrogen storage, hydrogen transportation and dehydrogenation equipment is configured in the cargo box (60) to form a cargo box (60) equipped with a hydrogen storage, hydrogen transportation and dehydrogenation equipment; the aforementioned cargo box (60) equipped with a hydrogen storage, hydrogen transportation and dehydrogenation equipment is fixed on the chassis (76) of the transport vehicle to form a whole, thus forming a special vehicle for hydrogen storage, hydrogen transportation and dehydrogenation;

[0082] The hydrogen outlet five (24) on the hydrogen buffer tank (23) is connected to the inlet three (20) of the hydrogen compressor two (21) via a pipe; the outlet four (22) of the hydrogen compressor two (21) is connected to the shell-side inlet of the heat exchanger one (26) via a pipe five (25); the shell-side outlet of the heat exchanger one (26) is connected to the shell-side inlet of the heat exchanger two (44) via a pipe seven (43); the shell-side outlet of the heat exchanger two (44) is connected to the inlet ten (54) of the gas-liquid mixer (53) via a pipe eight (45); and the outlet eight (52) of the gas-liquid mixer (53) is connected to the tubular fixed-bed catalytic reactor one (4) via a pipe. 8) The top inlet nine (51) is connected to the bottom outlet seven (47) of the tubular fixed-bed catalytic reactor one (48) and is connected to the tube-side inlet of heat exchanger two (44) through pipe nine (46). The tube-side outlet of heat exchanger two (44) is connected to the top inlet four (31) of tubular fixed-bed catalytic reactor two (39) through pipe six (42). The bottom outlet six (41) of tubular fixed-bed catalytic reactor two (39) is connected to the tube-side inlet of heat exchanger one (26). The tube-side outlet of heat exchanger one (26) is connected to the tube-side inlet of shell-and-tube condenser (18) through pipe four (19). The tube-side outlet of shell-and-tube condenser (18) is connected to the tube-side inlet of the tube-side condenser (18). The outlet of the process is connected to the inlet 2 (8) at the top of the gas-liquid separator (13) via pipe 1 (7). The outlet 2 (9) at the top of the gas-liquid separator (13) is connected to the inlet 1 (5) of the hydrogen compressor 1 (4) via pipe. The outlet 1 (3) of the hydrogen compressor 1 (4) is connected to the inlet of valve 1 (1) and the inlet of valve 2 (2) via pipe. The outlet of valve 1 (1) is equipped with a hydrogen outlet pipe (81). The outlet of valve 2 (2) is connected to the inlet 8 (50) and the inlet 7 (49) of the tubular fixed bed catalytic reactor 1 (48) via cold hydrogen pipe (29). The outlet of valve 2 (2) is connected to the inlet 8 (50) and the inlet 7 (49) of the tubular fixed bed catalytic reactor 1 (48) via cold hydrogen pipe (29). The valve 2 (2) is connected to the inlet 5 (34) and inlet 6 (38) of the tubular fixed bed catalytic reactor 2 (39). The outlet of the valve 2 (2) is connected to the inlet 10 (54) of the gas-liquid mixer (53) through the cold hydrogen pipeline (29). The bottom outlet 3 (12) of the gas-liquid separator (13) is connected to the inlet of the organic solvent pump (15) through the pipeline 11 (80). The outlet of the organic solvent pump (15) is connected to the inlet 11 (59) of the heating furnace (58) through the pipeline 3 (17). The outlet 9 (57) of the heating tube (56) in the heating furnace (58) is connected to the inlet 10 (54) of the gas-liquid mixer (53) through the pipeline 10 (55).

[0083] The tubular fixed-bed catalytic reactor (48) is a cylindrical metal sealed cylinder. The middle section of the cylinder is equipped with an upper sieve plate (78) and a lower sieve plate (79). The outer wall of the cylinder below the upper sieve plate (78) is equipped with an inlet eight (50), and the outer wall of the cylinder below the lower sieve plate (79) is equipped with an inlet seven (49). A solid catalyst (36) is placed between the upper sieve plate (78) and the lower sieve plate (79). The temperature sensing head of the thermometer two (40) is inserted into the solid catalyst (36). The top of the tubular fixed-bed catalytic reactor (48) is equipped with an inlet nine (51), and the bottom of the tubular fixed-bed catalytic reactor (48) is equipped with an outlet seven (47). The tubular fixed-bed catalytic reactor (48) is filled with liquid organic matter (11), and a pressure gauge three (30) is inserted into the liquid organic matter (11).

[0084] The tubular fixed-bed catalytic reactor II (39) is a cylindrical metal sealed cylinder. The middle section of the cylinder is equipped with an upper sieve plate II (33) and a lower sieve plate II (37). The outer wall of the cylinder below the upper sieve plate II (33) is equipped with an inlet V (34), and the outer wall of the cylinder below the lower sieve plate II (37) is equipped with an inlet VI (38). A solid catalyst (36) is placed between the upper sieve plate II (33) and the lower sieve plate II (37). The temperature sensing head of thermometer I (35) is inserted into the solid catalyst (36). The top of the tubular fixed-bed catalytic reactor II (39) is equipped with an inlet IV (31), and the bottom of the tubular fixed-bed catalytic reactor II (39) is equipped with an outlet VI (41). The tubular fixed-bed catalytic reactor II (39) is filled with liquid organic matter (11), and pressure gauge I (6) is inserted into the liquid organic matter (11).

[0085] The heating furnace (58) is a petrochemical cylindrical tube heating furnace, commonly used as a heating furnace for crude oil atmospheric and vacuum distillation; the heating furnace consists of a radiation chamber, a convection chamber, a waste heat recovery system, a burner, and a ventilation system; the heating furnace is equipped with a coil; the coil is a seamless high-temperature resistant steel pipe, and the seamless high-temperature resistant steel pipe contains flowing liquid organic material. Electric heating, fuel oil, or gas combustion is used to heat the outer wall of the coil in the heating chamber, thereby heating the flowing liquid organic material inside the seamless high-temperature resistant steel pipe.

