Organic liquid hydrogen storage reaction system

Abstract

The invention provides an organic liquid hydrogen storage reaction system. Comprising an organic liquid hydrogen storage hydrogenation reaction device and an organic liquid hydrogen storage dehydrogenation reaction device, the organic liquid hydrogen storage hydrogenation reaction device comprises an organic liquid hydrogen storage hydrogenation reaction container and an organic liquid hydrogen storage reaction chamber; the organic liquid hydrogen storage reaction chamber is communicated with a hydrogen-rich hydrogen oil placing container, a hydrogen placing container and a hydrogen-poor hydrogen oil placing container through pipelines respectively; the organic liquid hydrogen storage dehydrogenation reaction device comprises an organic liquid hydrogen storage dehydrogenation reaction container and an organic liquid hydrogen storage reaction chamber, and the organic liquid hydrogen storage reaction chamber is communicated with a hydrogen-rich hydrogen oil placing container, a hydrogen placing container and a hydrogen-poor hydrogen oil placing container through pipelines. By adopting the hydrogen storage device, different organic liquid hydrogen storage reaction chambers can be connected among the hydrogen-rich hydrogen oil placing container, the hydrogen placing container and the hydrogen-poor hydrogen oil placing container, so that more efficient hydrogen addition / dehydrogenation in the organic liquid hydrogen storage process is realized.

Description

Technical Field

[0001] The present application relates to the technical field of organic liquid hydrogen storage, and in particular to an organic liquid hydrogen storage reaction system. Background Art

[0002] Safe, economical and efficient hydrogen storage and transportation is a pain point in the development of the hydrogen energy industry. The storage and transportation of hydrogen energy is in the middle of the hydrogen energy industry chain, connecting hydrogen production and use, and is a key link in opening up the integrated chain of hydrogen energy production, storage and use.

[0003] At present, the development of my country's hydrogen energy industry is facing a prominent contradiction between supply and demand. The cost of hydrogen transportation accounts for about 30%-40% of the total cost. The high proportion of hydrogen storage and transportation costs seriously restricts the large-scale promotion and application of hydrogen energy in my country. In addition, the large-scale promotion of hydrogen energy must solve the safety problems in storage and transportation. Therefore, it is urgent to accelerate the breakthrough of new low-cost, high-efficiency, and intrinsically safe hydrogen storage and transportation technologies.

[0004] At present, the commonly used hydrogen storage and transportation technologies at home and abroad mainly include the following three technologies:

[0005] 1. The domestic mainstream high-pressure gaseous hydrogen storage and transportation technology has a market share of more than 95%. Its effective economic radius is within 100km, and its hydrogen carrying capacity is small (each long-tube trailer has an effective hydrogen carrying capacity of only 240-280kg), and once a vehicle accident occurs, serious negative situations are likely to occur.

[0006] 2. Pipeline hydrogen transportation. my country is piloting the construction of a thousand-kilometer-level hydrogen transportation demonstration pipeline. However, due to factors such as the maturity of the technology, construction costs, land acquisition, and construction approval, although it has the potential for large-scale promotion and application, it is still subject to many limitations in policies, land use, operation and maintenance, etc. in future development.

[0007] 3. Cryogenic liquid hydrogen technology: This technology compresses gaseous hydrogen into liquid hydrogen at high pressure and -253°C. It has two important disadvantages: the temperature of -253°C must always be maintained during storage and transportation, resulting in greater energy consumption; and the realization of cryogenic liquid hydrogen storage and transportation requires the construction of a new system of cryogenic liquid hydrogen transportation and storage facilities and equipment, which requires a large amount of investment.

[0008] Organic liquid hydrogen storage and transportation technology can directly use existing oil transportation equipment (oil trucks, tankers, etc.), and the transportation carrier is "hydrogen oil" (hydrogen-containing carrier) which is non-hazardous chemical, which can achieve intrinsically safe and low-cost transportation; at the same time, large oil storage tanks can be used to store hydrogen oil for a long time, across seasons, and on a large scale. Organic liquid hydrogen storage and transportation technology has the advantages of low cost and high safety among all hydrogen storage and transportation technologies, and is expected to break the bottleneck of large-scale storage and transportation of hydrogen energy. It is the preferred technical route recommended by the International Energy Agency among all hydrogen storage and transportation technologies.

