Hydrogenation reaction device adopting combined catalyst bed layer and hydrogenation method

Abstract

The invention discloses a hydrogenation reaction device adopting a combined catalyst bed layer and a hydrogenation method. The hydrogenation reaction device comprises a gas-liquid removal area, a hydrogenation reaction area and a liquid-gas removal area which are sequentially communicated from top to bottom, a plurality of longitudinally distributed combined catalyst bed layers are arranged in the hydrogenation reaction area, and a liquid raw material feeding hole is formed between the gas-liquid removal area and the uppermost combined catalyst bed layer; a hydrogen feeding hole is formed between the liquid degassing area and the lowermost combined catalyst bed layer; the combined catalyst bed layer comprises an upper fixing layer, a middle sandwich layer and a lower supporting layer, the fixing layer and the supporting layer are filled with modular catalyst units, the sandwich layer comprises one or more catalyst bags, each catalyst bag comprises catalyst particles and a wrapping assembly used for wrapping the catalyst particles, and the wrapping assemblies are used for wrapping the catalyst particles. The wrapping assembly is provided with holes allowing materials to penetrate but preventing catalyst particles from penetrating.

Description

Technical Field

[0001] The invention relates to the technical field of hydrogenation, and in particular to a hydrogenation reaction device and a hydrogenation method using a combined catalyst bed. Background Art

[0002] Oil hydrogenation technology is a process in which raw materials and hydrogen are catalyzed by a catalyst to improve the quality of oil products under certain reaction conditions (temperature and pressure). Hydrogenation technology is widely used in various fields such as petroleum refining, chemical industry, biochemical industry, food and medicine.

[0003] The fixed bed hydrogenation technology widely used in industry is the gas-liquid co-current trickle bed hydrogenation process, which is a technology in which the gas and liquid phases flow downward through a fixed catalyst bed in parallel, and the hydrogenation reaction is completed in this process. Generally speaking, the fixed bed gas-liquid co-current hydrogenation process is a trickle bed hydrogenation process, in which the liquid passes through the solid catalyst downward in the form of a liquid film. Under this flow condition, especially for large fixed bed gas-liquid co-current devices, there are the following significant problems: the liquid leads to uniform distribution, channeling and short-circuiting under low-speed and low-turbulence conditions, so that the catalyst cannot be fully wetted, the utilization rate of the catalyst and the reaction conversion rate are reduced, and it is also easy to cause uneven radial temperature distribution in the reactor, forming local hot spots, accelerating catalyst deactivation, and directly affecting the efficiency of catalytic hydrogenation reactions. In order to solve the above problems, fixed bed gas-liquid countercurrent hydrogenation has become a research hotspot and important development direction for fixed bed hydrogenation reaction processes based on its advantages of improving material turbulence, mass transfer and heat transfer efficiency, and improving catalyst utilization. However, the conventional fixed-bed countercurrent hydrogenation process is based on the gas phase passing through the catalyst bed at high speed in an upward flow, which is prone to catalyst particle floating and breakage, local retention of liquid or low turbulence or uneven reaction, resulting in local hot spots and catalyst coking. Therefore, technological progress is urgently needed to reflect the significant superiority of the fixed-bed countercurrent hydrogenation process technology.

[0004] Patent CN102041069B proposes a gas-liquid countercurrent hydrogenation method for diesel desulfurization, denitrogenation and aromatic saturation, in which hydrogen and diesel feedstock pass through the catalyst bed in a countercurrent manner under the conditions of diesel fraction hydrotreatment. The reactor is divided into at least two reaction zones, each of which is composed of at least one hydrogenation catalyst bed; the reactor diameter increases from the lower reaction zone to the upper reaction zone; a liquid accumulation zone is set at the diameter change of at least one reaction zone, and a liquid accumulation outlet pipeline is set at the bottom or side of the liquid accumulation zone to introduce the liquid in the liquid accumulation zone into the lower reaction zone of the reactor as a cooling stream. On the one hand, the patent changes the gas velocity by setting the reactor diameter change, the purpose is to prevent liquid flooding and maintain stable operation in the reactor, and on the other hand, introduces cooling streams to extract heat from the bed, but there are still problems such as floating and fragmentation of catalyst particles, local hot spots and catalyst coking.

