Organic liquid continuous hydrogen storage device and method thereof

Abstract

The application discloses a kind of organic liquid continuous hydrogen storage device and method thereof, organic liquid continuous hydrogen storage device includes feed system, preheating system, gas-liquid mixing system, fixed bed microreactor and gas-liquid separation system, the feed system includes hydrogen storage component and liquid storage component, the hydrogen storage component is connected the gas-liquid mixing system, the liquid storage component connects the preheating system, the preheating system connects the gas-liquid mixing system, the preheating system is used to preheat organic liquid hydrogen storage carrier, the gas-liquid mixing system is used to mix organic liquid hydrogen storage carrier with hydrogen;The gas-liquid mixing system, the fixed bed microreactor and the gas-liquid separation system are sequentially connected in order, the fixed bed microreactor is loaded with hydrogenation reaction catalyst, and the fixed bed microreactor is provided with reactor heating temperature control device outside.The application can realize one-step liquid hydrogen storage process, and realizes process continuity.

Description

Technical Field

[0001] This application relates to the field of chemical reaction engineering technology, and in particular to a continuous hydrogen storage device and method for organic liquids. Background Technology

[0002] Hydrogen storage technology has always been a major challenge in the development of hydrogen energy applications. Currently, hydrogen storage mainly involves high-pressure gaseous hydrogen storage and cryogenic liquefaction hydrogen storage. Both of these methods have high requirements for equipment and the environment, high operating costs, and potential safety hazards.

[0003] Organic liquid hydrogen storage technology uses organic liquids containing unsaturated bonds as hydrogen storage carriers. Under the action of a catalyst, these liquids undergo a reversible reaction with hydrogen, achieving hydrogen storage. It is safe to use, the equipment is simple, and transportation is convenient. Organic liquid hydrogen storage does not damage the main structure of the organic matter; hydrogen storage and transportation can be achieved through reversible hydrogenation and dehydrogenation processes. In traditional technologies, liquid hydrogen storage cannot achieve continuous operation. Summary of the Invention

[0004] Therefore, it is necessary to provide a continuous hydrogen storage device for organic liquids. The continuous hydrogen storage device for organic liquids of the present invention utilizes the high mixing efficiency and excellent mass and heat transfer performance of a microreactor to enhance interphase mass transfer during the reaction process. This significantly reduces the reactor volume, increases the reaction yield, lowers the reaction temperature and pressure, and improves production efficiency and safety.

[0005] One embodiment of this application provides an organic liquid continuous hydrogen storage device.

[0006] An organic liquid continuous hydrogen storage device includes a feeding system, a preheating system, a gas-liquid mixing system, a fixed-bed microreactor, and a gas-liquid separation system. The feeding system includes a hydrogen storage component and a liquid storage component. The hydrogen storage component is connected to the gas-liquid mixing system, the liquid storage component is connected to the preheating system, and the preheating system is connected to the gas-liquid mixing system. The preheating system is used to preheat the organic liquid hydrogen storage carrier, and the gas-liquid mixing system is used to mix the organic liquid hydrogen storage carrier with hydrogen. The gas-liquid mixing system, the fixed-bed microreactor, and the gas-liquid separation system are connected sequentially. The fixed-bed microreactor is filled with a hydrogenation reaction catalyst, and a reactor heating and temperature control device is provided externally to the fixed-bed microreactor.

[0007] In some embodiments, the organic liquid continuous hydrogen storage device further includes a circulating heating system connected between the fixed-bed microreactor and the preheating system. The thermal circulation system is used to circulate the liquid hydrogen storage product obtained from the fixed-bed microreactor to the preheating system through a circulation pipeline for heat exchange.

[0008] In some embodiments, the feeding system further includes a high-pressure infusion pump connected between the liquid storage assembly and the preheating system.

[0009] In some embodiments, the hydrogenation catalyst is selected from Ru / C, Ru / Al2O3, Pd / Al2O3, Pd / C, Ni / Al2O3, Ni / SiO2, Ru-Ni / Al2O3, Ru-Ni / SiO2, and Ru-Ni / Al2O3+SiO2.

[0010] In some embodiments, the outlet of the preheating system and the inlet of the gas-liquid mixing system are connected by a temperature control pipeline. The temperature control pipeline is equipped with a heater and a heat preservation control device. The heater and the heat preservation control device cooperate with each other to achieve the liquid temperature on the temperature control pipeline within a preset range.

