A kind of organic carrier hydrogen body hydrogenation reaction column reactor

Abstract

The application relates to a shell-and-tube reaction device for organic hydrogen carrier hydrogenation reaction, which comprises a shell, a material inlet and a material outlet provided on the shell for material inlet and outlet respectively, a catalytic reaction channel arranged in the shell, composed of a plurality of parallel tubes and extending along the axial direction of the shell, a hydrogenation catalyst laid in the parallel tubes to form a catalyst bed, and a heat exchange channel formed between the space outside the catalytic reaction channel and the shell and used as a temperature control fluid channel, wherein a heat exchange inlet and a heat exchange outlet are provided on the temperature control fluid channel for heat exchange medium inlet and outlet respectively, and the catalyst bed is arranged between the material inlet and the material outlet, wherein the heat exchange mechanism is arranged in the catalyst bed.

Description

Technical Field

[0001] This application relates to the field of chemical synthesis equipment technology, and in particular to a tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier. Background Technology

[0002] A tubular reactor (or multitubular reactor) is a type of continuous reactor widely used in gas-phase, liquid-phase, or gas-liquid phase reactions. Its core feature is the efficient heat transfer and reaction control achieved through a tube bundle structure. A tubular reactor is a reactor in which chemical reactions take place within tubes. Heat is transferred or supplied through the tube walls using a heat carrier, similar in structure to a shell-and-tube heat exchanger. The tubes are uniformly filled with catalyst, and the heat carrier flows between the tubes. To enhance heat transfer and continuously supply or remove reaction heat, the heat carrier must circulate. Different circulation methods are used depending on the type of heat carrier, such as internal circulation and external circulation.

[0003] The basic structure of a tubular reactor typically consists of hundreds to thousands of parallel, thin tubes (usually 10-50 mm in diameter and 1-10 m in length). The tubes are filled with catalyst (e.g., in a fixed bed) or empty for homogeneous reactions. The outer side is the shell, through which a heat transfer fluid (e.g., molten salt, thermal oil, or steam) is introduced to remove or provide the heat of reaction. Other key components include tube sheets (to fix the tube bundle), baffles (to optimize shell-side fluid distribution), and inlet / outlet distributors (to ensure uniform fluid distribution).

[0004] The working principle of a tubular reactor for hydrogenation is as follows: reactants enter from the top, are evenly distributed into each tube, react under the action of a catalyst, and the products flow out from the bottom. Radial heat transfer occurs through the tube walls and the shell-side heat carrier, avoiding hotspots or overheating.

[0005] Generally, the hydrogenation of organic hydrogen carriers (typically toluene / methylcyclohexane, carbazole / H12-carbazole, DBT / H18-DBT, etc. LOHC) is carried out in tubular reactors, which are liquid-solid-gas three-phase continuous fixed-bed reactors. They must ensure efficient dissolution / dispersion of hydrogen and remove the heat generated during hydrogenation to prevent hot spot deactivation.

[0006] This is because the hydrogenation reaction of organic hydrogen carriers is a strongly exothermic reaction, with an adiabatic temperature rise exceeding 1000K. Therefore, how to promptly remove the heat released by the reaction to maintain the reaction system in a steady state is a technical problem that needs to be considered in reactor and process design. Simultaneously, the start-up phase of the hydrogenation reaction requires heating the reactants. How to achieve a seamless connection between system heating and cooling, and how to maintain stable system operation after the reactants have been heated to the target temperature, are technical problems that need to be solved in this field. Summary of the Invention

[0007] To address the aforementioned problems, this invention provides a tubular reactor for hydrogenation of organic hydrogen carriers. Using this tubular reactor for hydrogenation can promptly remove the heat released during the reaction, achieve seamless integration of system heating and cooling, and maintain stable system operation after the reactants have been heated to the target temperature.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] A tubular reactor for hydrogenation of an organic hydrogen carrier includes: a shell, wherein the shell is provided with a material inlet and a material outlet for material to enter and exit respectively;

[0010] A catalytic reaction channel, disposed within the shell, consists of several parallel tubes extending axially along the shell; a hydrogenation catalyst is laid within the parallel tubes to form a catalyst bed; and

[0011] The heat exchange channel is the space between the outside of the catalytic reaction channel and the inside of the shell, forming a temperature-controlled fluid channel; the temperature-controlled fluid channel is provided with a heat exchange inlet and a heat exchange outlet for the heat exchange medium to enter and exit respectively.