[0005] Patent application CN116948701A proposes a hydrogenation process for blended bio-oil, wherein hydrogen enters from the gas-liquid contact zone, partially passes through the gas-liquid contact zone, the gas-liquid countercurrent zone, the gas-liquid separation zone and the gas phase reaction zone in sequence, and partially exchanges heat with the liquid phase material flowing out of the gas-liquid countercurrent zone and mixes into the liquid phase reaction zone; the raw material for blended bio-oil enters from the gas-liquid separation zone, partially converts into gas phase, and enters the gas phase reaction zone together with the gas phase material from the gas-liquid countercurrent zone for hydrogenation reaction, and the gas phase reaction product flows out from the top of the reactor; the liquid phase raw material in the gas-liquid separation zone enters the gas-liquid countercurrent zone, contacts with hydrogen countercurrent reaction and enters the gas-liquid contact zone, and the liquid phase material enters the gas-liquid contact zone downward for liquid phase hydrogenation reaction, and the liquid phase reaction product flows out from the bottom of the reactor. The patent sets the liquid flow state by partitioning, with the purpose of controlling the reaction temperature rise and timely removing the water generated by the hydrogenation of bio-oil, but it still does not solve the problems of catalyst particle floating and fragmentation, local hot spots and catalyst coking on hydrogenation efficiency and long-term operation of the device.

[0006] Therefore, for the fixed-bed gas-liquid countercurrent hydrogenation process, the development of new countercurrent hydrogenation technology, catalyst form and reactor structure is of great significance for improving mass transfer and heat transfer in the hydrogenation reaction process, solving problems such as catalyst particle floating and breakage, local hot spots and catalyst coking. Summary of the invention

[0007] In view of the above technical problems and the deficiencies in the art, the present invention provides a hydrogenation reaction device and a hydrogenation method using a combined catalyst bed.

[0008] [1] A hydrogenation reaction device using a combined catalyst bed, comprising a gas deliquidation zone, a hydrogenation reaction zone and a liquid degassing zone which are sequentially connected from top to bottom, wherein a plurality of combined catalyst beds are arranged vertically in the hydrogenation reaction zone, a liquid raw material feed port is arranged between the gas deliquidation zone and the uppermost combined catalyst bed, and a hydrogen feed port is arranged between the liquid degassing zone and the lowermost combined catalyst bed;

[0009] The combined catalyst bed includes an upper fixed layer, a middle sandwich layer and a lower support layer. The fixed layer and the support layer are filled with modular catalyst units. The sandwich layer contains one or more catalyst packages. The catalyst packages contain catalyst particles and a wrapping assembly for wrapping the catalyst particles. The wrapping assembly has holes that allow materials (gas, liquid, etc.) to pass through but prevent catalyst particles from passing through.

[0010] The liquid raw material feed port is connected to the top of the uppermost combined catalyst bed. The hydrogen feed port is connected to the bottom of the lowermost combined catalyst bed. The structures of the combined catalyst beds can be all the same, partly the same, or all different, preferably different. The diameters of the gas deliquidation zone, the hydrogenation reaction zone, and the liquid degassing zone can be the same or different, preferably the same.

[0011] The modular catalyst unit loaded with the fixed layer and the supporting layer is generally composed of an integral honeycomb substrate, a coating material and an active component; during the preparation process, the integral honeycomb monomer can be used as a substrate, and a step-by-step impregnation method of loading a high specific surface coating and active components can be adopted, and the thickness of the active component impregnation can be controlled by adjusting the coating amount; the modular catalyst unit can use commercial products as needed, or improve commercial products as needed, or can be prepared according to conventional knowledge in the field. The fixed layer and the supporting layer can be loaded with modular catalyst units of the same or different numbers of layers, preferably modular catalyst units of different numbers of layers.

[0012] The shapes of the modular catalyst units loaded with the fixed layer and the supporting layer can be independently any one or more combinations of cylindrical, rectangular, square, rhombus, polygonal, etc., preferably rectangular. The shapes of the modular catalyst units loaded with the fixed layer and the supporting layer can be the same or different. The modular catalyst units loaded with the fixed layer and the supporting layer can be provided with an array-arranged mutually penetrating hole structure, and the through hole size can be independently 1mm×1mm~10mm×10mm, preferably independently 3mm×3mm~8mm×8mm, such as 6mm×6mm, etc. The opening sizes of the modular catalyst units loaded with the fixed layer and the supporting layer can be the same or different.