[0086] The hydrogen compressor one (4) and hydrogen compressor two (21) mentioned above are hydrogen compressors, with models including QB, DSR, and FXY, each having different compression ratios and discharge capacities. Among them, the QB series is the basic model, the DSR series is the high-pressure model (≥15MPa), and the FXY series is the large-displacement model.

[0087] The gas-liquid separator (13) is a chemical industry gas-liquid separator. It is a closed tank. The top of the gas-liquid separator is equipped with an inlet two (8) and an outlet two (9). The bottom of the tank is equipped with an outlet three (12). The liquid level line (10) in the tank is located at 2 / 3 to 4 / 5 of the tank height. The outlet pipe on the side at 1 / 2 of the tank height is equipped with a sampling valve (14). The outlet pipe is inserted into the liquid organic matter.

[0088] The gas-liquid mixer (53) is an industrial gas-liquid two-phase mixing device. Its basic working principle is to use the mixing unit fixed in the pipe to change the flow state of the fluid in the pipe in order to achieve good dispersion and full mixing between different gas and liquid fluids.

[0089] The organic solvent pump (15) mentioned above is a pneumatic diaphragm pump or corrosion-resistant pump commonly used in the chemical industry. It is suitable for conveying various corrosive liquids, liquids containing particles, high viscosity, volatile organic compounds, flammable and highly toxic liquids.

[0090] The shell-and-tube condenser (18) is a conventional shell-and-tube heat exchanger used in the petrochemical industry.

[0091] The heat exchanger one (26) and heat exchanger two (44) are conventional shell-and-tube heat exchangers for the petrochemical industry, including a tube side and a shell side; the tube side contains flowing high-temperature liquid organic matter, and the shell side contains flowing cold hydrogen. The cold hydrogen is transformed into hot hydrogen after heat exchange, and the temperature of the high-temperature liquid organic matter decreases after heat exchange.

[0092] The transport vehicle (73) mainly includes: a cab, an engine (64), a generator (75), a clutch (68), a gearbox (69), a power take-off (65) mounted on the gearbox, a chassis (76), a vehicle drive shaft (74), and wheels (77); it is a modified vehicle that uses the power output shaft of the power take-off (65) connected to the vehicle gearbox (69) to drive the generator (75) to generate electricity, or a vehicle with an external power source to charge the on-board battery; the transport vehicle is a vehicle manufactured by a vehicle manufacturer or a modified diesel, gasoline, or new energy vehicle; the engine power of the transport vehicle is between 80 and 350 horsepower; the transport vehicle is equipped with an external power socket, or an external power source (220V or 380V) to provide electrical or thermal energy to the hydrogen storage and dehydrogenation equipment in the cargo box (60);

[0093] The cargo box (60) is the cargo box configured when the transport vehicle (73) leaves the factory. It is a cargo box modified according to the following structure: The top of the cargo box (60) is composed of two front top plates (62) and rear top plates (63) that can slide back and forth in parallel, and several sets of pulleys (61) at the bottom of the supporting slide plate; any top plate of the cargo box can be moved to one side of the other top plate in parallel, forming an open area of ​​about half of the top of the cargo box, so as to facilitate the operation, maintenance, replacement or hoisting of the equipment inside the cargo box; the movement of the front top plate (62) and the rear top plate (63) is operated by electric or manual operation; when the front top plate (62) and the rear top plate (63) of the cargo box return to their respective ends, the top of the cargo box will be completely sealed, and the top of the cargo box and each side door panel (70) will form a three-dimensional cargo box as a whole; the front top plate (62) and the rear top plate (63) The side panels (63) are locked and fixed. The left and right side panels (70) of the cargo box of the transport vehicle are divided into two parts, upper and lower. Each side panel (70) can extend upward or downward at any angle within the range of 0-90 degrees. The extended side panels (70) are controlled and stabilized by a hydraulic device (72). When all the extended side panels on the side of the cargo box are closed and the top of the cargo box is sealed, the upper, lower, front, back, left and right side panels of the cargo box are combined to form the cargo box as a whole. Each side panel (70), front top panel (62) and rear top panel (63) are fixed with a locking buckle (71). The left and right side panels (70) of the cargo box adopt the double-door structure of the postal express vehicle. The two doors are locked on the center line of the two doors and the two doors are opened to the left and right. The two side panels (70) and the rear door (32) of the cargo box adopt the box truck structure.

[0094] The technical principle of a hydrogen storage and dehydrogenation method using the aforementioned special vehicle is as follows:

[0095] 1. The power take-off unit configured in the vehicle engine drives the generator to produce 220V or 380V electricity to power the electrical equipment on the hydrogen storage and dehydrogenation devices.

[0096] 2. Hydrogen storage / dehydrogenation using liquid organic hydrogen storage technology (LOHC) involves the hydrogenation / dehydrogenation of organic hydrides under varying temperatures, pressures, and catalysts. Under the action of a solid catalyst, a pair of reversible reactions occur between unsaturated liquid organic compounds and hydrogen, utilizing catalytic hydrogenation and dehydrogenation. Hydrogenation achieves hydrogen storage (chemical bonding), while dehydrogenation releases hydrogen. In LOHC, hydrogen chemically bonds to the organic hydrocarbon support molecule under the action of a catalyst (hydrogenation). It can also be released through a reverse process (dehydrogenation); the mass hydrogen storage density is 5%-6%, with a large hydrogen storage capacity; the hydrogen storage material is a liquid organic compound (such as dibenzyltoluene, decahydronaphthalene, carbazole, N-ethylcarbazole, dimethylindole, benzene, and toluene), which can be transported at room temperature and pressure, making it convenient and safe; in principle, every unsaturated organic compound with a carbon-carbon double or triple bond can absorb hydrogen during hydrogenation; during hydrogenation and dehydrogenation, the catalyst can not only reduce the reaction temperature but also improve the reaction rate of chemical hydrogen storage technology;

[0097] 3. The apparent density of the DL-1 type solid catalyst of the present invention is approximately 2.7 g / cm³. 3 With a length of 4mm and a compressive strength of 162N / cm, it has a low hydrogenation / dehydrogenation catalytic reaction temperature and is an energy-saving hydrogenation / dehydrogenation catalyst. It has good hydrogenation / dehydrogenation catalytic activity and crush resistance, meeting the requirements of fixed bed packing.