[0009] Traditional organic liquid hydrogen storage reactions use fixed bed reactors to load granular catalysts. On the one hand, due to the large catalyst particle size, the dehydrogenation process is greatly affected by internal and external diffusion. On the other hand, channeling is prone to occur in traditional fixed bed reactors, and when performing hydrogenation or dehydrogenation treatment, separate hydrogenation equipment or dehydrogenation equipment is required, which has a complex structure and wastes a lot of manpower and material resources. Summary of the invention

[0010] The main purpose of the present application is to provide an organic liquid hydrogen storage reaction system, which can achieve more efficient addition / dehydrogenation in the organic liquid hydrogen storage process by connecting different organic liquid hydrogen storage reaction chambers between the hydrogen-rich hydrogen oil placement container, the hydrogen gas placement container and the hydrogen-poor hydrogen oil placement container.

[0011] In order to solve the aforementioned technical problems, the present application provides an organic liquid hydrogen storage reaction system, including an organic liquid hydrogen storage hydrogenation reaction device and an organic liquid hydrogen storage dehydrogenation reaction device;

[0012] The organic liquid hydrogen storage and hydrogenation reaction device comprises: an organic liquid hydrogen storage and hydrogenation reaction container and an organic liquid hydrogen storage reaction chamber, wherein the organic liquid hydrogen storage reaction chamber is connected to a hydrogen-rich hydrogen oil placement container, a hydrogen gas placement container and a hydrogen-poor hydrogen oil placement container through pipelines respectively;

[0013] The organic liquid hydrogen storage and dehydrogenation reaction device comprises: an organic liquid hydrogen storage and dehydrogenation reaction container and an organic liquid hydrogen storage reaction chamber. The organic liquid hydrogen storage reaction chamber is connected to a hydrogen-rich hydrogen oil placement container, a hydrogen gas placement container and a hydrogen-poor hydrogen oil placement container through pipelines.

[0014] Optionally, in some embodiments of the present invention, the organic liquid hydrogen storage and hydrogenation reaction vessel comprises a fiber cloth layer and a hollow tank body;

[0015] The fiber cloth layer covers the outer side of the hollow tank body, and the fiber cloth layer adsorbs the hydrogenation catalyst; the hollow tank body is provided with a plurality of through holes penetrating the hollow tank body, and a feed port is provided at one end of the hollow tank body.

[0016] Optionally, in some embodiments of the present invention, the organic liquid hydrogen storage reaction chamber is provided with a feed port connected to the feed port, a liquid outlet is provided at the bottom of the organic liquid hydrogen storage reaction chamber, and a gas outlet is provided at the top of the organic liquid hydrogen storage reaction chamber;

[0017] The feeding port is connected to the gas outlet end of the hydrogen storage container and the liquid outlet end of the hydrogen-poor hydrogen oil storage container at the same time, the gas outlet is connected to the gas inlet end of the hydrogen storage container, and the liquid outlet is connected to the liquid inlet end of the hydrogen-rich hydrogen oil storage container.

[0018] Optionally, in some embodiments of the present invention, the above also includes a gas-liquid mixer and a gas-liquid separator, the gas inlet end of the gas-liquid mixer is connected to the hydrogen storage container, the liquid inlet end of the gas-liquid mixer is connected to the hydrogen-poor hydrogen oil storage container, and the liquid outlet end of the gas-liquid mixer is connected to the feed port;

[0019] The inlet end of the gas-liquid separator is connected to the liquid outlet, the gas outlet end of the gas-liquid separator is connected to the hydrogen placement container, and the liquid outlet end of the gas-liquid separator is connected to the hydrogen-rich hydrogen oil placement container.

[0020] Optionally, in some embodiments of the present invention, the liquid outlet is provided with a liquid level controller, and the gas outlet is installed with a valve.

[0021] Optionally, in some embodiments of the present invention, the organic liquid hydrogen storage and dehydrogenation reaction container comprises a fiber cloth layer and a hollow tank body;

[0022] The fiber cloth layer covers the outside of the hollow tank body, and the fiber cloth layer adsorbs a dehydrogenation catalyst;

[0023] The hollow tank body is provided with a plurality of through holes penetrating the hollow tank body, and a feed port is provided at one end of the hollow tank body.

[0024] Optionally, in some embodiments of the present invention, the organic liquid hydrogen storage reaction chamber is provided with a feed port connected to the feed port, a liquid outlet is provided at the bottom of the organic liquid hydrogen storage reaction chamber, and a gas outlet is provided at the top of the organic liquid hydrogen storage reaction chamber;

[0025] The feed port is connected to the liquid outlet end of the hydrogen-rich hydrogen oil placement container, the gas outlet is connected to the gas inlet end of the hydrogen placement container, and the liquid outlet is connected to the liquid inlet end of the hydrogen-poor hydrogen oil placement container.

[0026] Optionally, in some embodiments of the present invention, a gas-liquid separator is provided between the liquid outlet and the hydrogen-depleted hydrogen oil placement container, and the gas outlet end of the gas-liquid separator is connected to the hydrogen placement container.