[0013] In some embodiments, a residual gas outlet may be provided at the top of the gas deliquidation zone of the hydrogenation reaction device.

[0014] In some embodiments, in the hydrogenation reaction device, a liquid reaction product outlet may be provided at the bottom of the liquid degassing zone.

[0015] In some embodiments, in the hydrogenation reaction unit, the number of combined catalyst beds in the hydrogenation reaction zone may be 2 to 6, such as 3, 4, etc.

[0016] In some embodiments, a liquid material distributor may be disposed on the upper portion of the combined catalyst bed to uniformly distribute the liquid material from above. The liquid material flowing downward is connected to the liquid material distributor.

[0017] In some embodiments, a gas material distributor may be provided at the lower part of the combined catalyst bed layer for uniformly distributing the gas material from below. The gas material such as hydrogen flowing upward is connected to the gas material distributor.

[0018] In some preferred examples, the hydrogenation reaction device is provided with a pulse hydrogen feed port between adjacent combined catalyst beds. The pulse hydrogen feed port can intermittently introduce pulse hydrogen. Furthermore, the pulse hydrogen feed port can be connected to a gas material distributor of an upper combined catalyst bed adjacent thereto. The hydrogen and other gaseous materials from the combined catalyst bed of the lower layer adjacent to the pulse hydrogen feed port rise together with the hydrogen introduced from the pulse hydrogen feed port and then are connected through the gas material distributor to enter the combined catalyst bed of the upper layer adjacent to the pulse hydrogen feed port.

[0019] The hydrogenation reaction device, the liquid material distributor and the gas material distributor can be independently any one or more combinations of tubular, plate, bubble, nozzle, jet, trough, disc, metal membrane tube, ceramic membrane tube, and microchannel.

[0020] In some embodiments, in the hydrogenation reaction device, the height of the catalyst package in each sandwich layer can be independently 50 to 1500 mm, preferably independently 50 to 1000 mm, for example, 100 mm, 115 mm, 130 mm, 150 mm, 155 mm, 180 mm, 200 mm, 260 mm, 300 mm, 337.5 mm, 450 mm, 600 mm, 675 mm, 900 mm, etc.

[0021] In some embodiments, in the hydrogenation reaction device, for any two adjacent combined catalyst beds, the volume of catalyst particles loaded in the sandwich layer in the lower combined catalyst bed (volume of catalyst package) can be independently less than or equal to the volume of catalyst particles loaded in the sandwich layer in the upper combined catalyst bed. Further, for any two adjacent combined catalyst beds, the volume of catalyst particles loaded in the sandwich layer in the lower combined catalyst bed can be independently 80% to 99% of the volume of catalyst particles loaded in the sandwich layer in the upper combined catalyst bed. Further, the volume of catalyst particles loaded in the sandwich layer in the lower combined catalyst bed can be independently 85% to 97% (for example, 90%) of the volume of catalyst particles loaded in the sandwich layer in the upper combined catalyst bed. The volume of catalyst particles loaded in the sandwich layer can be uniform or non-uniform as the combined catalyst bed changes from top to bottom.

[0022] In some embodiments, the height of the modular catalyst units loaded in the fixed layer and the supporting layer of the hydrogenation reaction device can be 50 to 1500 mm, preferably 100 to 900 mm, such as 150 mm, 250 mm, 300 mm, 450 mm, 600 mm, etc. The heights of the modular catalyst units loaded in the fixed layer and the supporting layer can be the same or different.

[0023] In some embodiments, in the hydrogenation reaction device, for any two adjacent combined catalyst beds, the volume of catalyst loaded in the fixed layer in the lower combined catalyst bed can be independently greater than or equal to the volume of catalyst loaded in the fixed layer in the upper combined catalyst bed. Further, for any two adjacent combined catalyst beds, the volume of catalyst loaded in the fixed layer in the lower combined catalyst bed can be independently 100% to 800% of the volume of catalyst loaded in the fixed layer in the upper combined catalyst bed, and further, the volume of catalyst loaded in the fixed layer in the lower combined catalyst bed can be independently 100% to 500% (e.g., 150%, 200%, etc.) of the volume of catalyst loaded in the fixed layer in the upper combined catalyst bed. The volume of catalyst loaded in the fixed layer can be uniform or non-uniform as the combined catalyst bed changes from top to bottom.