[0098] The method of the present invention is described in more detail below with reference to embodiments, but is not limited thereto.

[0099] Example

[0100] See Figure 1 , Figure 2 , Figure 3 , Figure 4 , Figure 5 and Figure 6The Dongfeng Chenglong M3V box truck (model LZ5161XXYLAS, engine: Yuchai YC4E160-33 / 160, 160 horsepower (or 120KW); the box is 7.65 meters long, 2.4 meters wide, and 2.5 meters high; with a load capacity of 10 tons) is used as the transport vehicle (73). The special vehicle for storing, transporting, and dehydrogenating hydrogen is parked at the water electrolysis hydrogen production plant. The vehicle engine (64) is started to drive the power take-off (65) to work. The power take-off (65) drives the generator (75) to generate electricity to power the electrical equipment on the special vehicle. The rear door (32) and side door (70) of the cargo box (60) are opened to facilitate personnel operation. The 99.99% hydrogen produced in the factory is added to the hydrogen buffer tank (23) through valve three (27). The room temperature hydrogen (or cold hydrogen) in the hydrogen buffer tank (23) is first transported to the shell side of heat exchanger one (26) for heat exchange, and then transported to the shell side of heat exchanger two (44) for heat exchange. The hot hydrogen after heat exchange is then transported to the LS-1-300 static gas-liquid mixer (53). At the same time, the ZCQ A -5.5 type self-priming organic solvent pump (15) transports toluene (11) (hereinafter also referred to as "oil") in the gas-liquid separator (13) to a heating furnace (58) heated by a 200,000 kcal fuel oil burner for indirect heating to 180-210°C. The heated toluene liquid organic matter (11) is then transported to a gas-liquid mixer (53). In the gas-liquid mixer (53), hydrogen and toluene liquid organic matter (11) are mixed. The mixed material continuously enters the tubular fixed-bed catalytic reactor (48), where it is directly mixed with the DL-1 type granular catalyst (36) in the tubular fixed-bed catalytic reactor (48). The hydrogenation catalytic reaction occurs in direct contact. In the first tubular fixed-bed catalytic reactor (48), the catalytic reaction pressure is controlled at 2.5 MPa and the temperature is controlled at 180-210℃. The material after the hydrogenation catalytic reaction is continuously discharged from the bottom outlet seven (47) of the first tubular fixed-bed catalytic reactor (48). After being cooled by heat exchange in the tube side of the second heat exchanger (44), the material enters the second tubular fixed-bed catalytic reactor (39) and directly contacts the DL-1 type granular catalyst (36) in the second tubular fixed-bed catalytic reactor (39) to undergo a hydrogenation catalytic reaction. In the second tubular fixed-bed catalytic reactor (39), the catalytic reaction pressure is controlled at 2.5 MPa.At 5 MPa and a temperature control of 180-210℃, the material after hydrogenation catalytic reaction is continuously discharged from the tubular fixed-bed catalytic reactor II (39). After heat exchange in heat exchanger I (26), it enters the shell-and-tube condenser (18) and is cooled to 25℃ with water. The cooled material is then transported to the gas-liquid separator (13). In the gas-liquid separator (13), the remaining greenhouse hydrogen (or cold hydrogen) that has not been absorbed in the tubular fixed-bed catalytic reactor II (50) separates from the liquid organic matter. The cold hydrogen is continuously recycled and utilized to absorb the hydrogenation reaction of the tubular fixed-bed catalytic reactor I (48) and the tubular fixed-bed catalytic reactor II (39). The heat released keeps the temperature of the hydrogen absorption catalytic reaction within the range of 180-210℃. Cold hydrogen overflows from the top of the gas-liquid separator (13) and enters the ZW-0.52 / 2-250 type hydrogen compressor (4). The hydrogen compressor (4) and the cold hydrogen pipeline (29) continuously circulate the cold hydrogen to the tubular fixed-bed catalytic reactor (48) and the tubular fixed-bed catalytic reactor (39) to cool the exothermic hydrogenation catalytic reaction. Alternatively, the hydrogen compressor (4) and the cold hydrogen pipeline (29) continuously circulate the cold hydrogen to the tubular fixed-bed catalytic reactor (48) to cool the exothermic hydrogenation catalytic reaction and transport it to the tubular fixed-bed catalytic reactor (39). The exothermic hydrogenation catalytic reaction is cooled in the second fixed-bed catalytic reactor (39) to maintain the hydrogenation catalytic reaction temperature in the range of 180-210℃. Alternatively, cold hydrogen is continuously transported through the gas-liquid mixer (53) to the hydrogenation catalytic reaction in the first fixed-bed catalytic reactor (48) using the first hydrogen compressor (4) and the cold hydrogen pipeline (29) to replenish the hydrogen feedstock. The liquid organic matter (11) in the gas-liquid separator (13) is continuously heated in the heater (58) using the organic solvent pump (15) and then enters the first fixed-bed catalytic reactor (48) and the tubular fixed-bed catalytic reactor (48) in sequence after passing through the gas-liquid mixer (53). The hydrogenation catalytic reaction is carried out in reactor two (39); after the catalytic reaction, hydrogen is absorbed by liquid organic matter (11) or stored in liquid organic matter (11). The hydrogenation catalytic reaction pressure is controlled at 2.5 MPa and the temperature is controlled at 180-210℃. In the exothermic hydrogenation catalytic reaction, the cold hydrogen generated by the gas-liquid separator (13) is transported through the cold hydrogen pipeline (29) to the tubular fixed bed catalytic reactor one (48) and the tubular fixed bed catalytic reactor two (39). The circulating cold hydrogen enters the catalytic reactor to cool the hydrogenation catalytic reaction and control and adjust to maintain the appropriate temperature required for the catalytic reaction.

