A continuous hydrogen release system

Abstract

The application discloses a continuous hydrogen release system, which comprises an organic liquid raw material tank, a column reactor, an oil bath heater and a product tank, the reaction cavity of the column reactor is connected with the liquid inlet and the liquid outlet of the oil bath heater respectively, a plurality of reaction column tubes are arranged in parallel in the reaction cavity, a hydrogen release catalyst is arranged in the reaction column tube, the liquid outlet of the organic liquid raw material tank is connected with the inlet of the reaction column tube, the outlet of the reaction column tube is connected with the feed inlet of the product tank, and the top of the product tank is provided with a hydrogen outlet.

Description

Technical Field

[0001] This invention belongs to the field of organic liquid hydrogen storage technology, specifically relating to a continuous hydrogen release system. Background Technology

[0002] Organic liquid hydrogen storage is a novel hydrogen storage technology. Compared to traditional high-pressure and liquid hydrogen storage technologies, it offers advantages such as higher energy density, greater safety and reliability, and easier storage and transportation. The hydrogen release process using organic liquid carriers requires a hydrogen release catalyst and must be carried out at relatively high temperatures, placing certain requirements on the reactor. To achieve large-scale hydrogen production, the organic liquid carrier must continuously flow within the reactor and release hydrogen continuously under the action of the catalyst. Simultaneously, the organic liquid carrier must have sufficient residence time within the reactor to ensure a good hydrogen release yield.

[0003] Currently, tubular fixed-bed reactors can well meet the requirements of the above-mentioned organic liquid carrier hydrogen release process. However, in actual production, due to the limitations of catalyst performance, the residence time of organic liquid in the reactor tubes is generally relatively long to ensure the degree of hydrogen release from the hydrogen-containing organic liquid. Therefore, the length of the reactor tubes is designed to be relatively long, and the corresponding catalyst loading also increases, increasing production costs. Summary of the Invention

[0004] In view of the above-mentioned prior art, the present invention provides a continuous hydrogen release system to solve the problems of large size and high application cost of existing organic liquid hydrogen release equipment.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: a continuous hydrogen release system is provided, comprising an organic liquid feedstock tank, a tubular reactor, an oil bath heater, and a product tank. The two ends of the reaction chamber of the tubular reactor are respectively connected to the inlet and outlet of the oil bath heater. Multiple reaction tubes are arranged in parallel within the reaction chamber, and a hydrogen release catalyst is arranged within the reaction tubes. The outlet of the organic liquid feedstock tank is connected to the inlet of the reaction tubes, the inlet of the reaction tubes is connected to the hydrogen supply end, the outlet of the reaction tubes is connected to the feed inlet of the product tank, and a hydrogen outlet is provided at the top of the product tank.

[0006] The beneficial effects of the above-mentioned technical solution of this invention are as follows: The organic liquid in the organic liquid raw material tank enters the reaction tube through the inlet of the reaction tube. Under the action of the hydrogen-degrading catalyst in the reaction tube, a hydrogen-degrading reaction occurs, and the resulting product enters the product tank from the outlet of the reaction tube. The oil bath heater introduces heat transfer oil into the reaction chamber of the tube reactor, thereby exchanging heat with the reaction tube in the reaction chamber. By setting multiple parallel reaction tubes in the reaction chamber, the length of the tube reactor can be effectively shortened, preventing the equipment from becoming too bulky.

[0007] Based on the above technical solution, the present invention can be further improved as follows.

[0008] Furthermore, the oil bath heater is equipped with a temperature controller for adjusting the temperature and feed rate of the heat transfer oil, and a temperature measuring thermocouple is installed in the reaction tube. The temperature controller is communicatively connected to the temperature measuring thermocouple.

[0009] The beneficial effects of the above-mentioned further technical solution of the present invention are as follows: the temperature controller is used to adjust the heating power of the oil bath heater and the inlet valve, thereby adjusting the temperature and inlet speed of the heat transfer oil, and thus adjusting the temperature in the reaction tube.