[0011] In some embodiments, the gas storage component is connected to the air inlet of the gas-liquid mixing system via a gas pipeline, and the gas pipeline is equipped with one or more of the following: a shut-off valve, a filter, a pressure regulating valve, a dryer, and a gas flow control system.

[0012] In some embodiments, the gas-liquid separation system includes a condenser and a gas-liquid separator, the condenser and the gas-liquid separator being sequentially connected to the fixed-bed microreactor, the gas outlet of the gas-liquid separator being connected to a gas buffer device and a drying tank, and the liquid outlet of the gas-liquid separator being connected to a filter and a sampling device.

[0013] Another embodiment of this application provides a method for continuous hydrogen storage of organic liquids.

[0014] A method for continuous hydrogen storage using an organic liquid, comprising the following steps:

[0015] The hydrogenation reaction catalyst of a predetermined mass is loaded into a fixed-bed microreactor;

[0016] Hydrogen and preheated organic liquid hydrogen storage carrier are mixed in a gas-liquid mixing system. The resulting gas-liquid mixture enters the fixed-bed microreactor and undergoes a catalytic hydrogenation reaction at a preset temperature, preset pressure, and preset flow rate to obtain liquid hydrogen storage products.

[0017] The liquid hydrogen storage product enters the gas-liquid separation system, and the separated liquid is the hydrogen storage product.

[0018] In some of these embodiments, the temperature of the preheated organic liquid hydrogen storage carrier is 30°C-100°C.

[0019] In some embodiments, during the catalytic hydrogenation reaction, the preset temperature is 30℃-100℃; the preset pressure is 1.0-3.0MPa; and the residence time of the gas-liquid mixture in the fixed-bed microreactor is 1-3min.

[0020] In some embodiments, the gas-liquid molar ratio of hydrogen to organic liquid hydrogen storage carrier is 3.3:1-6.5:1.

[0021] In some embodiments, the organic liquid hydrogen storage carrier is one or more of toluene, N-ethylcarbazole, N-methylcarbazole, N-propylcarbazole, N-ethylindole, and N-methylindole.

[0022] The above-mentioned organic liquid continuous hydrogen storage device can realize a one-step liquid hydrogen storage process, achieving continuous process. Compared with the traditional liquid hydrogen storage technology, the present invention has advantages such as high catalytic efficiency, low reaction pressure, low temperature, good safety, and low production cost.

[0023] The beneficial effects of the present invention are as follows: (1) In the continuous hydrogen storage reaction device system based on organic liquid in fixed bed microreactor, the gas, liquid and solid three-phase contact area in the fixed bed microreactor is large, the mass transfer efficiency is high, and the amount of catalyst and equipment volume can be reduced; the gas and liquid phases in the fixed bed microreactor are uniformly distributed, the heat transfer capacity is strong, local over-hydrogenation is avoided, the occurrence of by-products is reduced, and the service life of the catalyst is extended.

[0024] (2) The fixed-bed microreactor has multiple temperature measurement points to accurately control the reaction temperature and improve the reaction yield; the gas pipeline is equipped with shut-off valves, filters, pressure regulators, dryers and gas flow control systems, etc., to accurately control the reaction conditions for different hydrogenation reaction systems, further reduce by-products and improve selectivity.

[0025] (3) A preheating system is used to preheat the organic liquid hydrogen storage carrier before mixing it with hydrogen, which avoids the external heating of hydrogen in the fixed-bed microreactor and improves safety. At the same time, the high-temperature product is passed through the preheating system, which transfers some of the heat to the preheating system to achieve heat exchange, making full use of the heat of the liquid hydrogen storage product and recovering it, thereby reducing the energy consumption of the reaction.

[0026] (4) The present invention can achieve higher feed conversion rate and higher selectivity of full hydrogenation products by using lower reaction pressure, such as 1.0-3.0 MPa, lower reaction temperature, such as 30℃-100℃, and shorter residence time, such as 1-3 min. Attached Figure Description

[0027] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0028] To gain a more complete understanding of this application and its beneficial effects, the following description will be provided in conjunction with the accompanying drawings. In the following description, the same reference numerals denote the same parts.

[0029] Figure 1 This is a schematic diagram of an organic liquid continuous hydrogen storage device according to an embodiment of the present invention.