[0024] In some embodiments, in the hydrogenation reaction device, for any two adjacent combined catalyst beds, the volume of catalyst loaded in the support layer in the lower combined catalyst bed can be independently greater than or equal to the volume of catalyst loaded in the support layer in the upper combined catalyst bed. Further, for any two adjacent combined catalyst beds, the volume of catalyst loaded in the support layer in the lower combined catalyst bed can be independently 100% to 800% of the volume of catalyst loaded in the support layer in the upper combined catalyst bed. Further, the volume of catalyst loaded in the support layer in the lower combined catalyst bed can be independently 100% to 500% (e.g., 150%, 200%, etc.) of the volume of catalyst loaded in the support layer in the upper combined catalyst bed. The volume of catalyst loaded in the support layer can be uniform or non-uniform as the combined catalyst bed changes from top to bottom.

[0025] In some embodiments, for any combined catalyst bed, the porosity of the catalyst loaded in the fixed layer of the hydrogenation reaction device can be independently less than or equal to (preferably less than) the porosity of the catalyst loaded in the support layer. This is mainly because the fixed layer is located above the catalyst package, and a slightly lower porosity is conducive to achieving uniform distribution of materials and preventing the problem of material accumulation in the catalyst package, while the support layer is located below the catalyst package, and a slightly higher porosity is conducive to material circulation and heat diffusion, thereby preventing problems such as reaction heat accumulation and local hot spots.

[0026] In some embodiments, for the hydrogenation reaction device, for any combined catalyst bed, the void ratio of the catalyst loaded in the fixed layer is independently 50% to 75%, preferably independently 55% to 75%, for example 65%, etc., and the void ratio of the catalyst loaded in the supporting layer is independently 60% to 95%, preferably independently 70% to 90%, for example 75%, 80%, etc.

[0027] The height-to-diameter ratio of the hydrogenation reaction device may be 0.5 to 10:1, preferably 1 to 5:1, such as 2.0:1, 2.5:1, etc.

[0028] In the hydrogenation reaction device, grids can be independently arranged at the bottom of the fixed layer, sandwich layer and supporting layer to support and fix the catalyst loaded in the corresponding layer. Both sides of the grid can be used for material flow, so that the combined catalyst bed becomes a cage structure with internal support.

[0029] In the hydrogenation reaction device, the fixed layer and the support layer can be independently loaded with 1 to 20 layers, preferably 1 to 10 layers (eg 2 layers, 6 layers, 10 layers, etc.) of modular catalyst units.

[0030] In the hydrogenation reaction device, the catalyst packages can be stacked. The wrapping component can be a flexible wire mesh. Each catalyst package includes catalyst particles and a flexible wire mesh wrapped outside thereof. The flexible wire mesh plays an isolating role on the one hand to prevent the catalyst particles from floating or running away and causing breakage, and on the other hand can be appropriately squeezed and deformed by the catalyst particles.

[0031] In the hydrogenation reaction device, the hole size of the wrapping component can be 10-100 mesh, such as 12 mesh.

[0032] In the hydrogenation reaction device, the catalyst particles can be independently shaped in the form of a sphere, a toothed sphere, a sheet, a strip, a clover, a four-leaf clover, a hollow ring, a multi-hole column, or a combination of one or more of the following.

[0033] In the hydrogenation reaction device, the radial dimension of the cross section of the catalyst particles can be 0.5 to 10 mm, preferably 1 to 6 mm, such as 1 to 2 mm, 1.8 to 2.8 mm, etc.

[0034] In the hydrogenation reaction device, the catalyst particles are generally supported catalysts, wherein the catalyst carrier can be one or more of SiO2, Al2O3, SiO2-Al2O3, TiO2, activated carbon, MgO, molecular sieves, etc.

[0035] The hydrogenation reaction device described above can be loaded with a catalyst having a hydrogenation function in the hydrogenation reaction zone. The hydrogenation active component can be selected according to the type of hydrogenation reaction, such as any one or more of a hydrogenation saturation catalyst, a hydrodesulfurization catalyst, a hydrodenitrogenation catalyst, a hydrodemetallization catalyst, a hydrodeoxygenation catalyst, a hydrocracking catalyst, an aromatics hydrogenation saturation catalyst, etc.; the catalyst active component includes but is not limited to one or more combinations of precious metals, Co, Mo, Ni, W, Mg, Zn, rare earth elements, etc.; the catalyst active components can be the same or different; the catalytic activity can be the same or different, preferably the same. Here, the catalytic activity of the catalyst can be regulated during the preparation process by the size of the specific surface area of ​​the catalyst carrier, the nature of the active center on the surface, and the number of active centers per unit surface area.