[0010] Furthermore, a preheating mixing chamber is provided at the bottom of the reaction chamber.

[0011] The beneficial effect of the above-mentioned further technical solution of the present invention is that the organic liquid enters the preheating and mixing chamber before entering the reaction chamber to complete the preheating process. The preheating and mixing chamber can both preheat the raw materials and assist in the hydrogen release reaction, thereby improving the hydrogen production rate of the hydrogen-containing organic liquid in the system.

[0012] Furthermore, a buffer chamber is provided at the top of the reaction chamber, and a clamping filter plate for fixing the catalyst is provided between the bottom of the buffer chamber and the top of the reaction chamber. A catalyst support mesh for fixing the catalyst is provided between the top of the preheating mixing chamber and the bottom of the reaction chamber.

[0013] The beneficial effects of the above-mentioned further technical solutions of the present invention are: the clamp-type filter plate and the catalyst support mesh are used to fix the catalyst in the reaction chamber.

[0014] Furthermore, the top and bottom of the reaction tube are in contact with the clamp-on filter plate and the catalyst support mesh, respectively, and the mesh diameter of the clamp-on filter plate and the catalyst support mesh is 0.5~5μm.

[0015] The beneficial effect of the above-mentioned further technical solution of the present invention is that by contacting the top and bottom of the reaction tube with the clamp-type filter plate and the catalyst support mesh respectively, the catalyst can be prevented from being carried out of the reaction tube.

[0016] Furthermore, a heat transfer oil inlet is provided at the top of the side wall of the reaction chamber, and a heat transfer oil outlet is provided at the bottom of the side wall of the reaction chamber. The heat transfer oil inlet and outlet are respectively connected to the liquid outlet and liquid inlet of the oil bath heater. The inlet and outlet of the reaction tube are respectively located at the bottom and top of the reaction chamber.

[0017] The beneficial effects of the above-mentioned further technical solutions of the present invention are as follows: by setting the outlet and inlet of the oil bath heater at the top and bottom of the reaction chamber respectively, and setting the inlet and outlet of the reaction tube at the bottom and top of the reaction chamber respectively, the flow direction of the heat transfer oil in the reaction chamber is opposite to the flow direction of the organic liquid reaction, thereby increasing the heat exchange.

[0018] Furthermore, the top of the organic liquid raw material tank is equipped with a gas vent valve, the outlet of the organic liquid raw material tank is located at the bottom of the organic liquid raw material tank, the lower end of the outlet of the organic liquid raw material tank is equipped with a drain port, the outlet of the organic liquid raw material tank is connected to the inlet of the feed pump, and the outlet of the feed pump is connected to the inlet of the reaction tube.

[0019] The beneficial effects of the above-mentioned further technical solutions of the present invention are as follows: the gas vent valve is used to discharge the air in the organic liquid raw material tank, the drain port is used to discharge the organic liquid in the organic liquid raw material tank, and the feed pump is used to pump the organic liquid in the organic liquid raw material tank into the reaction tube.

[0020] Furthermore, a buffer tank, a hydrogen flow meter, and a flame arrester are sequentially installed at the hydrogen outlet of the product tank. An exhaust port is installed at the top of the product tank, a constant temperature heating jacket is installed on the outer wall of the product tank, and a drain port is installed at the bottom of the product tank.

[0021] The beneficial effects of the above-mentioned further technical solutions of this invention are as follows: the hydrogen flow meter is used to measure the hydrogen release flow rate at the hydrogen outlet. The exhaust port is used to discharge air from the product tank, the constant temperature heating jacket is used to maintain a constant temperature for the hydrogen-containing organic liquid in the product tank, and the gas outlet is connected to the flow meter to accurately measure the hydrogen release flow rate. The drain port is used to drain the liquid from the product tank.