[0030] Explanation of reference numerals in the attached figures

[0031] 10. Continuous liquid hydrogen storage device; 100. Feeding system; 101. Hydrogen storage assembly; 102. Liquid storage assembly; 200. Preheating system; 300. Gas-liquid mixing system; 400. Fixed-bed microreactor; 500. Gas-liquid separation system; 501. Condenser; 502. Gas-liquid separator; 601. Gas buffer device; 602. Drying tank; 603. Filter; 604. Sampling device; 701. Temperature control pipeline; 702. Gas pipeline. Detailed Implementation

[0032] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Many specific details are set forth in the following description to provide a thorough understanding of the present invention. However, the present invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0033] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this invention and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0034] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise explicitly limited. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0035] In this invention, unless otherwise explicitly specified and limited, "above" or "below" the second feature can mean that the first feature is in direct contact with the second feature, or that the first feature is in indirect contact with the second feature through an intermediate medium. Furthermore, "above," "over," and "on top" of the second feature can mean that the first feature is directly above or diagonally above the second feature, or simply that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature can mean that the first feature is directly below or diagonally below the second feature, or simply that the first feature is at a lower horizontal level than the second feature.

[0036] It should be noted that when an element is referred to as being "fixed to" or "set on" another element, it can be directly on the other element or there may be an intervening element. When an element is considered to be "connected to" another element, it can be directly connected to the other element or there may be an intervening element. The terms "vertical," "horizontal," "upper," "lower," "left," "right," and similar expressions used herein are for illustrative purposes only and do not represent the only possible implementation.

[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0038] This application provides an organic liquid continuous hydrogen storage device 10 to solve the problem that conventional liquid hydrogen storage technology cannot achieve continuous operation. The organic liquid continuous hydrogen storage device 10 will be described below with reference to the accompanying drawings.

[0039] The organic liquid continuous hydrogen storage device 10 provided in this application embodiment is exemplary; please refer to [link to example]. Figure 1 As shown, Figure 1This is a schematic diagram of the structure of the organic liquid continuous hydrogen storage device 10 provided in an embodiment of this application. The organic liquid continuous hydrogen storage device 10 of this application can be used for hydrogen storage purposes.

[0040] To more clearly illustrate the structure of the organic liquid continuous hydrogen storage device 10, the organic liquid continuous hydrogen storage device 10 will be described below in conjunction with the accompanying drawings.

[0041] For example, please refer to Figure 1 As shown, Figure 1 This is a schematic diagram of the structure of the organic liquid continuous hydrogen storage device 10 provided in the embodiments of this application. An organic liquid continuous hydrogen storage device 10 includes a feeding system 100, a preheating system 200, a gas-liquid mixing system 300, a fixed-bed microreactor 400, and a gas-liquid separation system 500.

[0042] The feeding system 100 includes a hydrogen storage component 101 and a liquid storage component 102. The hydrogen storage component 101 is connected to a gas-liquid mixing system 300. The liquid storage component 102 is connected to a preheating system 200. The preheating system 200 is connected to the gas-liquid mixing system 300 and is used to preheat the organic liquid hydrogen storage carrier. The gas-liquid mixing system 300 is used to mix the organic liquid hydrogen storage carrier with hydrogen. The gas-liquid mixing system 300, the fixed-bed microreactor 400, and the gas-liquid separation system 500 are connected sequentially. The fixed-bed microreactor 400 is filled with a hydrogenation reaction catalyst. A reactor heating and temperature control device is installed externally on the fixed-bed microreactor 400.

[0043] In some embodiments, the organic liquid continuous hydrogen storage device 10 further includes a circulating heating system. The circulating heating system is connected between the fixed-bed microreactor 400 and the preheating system 200, and the thermal circulation system is used to circulate the liquid hydrogen storage product obtained from the fixed-bed microreactor 400 to the preheating system 200 through a circulation pipeline for heat exchange.

[0044] In some embodiments, the feeding system 100 also includes a high-pressure delivery pump. The high-pressure delivery pump is connected between the liquid storage assembly 102 and the preheating system 200.

[0045] In some embodiments, the hydrogenation catalyst is selected from Ru / C, Ru / Al2O3, Pd / Al2O3, Pd / C, Ni / Al2O3, Ni / SiO2, Ru-Ni / Al2O3, Ru-Ni / SiO2, and Ru-Ni / Al2O3+SiO2. It should be noted that the " / " in the above indicates a combination of two substances, and the "+" indicates the superposition of two components.