[0036] In the hydrogenation reaction device, the gas deliquid zone can be provided with a component with a gas-liquid separation function to perform gas-liquid separation; the component with the gas-liquid separation function can be one or more of a baffle structure, a cyclone / centrifugal structure, a filler and a wire mesh structure; the liquid degassing zone can be provided with a liquid level control and a certain liquid level height to keep the liquid for a sufficient residence time to achieve liquid degassing, and a component with a liquid degassing function can be provided inside or not.

[0037] [2] Application of the hydrogenation reaction device according to [1] in a hydrogenation reaction. The hydrogenation reaction device can be used as the main hydrogenation reaction, pre-hydrogenation reaction or post-hydrogenation reaction in the hydrogenation process, and can also be connected in series or in parallel with gas-liquid co-current fixed bed hydrogenation, upflow or downflow liquid phase hydrogenation, ebullating bed hydrogenation, suspended bed hydrogenation and other processes.

[0038] [3] A hydrogenation method, using the hydrogenation reaction device described in [1].

[0039] In some embodiments, the hydrogenation method comprises:

[0040] The liquid raw material enters the hydrogenation reaction device through the liquid raw material feed port, and the hydrogen enters the hydrogenation reaction device through the hydrogen feed port. The liquid raw material and the hydrogen undergo a countercurrent hydrogenation reaction in the combined catalyst bed. The liquid material after the hydrogenation reaction enters the liquid degassing zone for degassing, and the gas material after the hydrogenation reaction enters the gas deliquidation zone for deliquidation.

[0041] In the hydrogenation method, the hydrogen gas from the hydrogen inlet can be continuously introduced. The hydrogen gas introduced from the hydrogen inlet is the main reaction hydrogen of the hydrogenation reaction.

[0042] In the hydrogenation method, pulse hydrogen can be intermittently introduced between adjacent combined catalyst beds. The pulse hydrogen can be introduced through a pulse hydrogen feed port.

[0043] In the hydrogenation method, the duration of a single pulse hydrogen injection between adjacent combined catalyst beds can be independently 10 to 120 seconds, such as 20 seconds, 30 seconds, 40 seconds, 60 seconds, etc., and the time interval between two adjacent pulse hydrogen injections can be independently 300 to 1200 seconds, such as 600 seconds, etc. The duration of a single injection between each pulse hydrogen and the time interval between two adjacent pulse hydrogen injections can be the same or different, and can be specifically set according to the reaction conditions.

[0044] In the hydrogenation method, the ratio of the single pulse hydrogen flow rate between each adjacent combined catalyst bed layer to the liquid raw material feed rate can be independently 1 to 100 Nm 3 / h:1m 3 / h, preferably 5 to 50 Nm 3 / h:1m 3 / h.

[0045] In the hydrogenation method, the single pulse hydrogen injection amount can be gradually increased along the flow direction of the liquid material. Further, the increasing rate can be 1% to 80%, preferably 10% to 50%, and the changing trend of the increasing rate can be uniform or non-uniform.

[0046] In the hydrogenation method, the space velocity of the modular catalyst unit loaded with the fixed layer and the supporting layer can be 2 to 30 h -1 , preferably 5 to 20 hours -1 , for example 8h -1 , 10h -1 , 12h -1 , 16h -1 wait.

[0047] In the hydrogenation method, the space velocity of the catalyst particles loaded in the sandwich layer can be 0.1 to 10 h -1 , preferably 0.5 to 4 hours -1 , for example 0.5h -1 、0.6h -1 , 0.8h -1 , 1h -1 , 2h -1 wait.

[0048] In the hydrogenation method, the space velocity of the modular catalyst units loaded in the fixed layer and the supporting layer is preferably not less than the space velocity of the catalyst particles loaded in the sandwich layer.