[0022] Furthermore, a heat exchanger is installed between the tubular reactor and the product tank. The inlet of the heat exchanger is connected to the outlet of the tubular reactor, the outlet of the heat exchanger is connected to the feed inlet of the product tank, and the liquid inlet and outlet of the heat exchanger are respectively connected to the organic liquid raw material tank.

[0023] The beneficial effects of the above-mentioned further technical solutions of the present invention are: the heat exchanger is used to exchange heat between the high-temperature separated hydrogen and organic liquid and the hydrogen-containing organic liquid carrier in the organic liquid raw material tank, which increases the thermal energy utilization efficiency of the system and further reduces the system energy consumption.

[0024] Furthermore, it also includes an inert gas supply end, which is connected to the organic liquid raw material tank and the product tank.

[0025] The beneficial effect of the above-mentioned further technical solution of the present invention is that the inert gas supply end is used to purge the air from the organic liquid raw material tank, the tubular reactor, the product tank and all gas / liquid pipelines in the system before the reaction.

[0026] The beneficial effects of this invention are:

[0027] 1. This invention adopts a blending preheating reaction method, which effectively utilizes the low-temperature reaction zone and improves the hydrogen release degree of hydrogen-containing organic liquids;

[0028] 2. This invention uses a parallel reactor tube array to adapt to different production requirements, improve reaction efficiency, and at the same time increase the heat exchange area inside the reactor to improve heat exchange efficiency and reduce energy consumption.

[0029] 3. The flow direction of the heat transfer oil in the reaction chamber is opposite to that of the organic liquid reactant, which increases the heat exchange. At the same time, the oil bath heater can automatically adjust the temperature and liquid inlet rate through the temperature controller, reducing equipment energy consumption and extending catalyst life.

[0030] 4. The system integrates a heat exchanger, which increases the system's thermal energy utilization efficiency and further reduces system energy consumption. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the structure of the present invention;

[0032] The components are as follows: 1. Reaction chamber; 2. Inert gas supply end; 3. Organic liquid raw material tank; 4. Feed pump; 5. Tubular reactor; 6. Oil bath heater; 7. Heat exchanger; 8. Product tank; 9. Reaction tubes; 10. Preheating and mixing chamber; 11. Buffer chamber; 12. Clamped filter plate; 13. Catalyst support mesh; 14. Buffer tank; 15. Hydrogen flow meter; 16. Flame arrester. Detailed Implementation

[0033] The specific embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0034] In embodiments of the present invention, such as Figure 1 As shown, a continuous hydrogen release system is provided, including an inert gas supply end 2, an organic liquid feedstock tank 3, a tubular reactor 5, an oil bath heater 6, a heat exchanger 7, and a product tank 8. The inert gas supply end 2 is connected to the organic liquid feedstock tank 3 and the product tank 8, thereby allowing nitrogen to be supplied to the organic liquid feedstock tank 3, the tubular reactor 5, the heat exchanger 7, the product tank 8, and all gas / liquid pipelines in the system.

[0035] The tubular reactor 5 includes a preheating mixing chamber 10, a reaction chamber 1, and a buffer chamber 11 arranged from bottom to top. The preheating mixing chamber 10 is connected to the reaction chamber 1, and the reaction chamber 1 is connected to the buffer chamber 11 via flanges. Multiple reaction tubes 9 are arranged in parallel within the reaction chamber 1. The inlet of each reaction tube 9 is connected to the preheating mixing chamber 10, and the outlet of each reaction tube 9 is connected to the buffer chamber 11. A hydrogen-degrading catalyst and a thermocouple are installed within each reaction tube 9. A clamping filter plate 12 for fixing the catalyst is installed between the bottom of the buffer chamber 11 and the top of the reaction chamber 1, and a catalyst support mesh 13 for fixing the catalyst is installed between the top of the preheating mixing chamber 10 and the bottom of the reaction chamber 1. The mesh diameter of the clamping filter plate 12 and the catalyst support mesh 13 is 0.5~5μm. The top and bottom of each reaction tube 9 are welded to the clamping filter plate and the catalyst support mesh, respectively, to prevent the catalyst from being carried out of the reaction tubes. The tubular reactor 5 is equipped with an air vent at the bottom and a feed inlet at the top, and an outlet at the top for discharging material.