[0027] Optionally, in some embodiments of the present invention, a liquid level controller is provided between the liquid outlet and the hydrogen-depleted hydrogen oil placement container.

[0028] Optionally, in some embodiments of the present invention, an adsorbent assembly is provided between the gas outlet and the hydrogen storage container.

[0029] An organic liquid hydrogen storage reaction system proposed in an embodiment of the present application includes a fiber cloth layer and a hollow tank body; the fiber cloth layer covers the outside of the hollow tank body, and the fiber cloth layer is adsorbed with a catalyst; the hollow tank body is provided with a plurality of through holes penetrating the hollow tank body, and a feed port is provided at one end of the hollow tank body.

[0030] By replacing the catalyst arranged on the fiber cloth layer, it is possible to select the hydrogenation process or the dehydrogenation process in the hydrogen storage process of the organic liquid. At the same time, the small diameter of the fiber cloth catalyst fiber is utilized to break the internal and external diffusion restrictions, and the dense holes of the fiber cloth are utilized to redistribute the hydrogen and hydrogen-poor hydrogen oil or hydrogen-rich hydrogen oil, thus overcoming the problem of channeling that is prone to occur in traditional fixed reactors. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 A schematic structural diagram of an organic liquid hydrogen storage reaction system provided in the first embodiment of the present invention;

[0032] Figure 2 A schematic structural diagram of an organic liquid hydrogen storage and hydrogenation reaction device provided in a second embodiment of the present invention;

[0033] Figure 3 A schematic structural diagram of an organic liquid hydrogen storage and hydrogenation reaction device in another installation mode provided for the second embodiment of the present invention;

[0034] Figure 4 A schematic structural diagram of an organic liquid hydrogen storage reaction device provided in a third embodiment of the present invention;

[0035] Figure 5 A schematic structural diagram of an organic liquid hydrogen storage reaction device in another installation manner provided in the third embodiment of the present invention.

[0036] Icons: 1. Organic liquid hydrogen storage reaction vessel; 101. Hollow tank body; 102. Fiber cloth layer; 103. Head; 2. Organic liquid hydrogen storage reaction chamber; 3. Gas-liquid mixer; 4. Gas-liquid separator; 5. Liquid level controller; 6. Valve; 7. Adsorbent assembly; 8. Hydrogen-poor hydrogen oil placement container; 9. Hydrogen-rich hydrogen oil placement container; 10. Hydrogen gas placement container.

[0037] The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0038] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] It should be noted that all directional indications in the embodiments of the present invention (such as up, down, left, right, front, back, etc.) are only used to explain the relative position relationship, movement status, etc. between the components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indication will also change accordingly.

[0040] In the present invention, unless otherwise clearly specified and limited, the terms "connection", "fixation", etc. should be understood in a broad sense. For example, "fixation" can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly defined. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0041] In addition, if there are descriptions involving "first", "second", etc. in the embodiments of the present invention, the descriptions of "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the meaning of "and / or" appearing in the full text includes three parallel schemes. Taking "A and / or B" as an example, it includes scheme A, or scheme B, or a scheme that satisfies both A and B. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the ability of ordinary technicians in the field to implement. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0042] In this application, the organic matter before hydrogenation is referred to as hydrogen-poor hydrogen oil, and the organic matter after hydrogenation is referred to as hydrogen-rich hydrogen oil, and the two are collectively referred to as hydrogen oil.

[0043] The present invention is further described in detail below in conjunction with the accompanying drawings so that those skilled in the art can implement the invention with reference to the description.

[0044] In order to achieve the above purpose, refer to Figure 1 The first embodiment of the present application provides an organic liquid hydrogen storage reaction vessel 1, a fiber cloth layer 102 and a hollow tank body 101; the fiber cloth layer 102 covers the outside of the hollow tank body 101, and the fiber cloth layer 102 adsorbs a catalyst; the hollow tank body 101 is provided with a plurality of through holes penetrating the hollow tank body 101, and a feed port is provided at one end of the hollow tank body 101. The fiber cloth catalyst has a small fiber diameter, which breaks the internal and external diffusion restrictions, and the dense holes of the fiber cloth are used to redistribute hydrogen and hydrogen oil, thereby overcoming the problem of channeling in traditional fixed through-reactors.