[0049] The hydrogenation method described above comprises the following steps: the total hydrogen (the sum of the main reaction hydrogen feed and each pulse hydrogen) and the liquid reaction raw material (m 3 / h) can be adjusted according to various hydrogenation reaction requirements, hydrogen consumption, catalyst activity changes, i.e., conversion rate and selectivity changes. In principle, the lowest total hydrogen-to-liquid ratio is the one that minimizes catalyst coking while ensuring the best hydrogenation reaction effect. In some embodiments, the feed ratio of total hydrogen to liquid raw material can be 1 to 1500 Nm 3 / h:1m 3 / h, preferably 5-600Nm 3 / h:1m 3 / h.

[0050] The hydrogenation method and the hydrogenation reaction process conditions are generally determined by those skilled in the art according to the properties of the raw materials, the quality requirements of the final product, etc. In some embodiments, the hydrogenation reaction temperature may be room temperature to 500° C., and the hydrogenation reaction pressure may be 0.1 to 20 MPaG.

[0051] The hydrogenation reaction device and hydrogenation method using a combined catalyst bed are applicable to various raw materials that can undergo hydrogenation reaction with hydrogen in the fields of petrochemical, medicine, food, etc., and can be crude oil and secondary processed oil such as crude oil, gasoline, kerosene, diesel, residual oil, heavy oil, wax oil, lubricating oil, deasphalted oil, biodiesel, animal oil or vegetable oil, coal tar, anthracene oil, etc.; it can also be various raw materials containing carbon-carbon double bonds, carbon-carbon triple bonds and organic functional groups that can undergo hydrogenation reaction in the fields of chemical, medicine, food, etc., such as olefin hydrogenation, alkyne hydrogenation, aldehyde compound hydrogenation, ketone compound hydrogenation, ester compound hydrogenation, nitro compound hydrogenation, carbonyl compound hydrogenation, nitrile compound hydrogenation and the like.

[0052] The present invention couples a specially designed combined catalyst bed with a countercurrent hydrogenation reaction process, controls the intermittent action of pulsed hydrogen on the combined catalyst bed, and can greatly enhance the material turbulence and mass transfer and heat transfer in the countercurrent hydrogenation process, solve the problems of uneven material distribution, local hot spots, catalyst coking, etc. in large countercurrent hydrogenation reactors, and effectively avoids the problem that conventional catalyst particles are easily damaged by collision under gas-liquid countercurrent conditions and cannot operate for a long period of time, thereby improving the overall efficiency of the countercurrent hydrogenation reaction process and extending the operation period of the device.

[0053] Although conventional fixed-bed countercurrent hydrogenation has more advantages and broader application prospects than cocurrent hydrogenation, there are still many problems in its actual application process, such as: the gas phase in the countercurrent hydrogenation process is upward, which makes the catalyst particles in a micro-suspended state prone to collision and breakage, and the inevitable product dust, on the one hand, blocks the catalyst bed, causing the local pressure drop to increase until it cannot operate, and on the other hand, causes serious problems such as material deviation and short circuit, which greatly reduces the efficiency of the hydrogenation reaction; in addition, hydrogenation reactions are all exothermic reactions, and most of the heat release is large, especially when the hydrogenation reaction rate is fast, a large amount of heat release will inevitably occur at the same time. For the hydrogenation process of conventional particle catalysts, the reaction heat is easy to accumulate and more local hot spots will appear, which brings more adverse effects. On the one hand, the catalyst surface is coked and deactivated, thereby reducing the service life of the catalyst; on the other hand, it leads to further intensification of side reactions, thereby affecting the hydrogenation reaction effect, product quality and even the energy consumption of the device.

[0054] In order to solve the above problems, the present invention designs a combined catalyst bed with a special structure, and applies pulsed hydrogen to the combined catalyst bed, that is, through the coupling of the combined catalyst bed and the countercurrent hydrogenation reaction process, the material turbulence and mass transfer and heat transfer enhancement effects are achieved, and the problems of uneven material distribution, local hot spots, catalyst coking, etc. in large hydrogenation reactors are solved, thereby greatly improving the reaction efficiency of the fixed bed gas-liquid countercurrent hydrogenation reaction process, extending the service life of the catalyst and the overall operation cycle of the device.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] 1) A special combined catalyst bed structure is set in the hydrogenation reaction zone, and each combined catalyst bed includes a fixed layer, a sandwich layer, and a support layer, wherein the fixed layer and the support layer are filled with modular catalyst units, and the sandwich layer is filled with catalyst packages. Compared with conventional catalyst beds, this special combined catalyst bed structure can not only ensure that the particle catalyst in the countercurrent reactor can only perform appropriate migration movement in a limited space such as the catalyst package, thereby avoiding serious collision and crushing of the catalyst, but also can respectively load modular catalyst units (catalyst unit modules) with different porosities through the fixed layer and the support layer to ensure uniform material distribution and mass and heat transfer, thereby effectively solving problems such as uneven reaction local hot spots and easy coking of catalyst particles.