[0012] The catalyst bed is disposed between the material inlet and the material outlet, wherein the heat exchange mechanism passes through the catalyst bed;

[0013] The reactant, an organic hydrogen-poor carrier, and hydrogen enter the material inlet of the tubular reactor. After passing through the catalyst bed, they are converted into the hydrogenation product, an organic hydrogen-rich carrier, at a suitable reaction temperature. The product then flows out from the material outlet of the tubular reactor. After gas-liquid separation, the liquid phase product and the remaining gaseous hydrogen are collected.

[0014] According to one embodiment of the present invention, the tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier further includes a mixing node connected to the material inlet; configured to mix organic hydrogen carrier and hydrogen gas, and then transport them to the catalytic reaction channel inside the shell.

[0015] According to one embodiment of the present invention, the tubular reaction device for hydrogenation reaction of organic hydrogen carrier has a cylindrical structure, and the material outlet is located at the opposite end of the material inlet; the mixture flowing out of the material outlet flows into the gas-liquid separation device through the pipeline for further separation, and the separated gas enters the hydrogen circulation pipeline.

[0016] According to one embodiment of the present invention, the tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier further includes a first three-way valve and a second three-way valve;

[0017] The heating fluid flows into the first three-way valve through the first input pipe, then enters the temperature-controlled fluid channel inside the shell through the heat exchange inlet, and finally flows from the heat exchange outlet to the second three-way valve, and then flows downstream through the second output pipe or circulates back to the front end of the first input pipe upstream.

[0018] According to one embodiment of the present invention, cooling water flows into the first three-way valve through the third input pipe, then enters the temperature-controlled fluid channel inside the shell through the fluid inlet, and finally flows from the heat exchange outlet to the second three-way valve, and then flows downstream through the fourth output pipe or circulates back to the front end of the third input pipe upstream.

[0019] According to one embodiment of the present invention, the tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier further includes one or more temperature measuring devices disposed in the catalytic reaction channel, configured to measure the temperature at a certain point in the catalyst bed space and display it on a corresponding digital display device.

[0020] According to one embodiment of the present invention, the tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier further includes a tube sheet assembled on the shell, the tube sheet having a tube assembly portion located inside the shell, the tube assembly portion being provided with a plurality of tube holes, and the plurality of tubes being respectively assembled in the corresponding tube holes.

[0021] According to one embodiment of the present invention, the catalytic reaction channel and the temperature-controlled fluid channel are alternately arranged in the cavity of the shell.

[0022] According to one embodiment of the present invention, the housing includes a shell body with both ends formed as open and a pair of semi-circular end caps, the pair of end caps respectively closing the corresponding ports of the shell body.

[0023] According to one embodiment of this utility model, when the tubular hydrogenation reactor is applied to the hydrogenation reaction of an organic hydrogen carrier, the reactants are unhydrogenated organic compounds that are liquid at room temperature and hydrogen gas; theoretically, after complete hydrogenation, the mass increment of the hydrogenated product relative to the unhydrogenated organic compound accounts for 4.5 to 7.3 wt% of the total mass of the hydrogenated product; the target temperature for stable operation of the hydrogenation reaction is in the range of 120 to 250°C; and the target pressure for stable operation of the hydrogenation reaction is in the range of 0.2 to 8 MPa.

[0024] The beneficial effects of this utility model are:

[0025] This invention provides a tubular reactor for hydrogenation of organic hydrogen carriers. Using this reactor for hydrogenation can promptly remove the heat released during the reaction, solving the problem of system overheating caused by strong exothermic reactions in the hydrogenation of liquid-phase organic compounds for hydrogen storage. It also addresses the switching between heating required for reaction start-up and heat dissipation needed once the reaction approaches or reaches a stable process, achieving seamless integration of system heating and cooling. Furthermore, it maintains stable system operation after the reactants are heated to the target temperature, providing a novel reactor structure for LOHC technology. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier according to the present invention.