[0101] Open valve (14) to take a sample and test the hydrogenation reaction of the liquid organic matter. When the hydrogen storage content in the liquid organic matter is higher than 5.0 wt% and the hydrogen storage density is higher than 50 kg / m³, the hydrogen storage is tested. 3When the hydrogen storage operation is completed, and the hydrogen storage capacity is greater than 5.0 wt% and the hydrogen storage density is greater than 50 kg / m³, the hydrogen storage operation is completed. 3 The liquid organic matter (hereinafter referred to as "hydrogen oil") is buffered in the gas-liquid separator (13), the tubular fixed-bed catalytic reactor one (48) and the tubular fixed-bed catalytic reactor two (39) for later use. The operation of hydrogen compressor one (4) and hydrogen compressor two (21) is stopped, the operation of organic volumetric pump (15) is stopped, and the circulation of cooling water in shell-and-tube condenser (18) is turned off. The rear door (32) and side door (70) of cargo box (60) are closed, and the generator (75) is stopped from generating electricity.

[0102] In this embodiment, the volume ratio (V / V) of liquid organic matter to hydrogen is 50:1; the volume hourly space velocity (VHSV) of the liquid organic matter is 5.0 h⁻¹. -1 The aforementioned hydrogen storage, transportation, and dehydrogenation vehicle is driven to a hydrogen vehicle refueling station, and the hydrogen stored in the vehicle is transported to the hydrogen vehicle refueling station's "Hydrogen Tube Bundle Container". The product model of the container is GJ06-4010-H2-20, the working pressure of the gas cylinder is 20MPa, the number of gas cylinders is 6, the total volume of the gas cylinders is 24.06m3, and the gas cylinder material is 413X.

[0103] Operation method for dehydrogenation or hydrogen release: Start the vehicle engine (64) to drive the power take-off (65) to work, and the power take-off (65) drives the generator (75) to generate electricity to power the electrical equipment on the special vehicle; open the rear door (32) and side door panel (70) of the cargo box (60) for easy operation; close valve two (2), close valve three (27), close hydrogen compressor two (21), open valve one (1), and connect the hydrogen outlet pipe (81) to the inlet of the hydrogen cylinder in the above-mentioned centralized box; then, start hydrogen compressor one (4) and start organic solvent pump (15) to rotate, and transfer the hydrogen from the gas-liquid separator (13) to the gas-liquid separator. The hydrogenated liquid organic matter (hereinafter referred to as "hydrogen oil") is transported to a heating furnace (58) and heated to 235-240°C. The heated "hydrogen oil" is then passed through a gas-liquid mixer (53) and sequentially enters a tubular fixed-bed catalytic reactor one (48) and a tubular fixed-bed catalytic reactor two (39) to allow the "hydrogen oil" to undergo a dehydrogenation catalytic reaction with the DL-1 type granular catalyst (36) in the tubular fixed-bed catalytic reactor one (48) and the tubular fixed-bed catalytic reactor two (39). The temperature of the dehydrogenation catalytic reaction is controlled at 235-240°C, the pressure is maintained at atmospheric pressure, and the space velocity of the solid catalyst is 4 h⁻¹. -1After being heated and reacted with a catalyst, the "hydrogen oil" decomposes into hydrogen and liquid organic matter. The mixture formed by the hydrogen and liquid organic matter enters the shell-and-tube condenser (18) and is condensed to room temperature. The mixture at room temperature is then transported to the gas-liquid separator (13) for gas-liquid separation. In the gas-liquid separator (13), hydrogen (cold hydrogen) overflows from the outlet (9) of the gas-liquid separator (13) and passes through the ZW-0.52 / 2-250 hydrogen compressor (4) (produced by Bengbu Aote Compression Machine Co., Ltd., air-cooled, equipment weight 180kg, power 37kw). The hydrogen gas is extracted (intake pressure 0.2MPa, outlet pressure 25MPa) and passed through valve 1 (1) and hydrogen outlet pipe (81) to be transported to the hydrogen cylinder in the container (model: GJ06-4010-H2-20) for storage and future use; the separated liquid organic matter is stored at the liquid level (10) of the gas-liquid separator (13). The liquid organic matter stored in the gas-liquid separator (13) is continuously extracted and transported to the heating furnace (58) for heating and temperature rise, and the above dehydrogenation catalytic reaction process is carried out in a cycle;

[0104] Open valve (14) to take a sample and detect the dehydrogenation catalytic reaction of liquid organic matter. When the amount of hydrogen stored in the liquid organic matter is less than 0.5 wt%, the dehydrogenation or hydrogen release ends: that is, turn off the operation of hydrogen compressor one (4), stop the operation of organic solvent pump (15), stop the operation of heating furnace (58), and at the same time close valve one (1); close the rear door (32) and side door (70) of cargo box (60), and stop the generator (75) from generating electricity;

[0105] The relevant process parameters for hydrogen storage and dehydrogenation of the aforementioned special-purpose vehicles are as follows:

[0106] (I) Special Purpose Vehicles

[0107] Vehicle type: Dongfeng Chenglong M3V box truck;

[0108] Vehicle dimensions: 7150×2500×3500 (mm);

[0109] Fuel type: diesel;

[0110] Vehicle model: LZ5161XXYLAS;

[0111] Vehicle engine: Yuchai YC4E160-33 / 160, 160 horsepower (or 120KW);

[0112] The power take-off unit is equipped with a generator with a power output of 80 kVA (or 80 kWh of electricity per hour) to power the hydrogen storage and dehydrogenation equipment.