[0057] 2) In the hydrogenation reaction device using a combined catalyst bed of the present invention, along the flow direction of the liquid reaction raw materials, from the 1st layer (uppermost layer) to the nth layer (lowermost layer, n is equal to the total number of layers of the combined catalyst bed), the volume or filling height of the catalyst package (catalyst particles) loaded in the sandwich layer gradually decreases, while the filling amount (volume) or filling height of the modular catalyst unit loaded in the fixed layer and the supporting layer gradually increases. This is mainly because as the hydrogenation reaction proceeds, the accumulation of reaction heat becomes larger and larger, resulting in a gradually increasing tendency for the catalyst particles to coke, and it is very important to improve material circulation and heat diffusion. The design method of the combined catalyst bed of the 1st layer to the nth layer of the present invention can not only ensure a high hydrogenation reaction efficiency, but also maintain good mass transfer and heat transfer capabilities.

[0058] 3) The combined catalyst bed hydrogenation reaction device of the present invention introduces a pulse of hydrogen between each section of the combined catalyst bed, and the amount of hydrogen per pulse gradually increases along the direction of the raw material hydrogenation reaction. This arrangement, on the one hand, enables the catalyst particles to reach a micro-suspension state through the instantaneous impact of the pulsed hydrogen, and quickly removes the scale and coking precursors between the catalyst particles, thereby preventing the coking precursors from further developing into coking materials that are difficult to remove, and extending the service life of the catalyst; on the other hand, the introduction of the pulsed hydrogen can also cause the catalyst particles to move within the limited catalyst package, constantly updating and exposing the catalyst surface, maximizing the catalytic effect of the catalyst particles, and ensuring the efficient conduct of the hydrogenation reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 The present invention is a schematic structural diagram of a hydrogenation reaction device using a combined catalyst bed. DETAILED DESCRIPTION

[0060] The present invention will be further described below in conjunction with the accompanying drawings and specific examples. It should be understood that these examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention. The operating methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturer.

[0061] See also Figure 1A hydrogenation reaction device 7 using a combined catalyst bed includes a gas deliquidation zone 10, a hydrogenation reaction zone 11 and a liquid degassing zone 12 which are sequentially connected from top to bottom. The hydrogenation reaction zone 11 includes a plurality of combined catalyst beds 15 distributed longitudinally. The combined catalyst bed 15 includes an upper fixed layer 16, a middle sandwich layer 17 and a lower support layer 18. The lower parts of the fixed layer 16, the sandwich layer 17 and the support layer 18 are all provided with a support grid 19 through which materials can flow freely. The fixed layer 16 and the support layer 18 are both composed of a number of modular catalyst units 20 arranged in a regular manner, and the sandwich layer 17 is formed by stacking a number of catalyst packages 2. The catalyst package 2 includes a catalyst external flexible isolation wire mesh 5 and catalyst particles 6 (conventional catalyst). The catalyst external flexible isolation wire mesh 5 is mainly used to prevent the catalyst particles 6 from running away and to allow the catalyst particles 6 to move in a limited space.

[0062] A liquid raw material feed port 1 is provided between the gas deliquification zone 10 and the hydrogenation reaction zone 11. The liquid raw material feed port 1 is connected to a liquid distributor 13. The liquid distributor 13 is provided at the upper position of the uppermost combined catalyst bed layer, and is used to evenly distribute the liquid feed on the surface of the catalyst bed layer. Liquid material distributors are also provided at the upper part of the remaining combined catalyst beds, and are used to evenly distribute the liquid material from above. The liquid material flowing downward is connected to the liquid material distributor.