[0045] The fiber cloth layer 102 of this embodiment wraps the hollow tank body 101, and the fiber cloth layer 102 is adsorbed with a catalyst; the hollow tank body 101 is provided with a plurality of through holes penetrating the hollow tank body 101, and a feed port is provided on one side of the hollow tank body 101. In actual use, hydrogen-rich hydrogen oil or hydrogen-poor hydrogen oil and hydrogen are first introduced into the hollow tank body 101, and then flow out of the hollow tank body 101 through the through holes, and in this process flow through the fiber cloth layer 102, and the catalyst in the fiber cloth layer 102 accelerates the dehydrogenation or hydrogenation reaction.

[0046] Among them, the hollow tank body 101 can be a cylindrical structure, the cross-sectional shape of the through hole is a long strip structure, and the material of the hollow tank body 101 can be metal, polymer material, ceramic, etc.; the fiber cloth layer 102 wraps the hollow tank body 101 through multiple layers of winding, and the fiber cloth layer 102 can include activated carbon fiber, activated carbon fiber felt, non-woven fabric and other fiber materials with certain adsorption properties. At the same time, a specific catalyst can be selected according to the dehydrogenation reaction or the hydrogenation reaction. When hydrogenation catalytic treatment is required, the catalyst can use one or more of Pt, Pd, Ru, Ni, Co, Al and other metals or metal oxides as a catalyst material; when dehydrogenation catalytic treatment is required, the catalyst can use one or more of Pt, Pd, Ir, Rh and other metals or metal oxides as a catalyst material.

[0047] At the same time, the catalyst can be prepared by using the fiber cloth layer 102 as a carrier: including but not limited to using impregnation method, ion sputtering method, precipitation deposition method, CVD and other technologies to construct the catalyst on the fiber cloth. Taking the impregnation fiber cloth catalyst as an example, the specific preparation method is as follows: one or more active metal salts (Pt salt, Pd salt, Ru salt, Ni salt, Cu salt, etc.) are configured into a solution to impregnate the fiber cloth, and after a series of treatments such as drying, calcination, reduction, etc., a catalyst with the fiber cloth as a carrier is formed.

[0048] It should be noted that the fiber cloth layer 102 of this embodiment is wound around the hollow tank body 101, which is only a preferred implementation of this embodiment to facilitate replacement of the fiber cloth layer 102 or addition of a new catalyst. In other embodiments, the fiber cloth layer 102 can also be arranged inside the hollow tank body 101.

[0049] Optionally, a sealing head 103 for fixing the fiber cloth layer 102 is provided at one end of the hollow tank body 101 away from the feed inlet in this embodiment.

[0050] The fiber cloth layer 102 can be fixed to the outside of the hollow tank by providing the sealing head 103. The hollow tank body 101 and the sealing head 103 can be detachably connected by means of threads or buckles.

[0051] It should be noted that in this embodiment, fixing the fiber cloth layer 102 by the sealing head 103 is only a preferred implementation of this embodiment. In other embodiments, the fiber cloth layer 102 can also be fixed by bundling or bonding.

[0052] The second embodiment of the present application provides an organic liquid hydrogen storage reaction device, including the above-mentioned organic liquid hydrogen storage reaction container 1, the organic liquid hydrogen storage reaction container 1 is arranged in the organic liquid storage reaction chamber, and the organic liquid hydrogen storage reaction chamber 2 is connected to the hydrogen-rich hydrogen oil placement container 9, the hydrogen gas placement container 10 and the hydrogen-poor hydrogen oil placement container 8 through pipelines.

[0053] The hydrogenation or dehydrogenation process of the organic liquid hydrogen storage process can be achieved by adjusting the catalyst in the organic liquid hydrogen storage reaction container 1 and the flow direction of the liquid or gas in the organic liquid hydrogen storage reaction device. The flow direction of the liquid or gas can be controlled by a water pump or a one-way valve.

[0054] Among them, refer to Figure 2 , the hydrogenation method of organic liquid hydrogen storage process is:

[0055] By adjusting the settings, the organic liquid hydrogen storage reaction chamber 2 is provided with a feeding port connected to the feeding port, the bottom of the organic liquid hydrogen storage reaction chamber 2 is provided with a liquid outlet, and the top of the organic liquid hydrogen storage reaction chamber 2 is provided with a gas outlet;

[0056] The feeding port is connected to the gas outlet end of the hydrogen placement container 10 and the liquid outlet end of the hydrogen-poor hydrogen oil placement container 8 at the same time, so that hydrogen and hydrogen-poor hydrogen oil can enter the organic liquid hydrogen storage reaction chamber 2, the gas outlet is connected to the gas inlet end of the hydrogen placement container 10, so that part of the hydrogen that has not reacted with the hydrogen-poor hydrogen oil enters the hydrogen placement container 10 for subsequent reactions, and the liquid outlet is connected to the liquid inlet end of the hydrogen-rich hydrogen oil placement container 9 for receiving the generated hydrogen-rich hydrogen oil.