[0046] In some embodiments, the outlet of the preheating system 200 and the inlet of the gas-liquid mixing system 300 are connected by a temperature control pipeline 701. The temperature control pipeline 701 is equipped with a heater and a heat preservation control device, which work together to achieve the liquid temperature on the temperature control pipeline 701 within a preset range.

[0047] In some embodiments, the gas storage assembly is connected to the air inlet of the gas-liquid mixing system 300 via a gas pipeline 702. One or more of the following are installed on the gas pipeline 702: a shut-off valve, a filter, a pressure regulating valve, a dryer, and a gas flow control system. The shut-off valve, filter, pressure regulating valve, dryer, and gas flow control system on the gas pipeline 702 are attached... Figure 1 Not shown in the image.

[0048] In some embodiments, the gas-liquid separation system 500 includes a condenser 501 and a gas-liquid separator 502. The condenser 501 and the gas-liquid separator 502 are sequentially connected to a fixed-bed microreactor 400. A gas buffer device 601 and a drying tank 602 are connected to the gas outlet of the gas-liquid separator 502. A filter 603 and a sampling device 604 are connected to the liquid outlet of the gas-liquid separator 502.

[0049] In some embodiments, hydrogen storage assembly 101 may be a hydrogen storage tank. Liquid storage assembly 102 may be a liquid storage tank.

[0050] Another embodiment of this application provides a method for continuous hydrogen storage of organic liquids.

[0051] A method for continuous hydrogen storage using an organic liquid, employing an organic liquid continuous hydrogen storage device 10, includes the following steps:

[0052] The hydrogenation reaction catalyst of a predetermined mass is loaded into the fixed-bed microreactor 400;

[0053] Hydrogen and preheated organic liquid hydrogen storage carrier are mixed in a gas-liquid mixing system 300. The resulting gas-liquid mixture enters a fixed-bed microreactor 400 and undergoes a catalytic hydrogenation reaction at a preset temperature, preset pressure, and preset flow rate to obtain liquid hydrogen storage products.

[0054] The liquid hydrogen storage product enters the gas-liquid separation system 500, and the separated liquid is the hydrogen storage product.

[0055] In some of these embodiments, the temperature of the preheated organic liquid hydrogen storage carrier is 30°C-100°C.

[0056] In some embodiments, during the catalytic hydrogenation reaction, the preset temperature is 30℃-100℃; the preset pressure is 1.0-3.0MPa; and the residence time of the gas-liquid mixture in the fixed-bed microreactor 400 is 1-3min.

[0057] In some embodiments, the gas-liquid molar ratio of hydrogen to organic liquid hydrogen storage carrier is 3.3:1-6.5:1.

[0058] In some embodiments, the organic liquid hydrogen storage carrier is one or more of toluene, N-ethylcarbazole, N-methylcarbazole, N-propylcarbazole, N-ethylindole, and N-methylindole.

[0059] The above-mentioned organic liquid continuous hydrogen storage device 10 can realize a one-step liquid hydrogen storage process and achieve continuous process. Compared with the traditional liquid hydrogen storage technology, the present invention has advantages such as high catalytic efficiency, low reaction pressure, low temperature, good safety and low production cost.

[0060] Example 1

[0061] This embodiment provides an organic liquid continuous hydrogen storage device 10.

[0062] An organic liquid continuous hydrogen storage device 10 includes a feeding system 100, a preheating system 200, a gas-liquid mixing system 300, a fixed-bed microreactor 400, a circulating heating system, and a gas-liquid separation system 500.

[0063] The feeding system 100 includes a hydrogen storage component 101, a liquid storage component 102, and a high-pressure delivery pump. The hydrogen storage component 101 is connected to the gas-liquid mixing system 300. The gas storage component is connected to the gas inlet of the gas-liquid mixing system 300 via a gas pipeline 702. One or more of the following are installed on the gas pipeline 702: a shut-off valve, a filter 603, a pressure regulating valve, a dryer, and a gas flow control system. The liquid storage component 102 is connected to the preheating system 200, and the high-pressure delivery pump is connected between the liquid storage component 102 and the preheating system 200.

[0064] The preheating system 200 is connected to the gas-liquid mixing system 300. The outlet of the preheating system 200 and the inlet of the gas-liquid mixing system 300 are connected by a temperature control pipeline 701. The temperature control pipeline 701 is equipped with a heater and a heat preservation control device, which work together to maintain the liquid temperature on the temperature control pipeline 701 within a preset range. The preheating system 200 is used to preheat the organic liquid hydrogen storage carrier. The gas-liquid mixing system 300 is used to mix the organic liquid hydrogen storage carrier with hydrogen gas. The gas-liquid mixing system 300, the fixed-bed microreactor 400, the circulating heating system, and the gas-liquid separation system 500 are connected sequentially.