[0036] The organic liquid feedstock tank 3 is equipped with a gas vent valve at the top. The outlet of the organic liquid feedstock tank 3 is located at the bottom, and a drain port is located below the outlet. The outlet of the organic liquid feedstock tank 3 is connected to the inlet of the feed pump 4, and the outlet of the feed pump 4 is connected to the inlet of the tubular reactor 5. A check valve is installed at the outlet of the feed pump 4 to prevent backflow of liquid or gas and damage to the feed pump 4.

[0037] A heat transfer oil inlet is located at the top of the side wall of reaction chamber 1, and a heat transfer oil outlet is located at the bottom of the side wall of reaction chamber 1. The heat transfer oil inlet and outlet are connected to the liquid outlet and liquid inlet of oil bath heater 6, respectively, so that the flow direction of the heat transfer oil is opposite to the flow direction of the organic liquid reactant. The oil bath heater 6 is equipped with a temperature controller for adjusting the temperature and liquid inlet rate of the heat transfer oil, and the temperature controller is communicatively connected to a temperature measuring thermocouple.

[0038] The outlet at the top of the tubular reactor 5 is connected to the inlet of the heat exchanger 7, the outlet of the heat exchanger 7 is connected to the inlet of the product tank 8, and the inlet and outlet of the heat exchanger 7 are connected to the organic liquid feedstock tank 3, so that the organic liquid and high-temperature hydrogen can transfer heat to the organic liquid in the organic liquid feedstock tank 3 after high-temperature hydrogen release.

[0039] The product tank 8 has a hydrogen outlet at its top. A buffer tank 14, a hydrogen flow meter 15, and a flame arrester 16 are sequentially installed at the hydrogen outlet, ensuring that the hydrogen gas discharged from the outlet is buffered by the buffer tank 14 before being measured by the hydrogen flow meter 15. A constant-temperature heating jacket is fitted over the outer wall of the product tank 8. A drain port is located at the bottom of the product tank 8. The drain port can be used to sample and test the degree of hydrogen release from the organic liquid.

[0040] Before the system starts operating, the reaction tubes 9 in the tubular reactor 5 are filled with a hydrogen-releasing catalyst, which is either a Ru-based noble metal catalyst or a Ni-based non-noble metal catalyst. Simultaneously, the organic liquid feedstock tank 3 contains a certain amount of hydrogen-containing organic liquid for the hydrogen-releasing reaction. The inert gas supplied to the inert gas supply end 2 can be either nitrogen or argon.

[0041] When the system is in operation, first open the gas valve at the inert gas supply end 2 to purge the air from the organic liquid feedstock tank 3, the tubular reactor 5, the heat exchanger 7, the product tank 8, and all gas / liquid pipelines in the system. Then, turn on the oil bath heater 6 to bring the heat transfer oil in the tubular reactor 5 to the preset temperature (120~200℃). Next, the organic liquid in the organic liquid feedstock tank 3 is pumped into the preheating mixing chamber 10 of the tubular reactor 5 through the feed pump 4, with the valve set to the open position. The hydrogen-containing organic liquid simultaneously enters the preheating mixing chamber 10 of the tubular reactor 5 to complete the preheating and pre-hydrogen release process. The preheated hydrogen-containing organic liquid enters the reaction tube 9 and undergoes a hydrogen release reaction under the action of the hydrogen release catalyst. The hydrogen-released organic liquid and the released hydrogen gas pass through the heat exchanger 7 and exchange heat with the finned air-cooled heat exchanger. After the heat exchange is completed, the hydrogen-released organic liquid and hydrogen gas enter the product tank 8. The hydrogen gas is discharged to the external system or space through the hydrogen outlet of the product tank 8 after being metered by a flow meter. Hydrogen-containing organic liquids can be sampled through the drain port of product tank 8 to test the current hydrogen release level of the organic liquid.