[0057] As an optional implementation mode, the present embodiment further includes a gas-liquid mixer 3 and a gas-liquid separator 4, the gas inlet end of the gas-liquid mixer 3 is connected to the hydrogen placement container 10, so that the hydrogen can enter the gas-liquid mixer 3, the liquid inlet end of the gas-liquid mixer 3 is connected to the hydrogen-poor hydrogen oil placement container 8, so that the hydrogen-poor hydrogen oil can enter the gas-liquid mixer 3, and the hydrogen and the hydrogen-poor hydrogen oil can be preliminarily mixed through the gas-liquid mixer 3, and the liquid outlet end of the gas-liquid mixer 3 is connected to the feeding port;

[0058] A gas-liquid separator 4 is provided between the organic liquid hydrogen storage reaction chamber 2 and the hydrogen-rich oil placement container 9, the inlet end of the gas-liquid separator 4 is connected to the liquid outlet, the gas outlet end of the gas-liquid separator 4 is connected to the hydrogen placement container 10, and the liquid outlet end of the gas-liquid separator 4 is connected to the hydrogen-rich oil placement container 9. By performing gas-liquid separation on the generated hydrogen-rich oil, a small amount of hydrogen can be prevented from being mixed in the hydrogen-rich oil, thereby improving the purity of the hydrogen-rich oil.

[0059] Among them, the organic liquid hydrogen storage reaction container 1 of this embodiment is arranged at the bottom of the organic liquid hydrogen storage reaction chamber 2, and the feed port is arranged on the side of the organic liquid hydrogen storage reaction container 1 close to the organic liquid hydrogen storage reaction chamber 2, and is connected with the feed port, so that the mixed hydrogen and hydrogen-depleted hydrogen oil enter the organic liquid hydrogen storage reaction chamber 2 from the bottom of the organic liquid hydrogen storage reaction container 1.

[0060] It should be noted that the aforementioned arrangement position of the organic liquid hydrogen storage reaction container 1 and the arrangement of the feed port at the bottom of the organic liquid hydrogen storage reaction chamber 2 are only an optional implementation of this embodiment. Figure 3 The organic liquid hydrogen storage reaction container 1 is arranged to be installed on the top of the organic liquid hydrogen storage reaction chamber 2 so that the mixed hydrogen gas and hydrogen-depleted hydrogen oil can flow through the organic liquid hydrogen storage reaction container 1 better.

[0061] Optionally, a liquid level controller 5 is provided between the organic liquid hydrogen storage reaction chamber 2 and the hydrogen-rich oil placement container 9 of the present embodiment; by providing the liquid level controller 5 to adjust the height of the liquid level in the organic liquid hydrogen storage reaction chamber 2, liquid sealing of hydrogen is achieved to prevent hydrogen from entering the hydrogen-rich oil placement container 9.

[0062] The gas outlet of the organic liquid hydrogen storage reaction chamber 2 is provided with a valve 6 to discharge the unreacted hydrogen.

[0063] Among them, valve 6 can use a back pressure valve, which realizes action through the elastic force of the built-in spring: when the system pressure is smaller than the set pressure, the diaphragm blocks the pipeline under the action of the spring force; when the system pressure is larger than the set pressure, the diaphragm compresses the spring, the pipeline is connected, and the liquid passes through the back pressure valve. The structure of the back pressure valve is similar to that of the one-way valve, but the opening pressure is greater than that of the one-way valve, which is between 0.2 and 1.6 MPa.

[0064] When the pressure in the pipeline or equipment container is unstable, the back pressure valve can maintain the required pressure in the pipeline so that the pump can output the flow normally. In addition, due to gravity or other effects, siphoning often occurs at the outlet of the pump. At this time, the back pressure valve can reduce the fluctuation of flow and pressure caused by siphoning. When a positive displacement pump such as a metering pump works under low system pressure, excessive delivery will occur. To prevent similar problems, the outlet of the metering pump must have a back pressure of at least 0.7 Bar, which is generally achieved by installing a back pressure valve at the outlet of the metering pump.

[0065] The heating component arranged in the organic liquid hydrogen storage reaction chamber 2 can be heated by electric heating, steam heating, microwave heating, etc. The hydrogenation reaction temperature ranges from 80 to 150°C.

[0066] Optionally, the hydrogen-rich hydrogen oil of this embodiment includes hydrogenated N-ethylcarbazole, hydrogenated N-propylcarbazole, hydrogenated N-methylindole, hydrogenated dimethylindole, methylcyclohexane, hydrogenated dibenzyltoluene and the like.