[0065] The fixed-bed microreactor 400 is loaded with a hydrogenation reaction catalyst. The hydrogenation reaction catalyst is selected from one of Ru / C, Ru / Al2O3, Pd / Al2O3, Pd / C, Ni / Al2O3, Ni / SiO2, Ru-Ni / Al2O3, Ru-Ni / SiO2, and Ru-Ni / Al2O3+SiO2. The fixed-bed microreactor 400 is externally equipped with a reactor heating and temperature control device.

[0066] A circulating heating system is connected between the fixed-bed microreactor 400 and the preheating system 200. The thermal circulation system is used to circulate the liquid hydrogen storage product obtained from the fixed-bed microreactor 400 to the preheating system 200 for heat exchange through a circulation pipeline.

[0067] In some embodiments, the gas-liquid separation system 500 includes a condenser 501 and a gas-liquid separator 502. The condenser 501 and the gas-liquid separator 502 are sequentially connected to a fixed-bed microreactor 400. A gas buffer device 601 and a drying tank 602 are connected to the gas outlet of the gas-liquid separator 502. The gas buffer device 601 may be a buffer tank. A filter 603 and a sampling device 604 are connected to the liquid outlet of the gas-liquid separator 502.

[0068] Example 2

[0069] This embodiment provides a method for continuous hydrogen storage using organic liquids.

[0070] A method for continuous hydrogen storage using an organic liquid, employing the organic liquid continuous hydrogen storage device 10 from Example 1, wherein the hydrogen reaction catalyst packed in the fixed-bed microreactor 400 is selected from Ru-Ni / SiO2. The method includes the following steps:

[0071] Step 1: Load the hydrogenation reaction catalyst of a predetermined mass into the fixed-bed microreactor 400;

[0072] Step 2: The temperature of the organic liquid hydrogen storage carrier in the storage liquid assembly 102 is preheated to 80℃. N-ethylcarbazole is selected as the organic liquid hydrogen storage carrier in the storage liquid assembly 102.

[0073] Hydrogen gas and a preheated organic liquid hydrogen storage carrier are mixed in a gas-liquid mixing system 300. The resulting gas-liquid mixture enters a fixed-bed microreactor 400, where the gas-liquid molar ratio of hydrogen to organic liquid hydrogen storage carrier is 4:1. The residence time of the gas-liquid mixture in the fixed-bed microreactor 400 is 1 min. A catalytic hydrogenation reaction is carried out at a preset temperature of 100℃, a preset pressure of 3.0 MPa, and a preset flow rate to obtain a liquid hydrogen storage product.

[0074] Step 3: The liquid hydrogen storage product enters the gas-liquid separation system 500, and the separated liquid is the hydrogen storage product.

[0075] The gas-liquid separation system 500 performs gas-liquid separation, and the resulting solution is analyzed. The conversion rate is >98%, and the selectivity of the fully hydrogenated product, dodecahydro-N-ethylcarbazole, is >97%.

[0076] Example 3

[0077] This embodiment provides a method for continuous hydrogen storage using organic liquids.

[0078] An organic liquid continuous hydrogen storage method is disclosed, using the organic liquid continuous hydrogen storage device 10 from Example 1, wherein the hydrogen reaction catalyst packed in the fixed-bed microreactor 400 is selected from Ru-Ni / SiO2. The organic liquid continuous hydrogen storage method is basically the same as that in Example 2, except that the temperature of the organic liquid hydrogen storage carrier is 100°C.

[0079] The gas-liquid separation system 500 performs gas-liquid separation, and the resulting solution is analyzed. The conversion rate is 100%, and the selectivity of the fully hydrogenated product, dodecahydro-N-ethylcarbazole, is >98%.

[0080] Example 4

[0081] This embodiment provides a method for continuous hydrogen storage using organic liquids.