[0042] Although specific embodiments of the present invention have been described in detail with reference to the accompanying drawings, this should not be construed as limiting the scope of protection of this patent. Various modifications and variations that can be made by those skilled in the art without inventive effort within the scope described in the claims are still within the scope of protection of this patent.

Claims

1. A continuous hydrogen release system, characterized in that: The system includes an organic liquid feedstock tank (3), a tubular reactor (5), an oil bath heater (6), and a product tank (8). The reaction chamber (1) of the tubular reactor (5) is connected at both ends to the inlet and outlet of the oil bath heater (6), respectively. Multiple parallel reaction tubes (9) are arranged inside the reaction chamber (1), and a hydrogen-degrading catalyst is installed inside each reaction tube (9). The outlet of the organic liquid feedstock tank (3) is connected to the inlet of the reaction tubes (9), and the outlet of the reaction tubes (9) is connected to the inlet of the product tank (8). A hydrogen outlet is located at the top of the product tank (8). The organic liquid raw material tank (3) is equipped with a gas vent valve at the top, the outlet of the organic liquid raw material tank (3) is located at the bottom of the organic liquid raw material tank (3), a drain port is provided at the lower end of the outlet of the organic liquid raw material tank (3), the outlet of the organic liquid raw material tank (3) is connected to the inlet of the feed pump (4), and the outlet of the feed pump (4) is connected to the inlet of the reaction tube (9). The product tank (8) is provided with a buffer tank (14), a hydrogen flow meter (15), and a flame arrester (16) in sequence at the hydrogen outlet. The top of the product tank (8) is provided with an exhaust port. The outer wall of the product tank (8) is provided with a constant temperature heating jacket. The bottom of the product tank (8) is provided with a drain port. A heat exchanger (7) is provided between the tubular reactor (5) and the product tank (8). The inlet of the heat exchanger (7) is connected to the outlet of the tubular reactor (5), and the outlet of the heat exchanger (7) is connected to the feed inlet of the product tank (8). The liquid inlet and liquid outlet of the heat exchanger (7) are respectively connected to the organic liquid raw material tank (3). It also includes an inert gas supply end (2), which is connected to the organic liquid raw material tank (3) and the product tank (8); A preheating mixing chamber (10) is provided at the bottom of the reaction chamber (1).

2. The continuous hydrogen release system according to claim 1, characterized in that: The oil bath heater (6) is equipped with a temperature controller for adjusting the temperature and inlet speed of the heat transfer oil, and the reaction tube (9) is equipped with a temperature measuring thermocouple. The temperature controller is communicatively connected to the temperature measuring thermocouple.

3. The continuous hydrogen release system according to claim 1, characterized in that: A buffer chamber (11) is provided at the top of the reaction chamber (1), and a clamping filter plate (12) for fixing the catalyst is provided between the bottom of the buffer chamber (11) and the top of the reaction chamber (1). A catalyst support mesh (13) for fixing the catalyst is provided between the top of the preheating mixing chamber (10) and the bottom of the reaction chamber (1).

4. The continuous hydrogen release system according to claim 3, characterized in that: The top and bottom of the reaction tube (9) are in contact with the clamp-type filter plate (12) and the catalyst support mesh (13), respectively, and the mesh diameter of the clamp-type filter plate (12) and the catalyst support mesh (13) is 0.5~5μm.

5. The continuous hydrogen release system according to claim 1, characterized in that: A heat transfer oil inlet is provided at the top of the side wall of the reaction chamber (1), and a heat transfer oil outlet is provided at the bottom of the side wall of the reaction chamber (1). The heat transfer oil inlet and the heat transfer oil outlet are respectively connected to the liquid outlet and liquid inlet of the oil bath heater (6). The inlet and outlet of the reaction tube (9) are respectively located at the bottom and top of the reaction chamber (1).

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