[0067] Hydrogen-poor hydrogen oil is the corresponding N-ethylcarbazole, N-propylcarbazole, N-methylindole, dimethylindole, toluene, dibenzyltoluene and other substances after dehydrogenation of hydrogen-rich hydrogen oil.

[0068] Specifically, the hydrogenation method of this embodiment is:

[0069] 1. First, hydrogen and hydrogen-poor oil in appropriate proportions are introduced into the gas-liquid mixer 3 to achieve sufficient mixing, and the mixed gas-liquid mixture is introduced into the organic liquid hydrogen storage reaction container 1; wherein the hydrogen and hydrogen-poor oil are both preheated.

[0070] 2. The fully mixed hydrogen and hydrogen-poor oil mixture undergoes a hydrogenation reaction under the action of the catalyst in the fiber cloth layer 102 of the organic liquid hydrogen storage reaction vessel 1, thereby converting the hydrogen-poor oil into hydrogen-rich oil. The hydrogen-rich oil and the incompletely reacted hydrogen enter the organic liquid hydrogen storage reaction chamber 2, thereby achieving natural separation of gas and liquid.

[0071] 3. The naturally separated hydrogen-rich oil maintains a certain liquid level in the organic liquid hydrogen storage reaction chamber 2 under the control of the liquid level controller 5, thereby achieving a liquid seal for hydrogen and preventing hydrogen from entering the liquid level controller 5 and the gas-liquid separator 4 as much as possible;

[0072] 4. When the viscosity of the hydrogen-rich oil is relatively low, the hydrogen and the hydrogen-rich oil are completely separated, and it is not necessary to install a gas-liquid separator 4 between the organic liquid hydrogen storage reaction chamber 2 and the hydrogen-rich oil placement container 9; when the viscosity of the hydrogen-rich oil is relatively high, since the hydrogen and the hydrogen-rich oil are mixed more, a small amount of hydrogen will be mixed in the hydrogen-rich oil, and it is necessary to install a gas-liquid separator 4 after the liquid level controller 5 to separate the hydrogen and pass it into the gas-liquid mixer 3, and the hydrogen-rich oil without hydrogen is obtained to enter the hydrogen-rich oil storage container;

[0073] 5. The hydrogen in the organic liquid hydrogen storage reaction chamber 2 is controlled by valve 6 to control the reaction pressure at the working pressure of the organic liquid hydrogen storage (3-6MPa). The output hydrogen is mixed with the hydrogen separated by the gas-liquid separator 4 and recycled, and enters the gas-liquid mixer 3 together with the newly added hydrogen and hydrogen-depleted hydrogen oil for full mixing to continue the hydrogenation process.

[0074] Reference Figure 4 The third embodiment of the present application provides a dehydrogenation method of an organic liquid hydrogen storage reaction device, wherein the organic liquid hydrogen storage reaction chamber is provided with a feed port connected to a feed port, a liquid outlet is provided at the bottom of the organic liquid hydrogen storage reaction chamber 2, and a gas outlet is provided at the top of the organic liquid hydrogen storage reaction chamber 2;

[0075] The feeding port is connected to the liquid outlet end of the hydrogen-rich oil placement container 9 to facilitate pouring the hydrogen-rich oil into the organic liquid hydrogen storage reaction container 1 in the organic liquid hydrogen storage reaction chamber 2. The gas outlet is connected to the gas inlet end of the hydrogen placement container 10, and the liquid outlet is connected to the liquid inlet end of the hydrogen-poor oil placement container 8.

[0076] Among them, the organic liquid hydrogen storage reaction container 1 is arranged at the bottom of the organic liquid hydrogen storage reaction chamber 2, and the feed port is arranged at the bottom of the organic liquid hydrogen storage reaction container 1, so that the hydrogen-rich hydrogen oil enters the organic liquid hydrogen storage reaction chamber 2 from the bottom of the organic liquid hydrogen storage reaction container 1.

[0077] It should be noted that the above-mentioned setting position of the organic liquid hydrogen storage reaction container 1 is only an optional implementation of this embodiment. Figure 5 The organic liquid hydrogen storage reaction container 1 is arranged to be installed on the top of the organic liquid hydrogen storage reaction chamber 2 so that the mixed hydrogen gas and hydrogen-depleted hydrogen oil can flow through the organic liquid hydrogen storage reaction container 1 better.

[0078] Optionally, a liquid level controller 5 is provided between the liquid outlet of the present embodiment and the hydrogen-poor hydrogen oil placement container 8, which has the same function as in the aforementioned embodiment, and adjusts the liquid level height of the hydrogen-poor hydrogen oil generated after the catalytic reaction of the hydrogen-rich hydrogen oil, thereby achieving liquid sealing of hydrogen and preventing hydrogen from entering.