[0082] An organic liquid continuous hydrogen storage method is disclosed, using the organic liquid continuous hydrogen storage device 10 from Example 1, wherein the hydrogen reaction catalyst packed in the fixed-bed microreactor 400 is selected from Ru / Al2O3. The organic liquid continuous hydrogen storage method is basically the same as in Example 2, except that: the temperature of the organic liquid hydrogen storage carrier is 30°C; toluene is selected as the organic liquid hydrogen storage carrier in the storage component 102; the residence time of the gas-liquid mixture in the fixed-bed microreactor 400 is 1 minute; and the system operates at a preset temperature of 40°C and a preset pressure of 3.0 MPa.

[0083] The gas-liquid separation system 500 performs gas-liquid separation, and the resulting solution is analyzed. The conversion rate is >100%, and the selectivity of the fully hydrogenated product methylcyclohexane is >99%.

[0084] Example 5

[0085] This embodiment provides a method for continuous hydrogen storage using organic liquids.

[0086] An organic liquid continuous hydrogen storage method is disclosed, using the organic liquid continuous hydrogen storage device 10 from Example 1, wherein the hydrogen reaction catalyst packed in the fixed-bed microreactor 400 is selected from Ru / -Ni Al2O3+SiO2. The organic liquid continuous hydrogen storage method is basically the same as in Example 2, except that: the temperature of the organic liquid hydrogen storage carrier is 80°C, the residence time of the gas-liquid mixture in the fixed-bed microreactor 400 is 1 min, and the preset temperature is 100°C and the preset pressure is 3.0 MPa.

[0087] The gas-liquid separation system 500 performs gas-liquid separation, and the resulting solution is analyzed. The conversion rate is >98%, and the selectivity of the fully hydrogenated product octahydro-N-ethylindole is >90%.

[0088] Example 6

[0089] This embodiment provides a method for continuous hydrogen storage using organic liquids.

[0090] An organic liquid continuous hydrogen storage method is disclosed, using the organic liquid continuous hydrogen storage device 10 from Example 1, wherein the hydrogen reaction catalyst packed in the fixed-bed microreactor 400 is selected from Ru / -Ni Al2O3. The organic liquid continuous hydrogen storage method is basically the same as in Example 2, except that: the temperature of the organic liquid hydrogen storage carrier is 80°C; N-propylcarbazole is selected as the organic liquid hydrogen storage carrier in the storage component 102; the residence time of the gas-liquid mixture in the fixed-bed microreactor 400 is 1 min; and the system operates at a preset temperature of 100°C and a preset pressure of 3.0 MPa.

[0091] The gas-liquid separation system 500 performs gas-liquid separation, and the resulting solution is analyzed. The conversion rate is >95%, and the selectivity of the fully hydrogenated product, dodecahydro-N-propylcarbazole, is >92%.

[0092] In summary, the beneficial effects of the present invention are as follows: (1) In the organic liquid continuous hydrogen storage reaction device system based on the fixed bed microreactor 400, the gas, liquid and solid three-phase contact area in the fixed bed microreactor 400 is large, the mass transfer efficiency is high, and the amount of catalyst and equipment volume can be reduced; the gas and liquid phases in the fixed bed microreactor 400 are uniformly distributed, the heat transfer capacity is strong, local over-hydrogenation is avoided, the occurrence of by-products is reduced, and the service life of the catalyst is extended.

[0093] (2) The fixed-bed microreactor 400 has multiple temperature measurement points to accurately control the reaction temperature and improve the reaction yield; the gas pipeline 702 is equipped with a shut-off valve, filter 603, pressure regulator, dryer and gas flow control system, etc., to accurately control the reaction conditions for different hydrogenation reaction systems, further reduce by-products and improve selectivity.

[0094] (3) A preheating system 200 is used to preheat the organic liquid hydrogen storage carrier before mixing it with hydrogen, avoiding external heating of hydrogen in the fixed-bed microreactor 400, thus improving safety. At the same time, the high-temperature product is transferred to the preheating system 200 through a circulating heating system to achieve heat exchange, making full use of the heat of the liquid hydrogen storage product and reducing reaction energy consumption.

[0095] (4) The present invention can achieve higher feed conversion rate and higher selectivity of full hydrogenation products by using lower reaction pressure, such as 1.0-3.0 MPa, lower reaction temperature, such as 30℃-100℃, and shorter residence time, such as 1-3 min.

[0096] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.