[0113] (ii) The diameter of tubular fixed-bed catalytic reactor one (48) or tubular fixed-bed catalytic reactor two (39) is 1.6 meters, the height is 2 meters, and the volume is 4 m³. 3 The catalyst packing height is 0.5 meters, and the catalyst packing volume is 1 m³. 3 Liquid organic matter occupies a volume of 3m³ 3 The gas-liquid separator (13) has a diameter of 1.6 meters and a length of 2 meters, which is a volume of 4 m³. 3 Its liquid organic matter loading capacity is 3m³ 3 The total loading of liquid organic matter in the tubular fixed-bed catalytic reactor one (48), the tubular fixed-bed catalytic reactor two (39), and the gas-liquid separator (13) is 8m³. 3 ;

[0114] (iii) The hydrogenation / dehydrogenation catalyst is: DL-1 type long strip catalyst with a crush resistance strength of 162 N / cm, an apparent density of about 2.7 g / cm3, and a length of 4 mm; the catalyst loading amount in the tubular fixed bed catalytic reactor one (48) is 2700 kg, the catalyst loading amount in the tubular fixed bed catalytic reactor two (39) is 2700 kg, and the total catalyst loading amount is 5400 kg.

[0115] (iv) The liquid organic matter in this embodiment is toluene (abbreviated as oil), with a density of 0.86 g / ml and a boiling point of 138.35~144.42℃. It is a liquid at room temperature. The total loading of the liquid organic matter (toluene) in the tubular fixed-bed catalytic reactor one (48), tubular fixed-bed catalytic reactor two (39), and gas-liquid separator (13) in the special vehicle is 6880 kg. (v) Hydrogenation catalytic reaction conditions: temperature is 180-210℃, pressure is 2.5 MPa, and liquid hourly space velocity of the liquid organic matter is 5 h⁻¹. -1 The hydrogen-to-oil ratio is 50:1;

[0116] (vi) Conditions for dehydrogenation catalytic reaction: Temperature is 235-240℃, pressure is atmospheric pressure, and the liquid hourly space velocity of the liquid organic matter is 4 h⁻¹. -1 ;

[0117] (vii) Hydrogen addition or hydrogen storage capacity: The hydrogen addition capacity is 5.0% (wt%) of the liquid organic matter, which is 344 kg, i.e. 6880 × 5.0%;

[0118] (viii) Dehydrogenation amount: The hydrogen content in the liquid organic matter after dehydrogenation is 0.5% (wt%), and the amount of hydrogen removed is 328.52 kg: that is, 344-344 kg × (5.0-0.5)%.

[0119] (ix) Heating furnace (58): The heating furnace (58) is heated by a diesel burner with a capacity of 100,000 kcal to raise the temperature of the liquid organic matter; the diesel comes from the fuel tank (16) of the transport vehicle (73);

[0120] (x) Cooling medium for shell-and-tube condenser (18): air cooling.

Claims

1. A special vehicle for hydrogen storage, transportation, and dehydrogenation, mainly composed of a cargo box (60) equipped with hydrogen storage, transportation, and dehydrogenation equipment, and a transport vehicle (73); the cargo box (60) is either a fixed cargo box or a movable cargo box on the vehicle; the hydrogen storage, transportation, and dehydrogenation equipment includes: Valve 1 (1), Valve 2 (2), Hydrogen Compressor 1 (4), Pressure Gauge 1 (6), Gas-Liquid Separator (13), Sampling Valve (14), Organic Solvent Pump (15), Shell-and-Tube Condenser (18), Hydrogen Compressor 2 (21), Hydrogen Buffer Tank (23), Heat Exchanger 1 (26), Valve 3 (27), Pressure Gauge 2 (28), Pressure Gauge 3 (30), Thermometer 1 (35), Tubular Fixed-Bed Catalytic Reactor 2 (39), Thermometer 2 (40) Heat exchanger 2 (44), tubular fixed bed catalytic reactor 1 (48), gas-liquid mixer (53) and heater (58); the hydrogen storage, hydrogen transportation and dehydrogenation equipment is configured in the cargo box (60) to form a cargo box (60) equipped with a hydrogen storage, hydrogen transportation and dehydrogenation equipment; the cargo box (60) equipped with a hydrogen storage, hydrogen transportation and dehydrogenation equipment is fixed on the chassis (76) of the transport vehicle to form a whole, forming a special vehicle for hydrogen storage, hydrogen transportation and dehydrogenation; The hydrogen outlet five (24) on the hydrogen buffer tank (23) is connected to the inlet three (20) of the hydrogen compressor two (21) via a pipe; the outlet four (22) of the hydrogen compressor two (21) is connected to the shell-side inlet of the heat exchanger one (26) via a pipe five (25); the shell-side outlet of the heat exchanger one (26) is connected to the shell-side inlet of the heat exchanger two (44) via a pipe seven (43); the shell-side outlet of the heat exchanger two (44) is connected to the inlet ten (54) of the gas-liquid mixer (53) via a pipe eight (45); and the outlet eight (52) of the gas-liquid mixer (53) is connected to the tubular fixed-bed catalytic reactor one (48) via a pipe. The top inlet nine (51) of the tubular fixed-bed catalytic reactor one (48) is connected to the bottom outlet seven (47) of the tubular fixed-bed catalytic reactor one (48) via pipe nine (46), and the tube-side inlet of the heat exchanger two (44) is connected to the top inlet four (31) of the tubular fixed-bed catalytic reactor two (39) via pipe six (42). The bottom outlet six (41) of the tubular fixed-bed catalytic reactor two (39) is connected to the tube-side inlet of the heat exchanger one (26), and the tube-side outlet of the heat exchanger one (26) is connected to the tube-side inlet of the shell-and-tube condenser (18) via pipe four (19). The tube-side outlet of the shell-and-tube condenser (18) is connected to the tube-side inlet of the condenser. The outlet is connected to the inlet 2 (8) at the top of the gas-liquid separator (13) via pipe 1 (7). The outlet 2 (9) at the top of the gas-liquid separator (13) is connected to the inlet 1 (5) of the hydrogen compressor 1 (4) via pipe. The outlet 1 (3) of the hydrogen compressor 1 (4) is connected to the inlet of valve 1 (1) and the inlet of valve 2 (2) via pipe. The outlet of valve 1 (1) is equipped with a hydrogen outlet pipe (81). The outlet of valve 2 (2) is connected to the inlet 8 (50) and the inlet 7 (49) of the tubular fixed-bed catalytic reactor 1 (48) via a cold hydrogen pipe (29). The outlet of valve 2 (2) is connected to the cold hydrogen pipe (29). The valve is connected to the inlet 5 (34) and inlet 6 (38) of the tubular fixed-bed catalytic reactor 2 (39) respectively. The outlet of the valve 2 (2) is connected to the inlet 10 (54) of the gas-liquid mixer (53) through the cold hydrogen pipeline (29). The bottom outlet 3 (12) of the gas-liquid separator (13) is connected to the inlet of the organic solvent pump (15) through the pipeline 11 (80). The outlet of the organic solvent pump (15) is connected to the inlet 11 (59) of the heating furnace (58) through the pipeline 3 (17). The outlet 9 (57) of the heating tube (56) in the heating furnace (58) is connected to the inlet 10 (54) of the gas-liquid mixer (53) through the pipeline 10 (55).