[0079] A gas-liquid separator 4 is provided between the liquid outlet and the hydrogen-poor oil placement container 8, and the gas outlet end of the gas-liquid separator 4 is connected to the hydrogen placement container 10. A gas-liquid separator 4 is provided between the organic liquid hydrogen storage reaction chamber 2 and the hydrogen-poor oil placement container 8, and the gas outlet end of the gas-liquid separator 4 is connected to the hydrogen placement container 10. By performing gas-liquid separation on the generated hydrogen-poor oil, a small amount of hydrogen can be prevented from being mixed in the hydrogen-poor oil, thereby improving the purity of the hydrogen-poor oil.

[0080] An adsorbent assembly 7 is provided between the gas outlet and the hydrogen placement container 10, wherein the adsorbent assembly 7 can be arranged behind the connection position between the gas-liquid separator 4 and the organic liquid hydrogen storage reaction chamber 2, so that the hydrogen in the organic liquid hydrogen storage reaction chamber 2 can be mixed with the hydrogen separated by the gas-liquid separator 4, and then a small amount of impurities mixed therein can be further adsorbed by the adsorbent assembly 7 before being output to the hydrogen placement container 10.

[0081] The heating component arranged in the organic liquid hydrogen storage reaction chamber 2 can be heated by electric heating, steam heating, microwave heating, etc.; the dehydrogenation reaction temperature is 120-240°C.

[0082] Specifically, the dehydrogenation method of this embodiment is:

[0083] 1. The preheated hydrogen-rich oil enters the organic liquid hydrogen storage reaction container 1. According to the preheating condition of the hydrogen-rich oil, conventional heating (including electric heating, steam heating, microwave heating, etc.) can be coupled in the organic liquid hydrogen storage reaction container 1 to reach the dehydrogenation reaction temperature (120-240°C). When the hydrogen-rich oil flows through the organic liquid hydrogen storage reaction container 1, a dehydrogenation reaction occurs on the fiber cloth catalyst of the organic liquid hydrogen storage reaction container 1;

[0084] 2. The hydrogen-poor hydrogen oil and hydrogen produced after the reaction in the organic liquid hydrogen storage reaction vessel 1 enter the organic liquid hydrogen storage reaction chamber 2 to achieve natural separation of gas and liquid;

[0085] 3. The naturally separated hydrogen-poor hydrogen oil maintains a certain liquid level in the organic liquid hydrogen storage reaction chamber 2 under the control of the liquid level controller 5, thereby achieving a liquid seal for hydrogen and reducing the amount of hydrogen entering the liquid level controller 5 and the gas-liquid separator 4;

[0086] 4. When the viscosity of the hydrogen-rich oil is relatively low, the hydrogen and the hydrogen-rich oil are completely separated, and the gas-liquid separator 4 may not be added; when the viscosity of the hydrogen-rich oil is relatively high, the hydrogen and the hydrogen-rich oil are more mixed, and a small amount of hydrogen will be mixed in the hydrogen-rich oil. It is necessary to add a gas-liquid separator 4 after the liquid level controller 5 to separate the hydrogen, and the obtained hydrogen-poor oil without hydrogen enters the hydrogen-poor oil storage container;

[0087] 5. The hydrogen in the organic liquid hydrogen storage reaction chamber 2 is mixed with the hydrogen separated by the gas-liquid separator 4, and then further adsorbed by the adsorbent component 7 to remove a small amount of impurities mixed therein, and then output to the hydrogen-using end. When the hydrogen-using end does not require high purity of hydrogen, the adsorbent component 7 can be omitted. When the hydrogen-using end has requirements for hydrogen pressure, a double pressure valve can be added before the hydrogen outlet to adjust the pressure.

[0088] The adsorbent assembly 7 can use canned activated carbon or molecular sieve and other structures, which are connected in series to the pipeline. The above-mentioned connection methods can achieve communication between devices through stainless steel seamless pipes.

[0089] It can be understood that the organic liquid hydrogen storage reaction container 1, the gas-liquid mixer 3, the gas-liquid separator 4, the organic liquid hydrogen storage hydrogenation reaction device or the organic liquid hydrogen storage reaction device of this embodiment are all modular structures, and detachable connections are achieved through threads or bolts, so that different catalysts can be selected according to the organic liquid hydrogen storage hydrogenation process or the organic liquid hydrogen storage dehydrogenation process, thereby realizing the simultaneous use of dehydrogenation and hydrogenation of a set of equipment.

[0090] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. It is obvious to those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and the present application can be implemented in other specific forms without departing from the spirit or basic features of the present application.