[0027] Reference numerals in the attached diagram: 1-Shell; 2-Catalytic reaction channel; 3-Hydrogenation catalyst; 4-Temperature-controlled fluid channel; 5-Material inlet; 6-Material outlet; 7-Organic hydrogen carrier; 8-Hydrogen; 9-Mixing node; 10-Gas-liquid separator; 11-First input pipe; 12-Second input pipe; 13-Third input pipe; 14-Fourth output pipe; 15-Temperature measuring point; 16-Tube sheet. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] Embodiments of the present invention, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The terms "first," "second," "third," etc. (if present) in the specification, claims, and drawings of the present invention are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that the objects thus described can be interchanged where appropriate. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. Directional terms used in the present invention, such as: up, down, left, right, front, back, inside, outside, side, etc., are only for the purpose of referring to the drawings. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. Furthermore, the repetition of reference numerals and / or reference letters in different examples of the present invention is for simplification and clarity purposes and does not in itself indicate a relationship between the various embodiments and / or arrangements discussed.

[0030] like Figure 1 As shown, this utility model provides a tubular reaction device for hydrogenation reaction of organic hydrogen carrier, including a shell 1, a catalytic reaction channel 2 and a heat exchange channel.

[0031] The shell 1 is provided with a material inlet 5 and a material outlet 6 for material to enter and exit; the catalytic reaction channel 2 is set inside the shell 1, and is composed of several parallel tubes that extend along the axial direction of the shell 1; the hydrogenation catalyst 3 is laid in the parallel tubes to form a catalyst bed.

[0032] The heat exchange channel is the space between the outside of the catalytic reaction channel 2 and the inside of the shell 1, forming a temperature-controlled fluid channel 4; the temperature-controlled fluid channel 4 is provided with a heat exchange inlet and a heat exchange outlet for the heat exchange medium to enter and exit respectively, and is located inside the shell 1; the catalyst bed is located between the material inlet 5 and the material outlet 6, wherein the heat exchange mechanism passes through the catalyst bed.

[0033] That is, the reactor chamber contained in the shell 1 is generally divided into two non-communicating spaces: one is a catalytic reaction channel 2 composed of several parallel tubes, in which hydrogenation catalyst 3 is filled to form a catalyst bed; the other part of the space is the space outside the parallel tubes and inside the shell 1, which serves as a temperature control fluid channel 4 to control the reaction temperature inside the tubes, especially the catalyst bed.

[0034] like Figure 1 As shown, the hydrogenation tubular reactor also includes a mixing node 9 connected to the material inlet 5, used to mix the reactants, and then transport the mixed materials to the catalytic reaction channel 2 inside the shell 1.

[0035] In this invention, the reactants are hydrogen gas 8 and a hydrogen-poor state material (term symbol: H0-LOHC) of an organic hydrogen carrier, denoted as organic hydrogen carrier 7.

[0036] Specifically, the hydrogenation tubular reactor can have a cylindrical structure, with the material outlet 6 located at the opposite end of the material inlet 5. One end of several parallel tubes converges to form a channel, serving as the overall reactant inlet 5; simultaneously, the other ends of the tubes also converge to form a channel, serving as the overall reactant outlet 6. The reaction mixture flowing out of the material outlet 6 flows through a pipeline into a gas-liquid separator 10 for further separation, and the separated gas enters the hydrogen circulation pipeline.

[0037] from Figure 1 The flow can be seen from the organic hydrogen carrier H0-LOHC, the direction of hydrogen flow into the reactor, and the direction of reaction product flow out of the reactor. The organic hydrogen-poor carrier and hydrogen enter the material inlet 5 of the tubular reactor, pass through the catalyst bed, and are converted into the hydrogenation product organic hydrogen-rich carrier at a suitable reaction temperature. The product then flows out from the material outlet 6 of the tubular reactor, where gas-liquid separation is performed, and the liquid product and residual gaseous hydrogen are collected.

[0038] In this utility model, such as Figure 1 As shown, the hydrogenation tubular reactor also includes a first three-way valve and a second three-way valve.

[0039] Specifically, the flow of heating fluid or cooling water is controlled according to the required reaction temperature of the catalyst bed:

[0040] The heating fluid is introduced, flows into the first three-way valve through the first input pipe 11, and then enters the temperature control fluid channel 4 inside the shell 1 through the heat exchange inlet. Finally, it flows from the heat exchange outlet to the second three-way valve, and then flows downstream through the second output pipe 12 or circulates back to the front end of the upstream first input pipe 11.