2. A special vehicle for hydrogen storage, transportation, and dehydrogenation according to claim 1, characterized in that: The tubular fixed-bed catalytic reactor (48) is a cylindrical metal sealed cylinder. The middle section of the cylinder is equipped with an upper sieve plate (78) and a lower sieve plate (79). The outer wall of the cylinder below the upper sieve plate (78) is equipped with an inlet eight (50), and the outer wall of the cylinder below the lower sieve plate (79) is equipped with an inlet seven (49). A solid catalyst (36) is placed between the upper sieve plate (78) and the lower sieve plate (79). The temperature sensing head of the thermometer two (40) is inserted into the solid catalyst (36). The top of the tubular fixed-bed catalytic reactor (48) is equipped with an inlet nine (51), and the bottom of the tubular fixed-bed catalytic reactor (48) is equipped with an outlet seven (47). The tubular fixed-bed catalytic reactor (48) is filled with liquid organic matter (11), and a pressure gauge three (30) is inserted into the liquid organic matter (11). The tubular fixed-bed catalytic reactor II (39) is a cylindrical metal sealed cylinder. The middle section of the cylinder is equipped with an upper sieve plate II (33) and a lower sieve plate II (37). The outer wall of the cylinder below the upper sieve plate II (33) is equipped with an inlet V (34), and the outer wall of the cylinder below the lower sieve plate II (37) is equipped with an inlet VI (38). A solid catalyst (36) is placed between the upper sieve plate II (33) and the lower sieve plate II (37). The temperature sensing head of thermometer I (35) is inserted into the solid catalyst (36). The top of the tubular fixed-bed catalytic reactor II (39) is equipped with an inlet IV (31), and the bottom of the tubular fixed-bed catalytic reactor II (39) is equipped with an outlet VI (41). The tubular fixed-bed catalytic reactor II (39) is filled with liquid organic matter (11), and pressure gauge I (6) is inserted into the liquid organic matter (11). The heating furnace (58) is a cylindrical tube heating furnace, which consists of a radiation chamber, a convection chamber, a waste heat recovery system, a burner and a ventilation system. The hydrogen compressor one (4) and hydrogen compressor two (21) mentioned above are hydrogen compressors; The gas-liquid separator (13) is a chemical industry gas-liquid separator. It is a closed tank. The top of the gas-liquid separator is equipped with an inlet two (8) and an outlet two (9). The bottom of the tank is equipped with a bottom outlet three (12). The liquid level line (10) in the tank is located at 2 / 3 to 4 / 5 of the height of the tank. The outlet pipe on the side at 1 / 2 of the height of the tank is equipped with a sampling valve (14). The outlet pipe is inserted into the liquid organic matter. The gas-liquid mixer (53) described above is an industrial "gas-liquid" two-phase mixing device; The organic solvent pump (15) mentioned above is a pneumatic diaphragm pump or a corrosion-resistant pump; The shell-and-tube condenser (18) described above belongs to the category of shell-and-tube heat exchangers; The heat exchanger one (26) and heat exchanger two (44) are shell-and-tube heat exchangers; The transport vehicle (73) mainly includes: a cab, an engine (64), a generator (75), a clutch (68), a gearbox (69), a power take-off (65) mounted on the gearbox, a chassis (76), a vehicle drive shaft (74), and wheels (77); it is a modified vehicle that uses the power output shaft of the power take-off (65) connected to the vehicle gearbox (69) to drive the generator (75) to generate electricity, or a vehicle that has an external power source to charge the on-board battery; the transport vehicle is a vehicle manufactured by a vehicle manufacturer or a modified diesel, gasoline, or new energy vehicle; the engine power of the transport vehicle is 80-350 horsepower; the transport vehicle is equipped with an external power socket, or uses an external power source to provide electrical or thermal energy to the hydrogen storage and dehydrogenation equipment in the cargo box (60); The cargo box (60) is the cargo box configured when the transport vehicle (73) leaves the factory. The cargo box is modified according to the following structure: the top of the cargo box (60) is composed of two front top plates (62) and rear top plates (63) that can slide back and forth in parallel, and several sets of pulleys (61) at the bottom of the supporting slide plate; any top plate of the cargo box can be moved to one side of the other top plate in parallel, forming an open area of ​​about half of the top of the cargo box, so as to facilitate the operation, maintenance, replacement or hoisting of the equipment inside the cargo box; the movement of the front top plate (62) and the rear top plate (63) is operated by electric or manual operation; when the front top plate (62) and the rear top plate (63) of the top of the cargo box return to their respective ends, the top of the cargo box will be completely sealed, and the top of the cargo box and each side door panel (70) combine to form a three-dimensional cargo box as a whole; the front top plate (62) and the rear top plate (63) The top panel (63) is locked and fixed. The left and right side doors (70) of the cargo box of the transport vehicle are divided into upper and lower parts. Each side door (70) can extend upward or downward at any angle within the range of 0-90 degrees. The extended side door (70) is controlled and stabilized by a hydraulic device (72). When all the extended side doors on the side of the cargo box are closed and the top of the cargo box is sealed, the upper, lower, front, back, left and right side panels of the cargo box are combined to form the cargo box as a whole. Each side door (70), the front top panel (62) and the rear top panel (63) are fixed with a locking buckle (71). The left and right side doors (70) of the cargo box adopt the double-door structure of the postal express vehicle. The lock is on the center line of the two doors, and the two doors open to the left and right. The two side doors (70) and the rear door (32) of the cargo box adopt the box truck structure.