Claims

1. An organic liquid hydrogen storage reaction system, characterized in that: It includes an organic liquid hydrogen storage hydrogenation reaction device and an organic liquid hydrogen storage dehydrogenation reaction device; The organic liquid hydrogen storage and hydrogenation reaction device comprises: an organic liquid hydrogen storage and hydrogenation reaction container and an organic liquid hydrogen storage reaction chamber, wherein the organic liquid hydrogen storage reaction chamber is connected to a hydrogen-rich hydrogen oil placement container, a hydrogen gas placement container and a hydrogen-poor hydrogen oil placement container through pipelines respectively; The organic liquid hydrogen storage and dehydrogenation reaction device comprises: an organic liquid hydrogen storage and dehydrogenation reaction container and an organic liquid hydrogen storage reaction chamber, wherein the organic liquid hydrogen storage reaction chamber is connected to a hydrogen-rich hydrogen oil placement container, a hydrogen gas placement container and a hydrogen-poor hydrogen oil placement container through pipelines.

2. The organic liquid hydrogen storage reaction system according to claim 1, characterized in that: The organic liquid hydrogen storage and hydrogenation reaction container comprises a fiber cloth layer and a hollow tank body; The fiber cloth layer covers the outer side of the hollow tank body, and the fiber cloth layer adsorbs a hydrogenation catalyst; The hollow tank body is provided with a plurality of through holes penetrating the hollow tank body, and a feed port is provided at one end of the hollow tank body.

3. The organic liquid hydrogen storage reaction system according to claim 2, characterized in that: The organic liquid hydrogen storage reaction chamber is provided with a feed port connected to the feed port, a liquid outlet is provided at the bottom of the organic liquid hydrogen storage reaction chamber, and a gas outlet is provided at the top of the organic liquid hydrogen storage reaction chamber; The feeding port is connected to the gas outlet end of the hydrogen storage container and the liquid outlet end of the hydrogen-poor hydrogen oil storage container at the same time, the gas outlet is connected to the gas inlet end of the hydrogen storage container, and the liquid outlet is connected to the liquid inlet end of the hydrogen-rich hydrogen oil storage container.

4. The organic liquid hydrogen storage reaction system according to claim 3, characterized in that: It also includes a gas-liquid mixer and a gas-liquid separator, wherein the gas inlet end of the gas-liquid mixer is connected to the hydrogen storage container, the liquid inlet end of the gas-liquid mixer is connected to the hydrogen-depleted hydrogen oil storage container, and the liquid outlet end of the gas-liquid mixer is connected to the feed port; The inlet end of the gas-liquid separator is connected to the liquid outlet, the gas outlet end of the gas-liquid separator is connected to the hydrogen storage container, and the liquid outlet end of the gas-liquid separator is connected to the hydrogen-rich hydrogen oil storage container.

5. The organic liquid hydrogen storage reaction system according to claim 3, characterized in that: The liquid outlet is provided with a liquid level controller, and the gas outlet is installed with a valve.

6. The organic liquid hydrogen storage reaction system according to claim 1, characterized in that: The organic liquid hydrogen storage and dehydrogenation reaction container comprises a fiber cloth layer and a hollow tank body; The fiber cloth layer covers the outer side of the hollow tank body, and the fiber cloth layer adsorbs a dehydrogenation catalyst; The hollow tank body is provided with a plurality of through holes penetrating the hollow tank body, and a feed port is provided at one end of the hollow tank body.

7. The organic liquid hydrogen storage reaction system according to claim 6, characterized in that: The organic liquid hydrogen storage reaction chamber is provided with a feed port connected to the feed port, a liquid outlet is provided at the bottom of the organic liquid hydrogen storage reaction chamber, and a gas outlet is provided at the top of the organic liquid hydrogen storage reaction chamber; The feeding port is connected to the liquid outlet of the hydrogen-rich hydrogen oil placement container, the gas outlet is connected to the gas inlet of the hydrogen placement container, and the liquid outlet is connected to the liquid inlet of the hydrogen-poor hydrogen oil placement container.

8. The organic liquid hydrogen storage reaction system according to claim 7, characterized in that: A gas-liquid separator is provided between the liquid outlet and the hydrogen-depleted hydrogen oil placement container, and the gas outlet end of the gas-liquid separator is connected to the hydrogen placement container.

9. The organic liquid hydrogen storage reaction system according to claim 7, characterized in that: A liquid level controller is provided between the liquid outlet and the hydrogen-depleted hydrogen oil placement container.

10. The organic liquid hydrogen storage reaction system according to claim 7, characterized in that: An adsorbent component is arranged between the gas outlet and the hydrogen storage container.

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