[0097] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0098] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A continuous hydrogen storage device for organic liquids, characterized in that, The system includes a feeding system, a preheating system, a gas-liquid mixing system, a fixed-bed microreactor, and a gas-liquid separation system. The feeding system includes a hydrogen storage component and a liquid storage component. The hydrogen storage component is connected to the gas-liquid mixing system, and the liquid storage component is connected to the preheating system. The preheating system is connected to the gas-liquid mixing system. The preheating system is used to preheat the organic liquid hydrogen storage carrier. The gas-liquid mixing system is used to mix the organic liquid hydrogen storage carrier with hydrogen. The outlet of the preheating system and the inlet of the gas-liquid mixing system are connected by a temperature-controlled pipeline. The temperature-controlled pipeline is equipped with a heater and a heat preservation control device. The heat preservation and control devices work together to achieve the liquid temperature on the temperature control pipeline within a preset range; the gas-liquid mixing system, the fixed-bed microreactor, and the gas-liquid separation system are connected sequentially; the fixed-bed microreactor is filled with a hydrogenation reaction catalyst, and a reactor heating and temperature control device is installed outside the fixed-bed microreactor; the organic liquid continuous hydrogen storage device also includes a circulating heating system, which is connected between the fixed-bed microreactor and the preheating system; the thermal circulation system is used to circulate the liquid hydrogen storage product obtained from the fixed-bed microreactor to the preheating system through a circulation pipeline for heat exchange.

2. The organic liquid continuous hydrogen storage device according to claim 1, characterized in that, The feeding system also includes a high-pressure liquid pump, which is connected between the liquid storage component and the preheating system.

3. The organic liquid continuous hydrogen storage device according to claim 1, characterized in that, The hydrogenation catalyst is selected from one of Ru / C, Ru / Al2O3, Pd / Al2O3, Pd / C, Ni / Al2O3, Ni / SiO2, Ru-Ni / Al2O3, Ru-Ni / SiO2, and Ru-Ni / Al2O3+SiO2.

4. The organic liquid continuous hydrogen storage device according to any one of claims 1-3, characterized in that, The hydrogen storage component is connected to the gas inlet of the gas-liquid mixing system via a gas pipeline, which is equipped with one or more of the following: a shut-off valve, a filter, a pressure regulating valve, a dryer, and a gas flow control system.

5. The organic liquid continuous hydrogen storage device according to any one of claims 1-3, characterized in that, The gas-liquid separation system includes a condenser and a gas-liquid separator. The condenser and the gas-liquid separator are sequentially connected to the fixed-bed microreactor. The gas outlet of the gas-liquid separator is connected to a gas buffer device and a drying tank, and the liquid outlet of the gas-liquid separator is connected to a filter and a sampling device.

6. A method for continuous hydrogen storage with an organic liquid, characterized in that, Using the organic liquid continuous hydrogen storage device according to any one of claims 1-5, the following steps are included: The hydrogenation reaction catalyst of a predetermined mass is loaded into a fixed-bed microreactor; Hydrogen and a preheated organic liquid hydrogen storage carrier are mixed in a gas-liquid mixing system with a gas-liquid molar ratio of 3.3:1 to 6.5:

1. The resulting gas-liquid mixture enters the fixed-bed microreactor and undergoes a catalytic hydrogenation reaction at a preset temperature of 30℃-100℃, a preset pressure of 1.0-3.0 MPa, and a preset flow rate to obtain a liquid hydrogen storage product. The liquid hydrogen storage product enters the circulating heating system connected between the fixed-bed microreactor and the preheating system. The thermal circulation system circulates the liquid hydrogen storage product back to the preheating system through a circulation pipeline for heat exchange. A heater and a heat preservation control device are installed on the temperature control pipeline connected between the liquid outlet of the preheating system and the liquid inlet of the gas-liquid mixing system to maintain the liquid temperature on the temperature control pipeline within a preset range. The liquid hydrogen storage product enters the gas-liquid separation system, and the separated liquid is the hydrogen storage product.

7. The method for continuous hydrogen storage of organic liquids according to claim 6, characterized in that, The temperature of the preheated organic liquid hydrogen storage carrier is 30℃-100℃.

8. The method for continuous hydrogen storage of organic liquids according to claim 6, characterized in that, During the catalytic hydrogenation reaction, the residence time of the gas-liquid mixture in the fixed-bed microreactor is 1-3 minutes.

9. The method for continuous hydrogen storage of organic liquids according to any one of claims 6-8, characterized in that, The organic liquid hydrogen storage carrier is one or more of toluene, N-ethylcarbazole, N-methylcarbazole, N-propylcarbazole, N-ethylindole, and N-methylindole.

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