3. A method for storing, transporting, and dehydrogenating hydrogen, comprising the following steps: (i) 99.99% hydrogen produced by water electrolysis, natural gas production, methanol reforming, or coke oven gas production is added to the hydrogen buffer tank (23) via valve three (27) for later use; (ii) Hydrogen storage: using compressor two (21), the room temperature hydrogen in the hydrogen buffer tank (23) is first sent to the shell side of heat exchanger one (26) for heat exchange, and then sent to the shell side of heat exchanger two (44) for heat exchange. After the room temperature hydrogen is heated and converted into hot hydrogen, it is sent to the gas-liquid mixer (53). Simultaneously, the liquid organic matter (11) in the gas-liquid separator (13) is transported to the heating tube (56) in the heating furnace (58) for indirect heating using an organic solvent pump (15). The heated liquid organic matter (11) is then transported to the gas-liquid mixer (53). In the gas-liquid mixer (53), hydrogen and liquid organic matter (11) are mixed to form a gas-liquid homogeneous material. This gas-liquid homogeneous material is continuously pumped from the top of the tubular fixed-bed catalytic reactor (48). Inlet 9 (51) enters the tubular fixed-bed catalytic reactor 1 (48). The gas-liquid mixed material directly contacts the solid catalyst (36) in the tubular fixed-bed catalytic reactor 1 (48) to undergo a hydrogenation catalytic reaction. In the tubular fixed-bed catalytic reactor 1 (48), the catalytic reaction pressure is controlled at 1.5-8.0 MPa and the temperature is controlled at 130-210℃. The material after the hydrogenation catalytic reaction is continuously discharged from the bottom outlet 7 (47) of the tubular fixed-bed catalytic reactor 1 (48). After being cooled by heat exchange in the tube side of heat exchanger 2 (44), the material enters the tubular fixed-bed catalytic reactor 2 (39) through pipe 6 (42) and the top inlet 4 (31) of the tubular fixed-bed catalytic reactor 2 (39), and directly contacts the solid catalyst (36) in the tubular fixed-bed catalytic reactor 2 (39) to undergo a hydrogenation catalytic reaction. In the tubular fixed-bed catalytic reactor 2 (39), the catalytic reaction pressure is controlled at 1.5-8.0 MPa.At 0 MPa and a temperature controlled at 130-210℃, the material after hydrogenation catalytic reaction is continuously discharged from the bottom outlet six (41) of the tubular fixed-bed catalytic reactor two (39). After heat exchange through the tube side of heat exchanger one (26), the material discharged from heat exchanger one (26) enters the shell-and-tube condenser (18) through pipe four (19) and is cooled to room temperature with water, so that the discharged hot material becomes room temperature material. The room temperature material is then transported to the gas-liquid separator (13) through pipe one (7) and the top inlet two (8) of the gas-liquid separator (13). In the gas-liquid separator (13), the tubular fixed-bed catalytic reactor one (48) and the tubular fixed-bed catalytic reactor two (39) are not The remaining room-temperature hydrogen or cold hydrogen absorbed separates from the liquid organic matter. The separated cold hydrogen is then transported to the hydrogenation reactor for recycling. The cold hydrogen absorbs the heat released during the hydrogenation reaction in the tubular fixed-bed catalytic reactor 1 (48) and the tubular fixed-bed catalytic reactor 2 (39), maintaining the hydrogen absorption catalytic reaction temperature in the range of 130-210℃. The cold hydrogen overflows from the top outlet 2 (9) of the gas-liquid separator (13) and enters the inlet 1 (5) of the hydrogen compressor 1 (4). Using the hydrogen compressor 1 (4) and the cold hydrogen pipeline (29), the cold hydrogen is continuously circulated to the inlet 8 (50) and inlet 7 (49) of the tubular fixed-bed catalytic reactor 1 (48) for release. The hot hydrogenation catalytic reaction is cooled down, or cold hydrogen is transported to inlet five (34) and inlet six (38) of tubular fixed-bed catalytic reactor two (39) using hydrogen compressor one (4) and cold hydrogen pipeline (29) to cool down the exothermic hydrogenation catalytic reaction and maintain the hydrogen absorption catalytic reaction temperature in the range of 130-210℃. Alternatively, cold hydrogen is transported to inlet ten (54) of gas-liquid mixer (53) using hydrogen compressor one (4) and cold hydrogen pipeline (29) to replenish the hydrogen feedstock for the hydrogenation catalytic reaction in tubular fixed-bed catalytic reactor one (48). Liquid organic matter (11) in gas-liquid separator (13) is extracted from bottom outlet three (12) using organic solvent pump (15) and passed through the pipe After passing through inlet eleven (59) of the third channel (17) and the heating furnace (58), the liquid organic matter (11) is fed into the heating furnace (58) for heating and temperature rise. Then, it is fed into inlet ten (54) of the gas-liquid mixer (53) through outlet nine (57). In the gas-liquid mixer (53), the heated liquid organic matter (11) is mixed evenly with the heat-exchanged hydrogen to form a gas-liquid mixed material. The material first enters the tubular fixed-bed catalytic reactor one (48) and then enters the tubular fixed-bed catalytic reactor two (39) for hydrogenation catalytic reaction. After the catalytic reaction, the hydrogen is absorbed by the liquid organic matter (11) or the hydrogen is stored in the liquid organic matter (11). The hydrogenation catalytic reaction pressure is controlled at 1.5-8.0 MPa, temperature controlled at 130-210℃; in the exothermic hydrogenation catalytic reaction, the cold hydrogen generated by the gas-liquid separator (13) is transported through the cold hydrogen pipeline (29) to the inlet eight (50) and inlet seven (49) of the tubular fixed-bed catalytic reactor (48), or the cold hydrogen generated by the gas-liquid separator (13) is transported through the cold hydrogen pipeline (29) to the inlet five (34) and inlet six (38) of the tubular fixed-bed catalytic reactor (39), using the cold hydrogen to cool the hydrogenation catalytic reaction in the catalytic reactor, and controlling and adjusting to maintain the appropriate temperature required for the catalytic reaction; Open valve (14) to take a sample and test the hydrogenation reaction of liquid organic matter. When the hydrogen storage content in the liquid organic matter is higher than 6 wt% and the hydrogen storage density is higher than 60 kg / m³, the hydrogen storage reaction is tested. 