[0041] When the catalyst bed needs to be cooled and heat exchanged, cooling water is introduced. The cooling water flows into the first three-way valve through the third input pipe 13, then enters the temperature-controlled fluid channel 4 in the shell 1 through the fluid inlet, and finally flows from the heat exchange outlet to the second three-way valve. After that, it flows downstream through the fourth output pipe 14 or is circulated back to the front end of the third input pipe 13 upstream.

[0042] Preferably, the housing 1 is made of a rigid material, such as stainless steel, iron, titanium alloy, aluminum alloy, enamel, etc., with stainless steel being the preferred material.

[0043] According to this invention, the hydrogenation tubular reactor further includes one or more temperature measuring devices, preferably thermocouples, disposed within the catalytic reaction channel 2, for measuring the temperature at a certain point in the catalyst bed space and displaying it on a corresponding digital display device. Since the bed temperature is not uniform, multiple temperature measuring points 15 can be configured as needed.

[0044] Specifically, the hydrogenation tubular reactor also includes a tube sheet mounted on the reactor shell 1. The tube sheet has a tube assembly portion located inside the reactor shell 1. The tube assembly portion is provided with multiple tube holes, and the multiple tubes are respectively assembled in the corresponding tube holes.

[0045] Preferably, the shell 1 includes a shell body with both ends formed as open and a pair of semi-circular end caps, the pair of end caps respectively closing the corresponding ports of the shell body.

[0046] In one embodiment of the present invention, the shell body may further include a plurality of shell segments arranged along the axial direction of the shell 1, and the plurality of shell segments can be assembled together to form the shell 1 (not shown in the figure).

[0047] The general process flow of the hydrogenation tubular reactor used in this invention is as follows:

[0048] The reactants H0-LOHC and hydrogen are reacted according to... Figure 1 As indicated by the middle arrow, the materials converge at a mixing node 9 for mixing, and then simultaneously enter the reactor inlet 5. After passing through the catalyst bed, they are converted into hydrogenation products, namely the hydrogen-rich carrier Hn-LOHC, an organic hydrogen carrier, at a suitable reaction temperature. These products then flow out from the reactor inlet 6 and proceed downstream to processing equipment in the direction of the arrow. For example, they flow to the downstream gas-liquid separator 10, where the liquid phase product is collected after separation, and the remaining gas phase is recycled back to the hydrogen storage tank for a cycle.

[0049] The reaction temperature is controlled as follows: when the material space velocity in the reaction channel reaches the target process value, heat transfer oil in the range of 100 to 280°C is used as the initial temperature control fluid, and its specific temperature and flow rate are adjusted according to whether the reaction temperature has reached the process objective.

[0050] The initial temperature-controlled fluid flows into the first three-way valve via the first input pipe 11, then enters the temperature-controlled fluid channel 4 of the reactor, and flows out through the second output pipe 12 in the direction of the arrow, returning to the heat transfer oil storage tank for further temperature regulation. When the heat transfer oil temperature at the outlet of the second output pipe 12 begins to rise spontaneously (above the inlet temperature), the temperature-controlled fluid can be switched to room temperature cooling water via the three-way valve, and the temperature measured at the temperature measuring point 15 is maintained within the target reaction temperature range by fine-tuning the flow rate. The cooling water flows into the first three-way valve via the third input pipe 13, then enters the temperature-controlled fluid channel 4 inside the shell 1 via the fluid inlet, and finally flows from the heat exchange outlet to the second three-way valve, then flows downstream via the fourth output pipe 14 or is circulated back to the front end of the third input pipe 13 upstream. In larger reactors, the heated room temperature water can be used as hot water.

[0051] In this invention, the reactants are unhydrogenated organic compounds (including pure substances or mixtures) that are liquid at room temperature and hydrogen gas; theoretically, after complete hydrogenation, the mass increment of the hydrogenated product relative to the unhydrogenated organic compound is in the range of 4.5 to 7.3 wt% of the total mass of the hydrogenated product; the target temperature for stable operation of the hydrogenation reaction is in the range of 120 to 250°C; and the target pressure for stable operation of the hydrogenation reaction is in the range of 0.2 to 8 MPa.

[0052] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A tubular reaction apparatus for hydrogenation reaction of an organic hydrogen carrier, characterized in that, include: The housing (1) is provided with a material inlet (5) and a material outlet (6) for material to enter and exit respectively. The catalytic reaction channel (2) is set inside the shell (1), consisting of several parallel tubes and extending along the axial direction of the shell (1), and the hydrogenation catalyst (3) is laid inside the parallel tubes to form a catalyst bed. as well as The heat exchange channel is the space between the outside of the catalytic reaction channel (2) and the inside of the shell (1), forming a temperature-controlled fluid channel (4); the temperature-controlled fluid channel (4) is provided with a heat exchange inlet and a heat exchange outlet for the heat exchange medium to enter and exit respectively; The catalyst bed is disposed between the material inlet (5) and the material outlet (6), wherein the heat exchange channel passes through the catalyst bed; The reactant organic hydrogen-poor carrier and hydrogen enter the material inlet (5) of the tubular reactor. After passing through the catalyst bed, they are converted into the hydrogenation product organic hydrogen-rich carrier at a suitable reaction temperature and flow out from the material outlet (6) of the tubular reactor. Then, gas-liquid separation is performed, and the liquid phase product and the remaining gas phase hydrogen are collected.

2. The tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier according to claim 1, characterized in that, It also includes a mixing node (9) connected to the material inlet (5); configured to mix the organic hydrogen-poor carrier (7) with hydrogen (8) and then deliver it to the catalytic reaction channel (2) inside the shell (1).

3. The tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier according to claim 1, characterized in that, The tubular reactor for hydrogenation reaction has a cylindrical structure, and the material outlet (6) is located at the opposite end of the material inlet (5). The mixture flowing out of the material outlet (6) flows into the gas-liquid separator (10) through the pipeline for further separation, and the separated gas enters the hydrogen circulation pipeline.

4. The tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier according to claim 1, characterized in that, It also includes a first three-way valve and a second three-way valve; the heating fluid flows into the first three-way valve through the first input pipe (11), then enters the temperature control fluid channel (4) in the shell (1) through the heat exchange inlet, and finally flows from the heat exchange outlet to the second three-way valve, and flows downstream through the second output pipe (12) or circulates back to the front end of the upstream first input pipe (11).

5. The tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier according to claim 4, characterized in that, Cooling water flows into the first three-way valve through the third input pipe (13), then enters the temperature-controlled fluid channel (4) inside the shell (1) through the fluid inlet, and finally flows from the heat exchange outlet to the second three-way valve. After that, it flows downstream through the fourth output pipe (14) or is circulated back to the front end of the third input pipe (13) upstream.

6. The tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier according to claim 1, characterized in that, It also includes one or more temperature measuring devices disposed in the catalytic reaction channel (2), configured to measure the temperature at a certain point in the catalyst bed space and display it on a corresponding digital display device.

7. The tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier according to claim 1, characterized in that, It also includes a tube sheet (16) assembled on the housing (1), the tube sheet (16) having a tube assembly portion located inside the housing (1), the tube assembly portion being provided with a plurality of tube holes, and the plurality of tubes being respectively assembled in the corresponding tube holes.

8. The tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier according to claim 1, characterized in that, The catalytic reaction channel (2) and the temperature-controlled fluid channel (4) are alternately arranged in the cavity of the housing (1).

9. The tubular reaction apparatus for hydrogenation reaction of organic hydrogen carrier according to claim 1, characterized in that, The shell (1) includes a shell body with both ends formed as open and a pair of semi-circular end caps, the pair of end caps respectively closing the corresponding ports of the shell body.

10. The tubular reaction apparatus for hydrogenation reaction of organic hydrogen carriers according to any one of claims 1 to 9, characterized in that, When the tubular hydrogenation reactor is used for hydrogenation of organic hydrogen carriers, the reactants are unhydrogenated organic compounds that are liquid at room temperature and hydrogen gas. Theoretically, after complete hydrogenation, the mass increment of the hydrogenated product relative to the unhydrogenated organic compound is 4.5~7.3 wt% of the total mass of the hydrogenated product. The target temperature for stable operation of the hydrogenation reaction is 120~250°C. o C; The target pressure for stable operation of the hydrogenation reaction is 0.2~8MPa.

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