3 When the hydrogen storage operation is completed, the hydrogen storage capacity is greater than 6 wt% and the hydrogen storage density is greater than 60 kg / m³. 3 The liquid organic matter is buffered in the gas-liquid separator (13), the tubular fixed-bed catalytic reactor one (48), and the tubular fixed-bed catalytic reactor two (39) for later use. The operation of hydrogen compressor one (4) and hydrogen compressor two (21) is stopped, the operation of organic solvent pump (15) is stopped, and the circulation of cooling water in the shell-and-tube condenser (18) is shut off. Multiple sets of tubular fixed-bed catalytic reactors lower than the height of the cargo box are configured for joint use to increase the hydrogen storage or dehydrogenation capacity per unit time. The hydrogen-to-oil volume ratio of liquid organic matter to hydrogen is 50-300:1; the volume hourly space velocity of liquid organic matter is 2.0-5.0 h⁻¹. -1 ; (iii) Hydrogen transportation: a special vehicle for storing, transporting and dehydrogenating hydrogen after storing hydrogen as described in (ii) above is driven to a place where hydrogen is needed, and the hydrogen stored in the special vehicle for storing, transporting and dehydrogenating hydrogen is delivered to the enterprise that uses hydrogen. (iv) Dehydrogenation: Close valve 2 (2), close valve 3 (27), close hydrogen compressor 2 (21), open valve 1 (1), and connect the hydrogen outlet pipe (81) to the hydrogen storage tank of the hydrogen-using enterprise; then, start hydrogen compressor 1 (4) and start organic solvent pump (15) to transport the hydrogenated liquid organic matter in gas-liquid separator (13) to heating furnace (58) to raise the temperature to the temperature required for dehydrogenation catalytic reaction. After the heated liquid organic matter passes through gas-liquid mixer (53), it enters tubular fixed bed catalytic reactor 1 (48) and tubular fixed bed catalytic reactor 2 (39) in sequence, so that the liquid organic matter reacts with the solid catalyst (36) in tubular fixed bed catalytic reactor 1 (48) and tubular fixed bed catalytic reactor 2 (39) to carry out dehydrogenation catalytic reaction. The temperature of the dehydrogenation catalytic reaction is controlled at 150-260℃, the pressure is maintained at atmospheric pressure, and the space velocity of the solid catalyst is 2-5h. -1 After being heated and catalyzed, the liquid organic matter undergoes a decomposition reaction, and hydrogen is released. The mixture formed by hydrogen and liquid organic matter enters the shell-and-tube condenser (18) through pipe four (19) and is condensed to room temperature. The mixture at room temperature is then transported to the gas-liquid separator (13) for gas-liquid separation. In the gas-liquid separator (13), hydrogen overflows from the gas-liquid separator (13) outlet two (9), is extracted by the hydrogen compressor one (4), and is transported to the hydrogen buffer tank of the hydrogen-using enterprise for later use through valve one (1) and hydrogen outlet pipe (81). The separated liquid organic matter is stored at the liquid level line (10) of the gas-liquid separator (13). Using an organic solvent pump (15), the liquid organic matter stored in the gas-liquid separator (13) is continuously extracted and transported to the heating furnace (58) for heating and temperature rise, and the above dehydrogenation catalytic reaction process is carried out in a cycle. Open valve (14) to take a sample and detect the dehydrogenation catalytic reaction of liquid organic matter. When the amount of hydrogen stored in the liquid organic matter is less than 0.1-0.5 wt%, the dehydrogenation or hydrogen release ends: that is, turn off the operation of hydrogen compressor one (4), stop the operation of organic solvent pump (15), stop the operation of heating furnace (58), and close valve one (1) at the same time.

4. The method according to claim 3, characterized in that: The solid catalyst (36) is a long strip or granular DL-1 type solid catalyst. The production method of the DL-1 type solid catalyst is as follows: 3% (wt%) tungsten trioxide powder (WO3), 7% (wt%) cobalt tetroxide powder (Co3O4), 45% (wt%) nickel-aluminum alloy powder (nickel / aluminum ratio 1:1) and 45% (wt%) boehmite powder were mixed evenly in a weight ratio. A certain amount of 6% nitric acid solution was added for binding, and the mixture was extruded into strips with a diameter of 4 mm. The strips were dried at 120°C for 5-8 hours, and then calcined in a muffle furnace at 848°C for 5 hours. After cooling to room temperature, the semi-finished DL-1 alloy was obtained. The semi-finished DL-1 alloy was then activated by leaching with a 5-6 mol / L NaOH solution at 70-90°C. After NaOH solution leaching and activation, the DL-1 type solid catalyst was obtained. The catalyst was rinsed with distilled water or deionized water until neutral to remove any residual sodium aluminate. The catalyst was then sealed in a vacuum bag and stored for later use to prevent oxidation from exposure to air.

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