[0063] A main hydrogen feed port 3 is provided between the hydrogenation reaction zone 11 and the liquid degassing zone 12, and the main hydrogen feed port 3 is connected to a hydrogen distributor 14, which is provided at the lower part of the lowest combined catalyst bed layer to achieve uniform distribution of hydrogen feed. A gas material distributor is also provided at the lower part of the remaining combined catalyst beds to uniformly distribute the gas materials from below. The gas materials such as hydrogen flowing upward are connected to the gas material distributor.

[0064] A pulse hydrogen feed port 4 is provided between each layer of the combined catalyst bed. The pulse hydrogen introduced can improve turbulent mass transfer, uniform reaction heat, and rapid descaling and decoking, so that the catalyst surface is quickly renewed, the service life of the catalyst is extended, and the hydrogenation reaction is ensured to be carried out efficiently. The pulse hydrogen feed port 4 can be connected to the gas material distributor of the upper combined catalyst bed adjacent thereto. The hydrogen and other gaseous materials from the combined catalyst bed of the lower layer adjacent to the pulse hydrogen feed port rise together with the hydrogen introduced from the pulse hydrogen feed port, and then are connected through the gas material distributor to enter the combined catalyst bed of the upper layer adjacent to the pulse hydrogen feed port.

[0065] A residual gas outlet 8 is provided at the top of the gas deliquidation zone 10. A liquid reaction product outlet 9 is provided at the bottom of the liquid degassing zone 12. The diameters of the gas deliquidation zone 10, the hydrogenation reaction zone 11 and the liquid degassing zone 12 are the same. Along the flow direction of the hydrogen, the amount of pulsed hydrogen introduced through the pulsed hydrogen feed port decreases successively. Along the flow direction of the liquid, the height or volume of the catalyst package 2 filled in the sandwich layer 17 in the combined catalyst bed gradually decreases. The modular catalyst unit 20 is provided with an array-arranged mutually through hole structure, and the through hole sizes on its surface are independently 1 mm×1 mm to 10 mm×10 mm, preferably independently 3 mm×3 mm to 8 mm×8 mm.

[0066] For any combined catalyst bed, the void ratio of the catalyst loaded in the fixed layer 16 is smaller than the void ratio of the catalyst loaded in the support layer 18 .

[0067] A hydrogenation method, using the above Figure 1 The hydrogenation reaction device 7 using a combined catalyst bed shown comprises:

[0068] The liquid raw material and the main hydrogen feed are introduced into the upper and lower parts of the hydrogenation reaction device 7 using a combined catalyst bed through the liquid raw material feed port 1 and the main hydrogen feed port 3 respectively, and the pulse hydrogen is introduced into the space between each combined catalyst bed of the hydrogenation reaction device through the pulse hydrogen feed port 4; the liquid raw material and the main hydrogen feed undergo a countercurrent hydrogenation reaction in the combined catalyst bed loaded in the hydrogenation reactor 7, and during the reaction, pulse hydrogen is intermittently introduced from the position between each combined catalyst bed according to the reaction time program; the liquid material after the hydrogenation reaction is completed enters the liquid degassing zone 12 for degassing, and leaves the bottom of the hydrogenation reaction device as a liquid reaction product 9; the gaseous material after the hydrogenation reaction is completed enters the gas deliquidation zone 10 for deliquidation, and leaves the top of the hydrogenation reaction device as the residual gas 8 of the hydrogenation reaction.

[0069] The hydrogenation reaction device using the combined catalyst bed and the hydrogenation method thereof are respectively applied to maleic anhydride hydrogenation and biomass sugar (glucose) solution hydrogenation processes.

[0070] The properties of maleic anhydride raw material and γ-butyrolactone solvent are shown in Tables 1 and 2, and the properties of maleic anhydride hydrogenation catalyst are shown in Table 3; the properties of biomass sugar (glucose) hydrogenation raw material are shown in Table 4, and the properties of biomass sugar (glucose) solution hydrogenation catalyst are shown in Table 5. All the above raw materials are commercially available, and all hydrogenation catalysts are homemade.

[0071] Table 1 Maleic anhydride raw material properties

[0072]

[0073] Table 2 Properties of γ-butyrolactone raw materials (solvents)

[0074]

[0075] Table 3 Properties of Maleic Anhydride Hydrogenation Catalyst

[0076]

[0077] Table 4 Biomass sugar (glucose) solution raw materials

[0078] project index Characteristics Colorless transparent liquid Concentration, mol / L 1.5

[0079] Table 5 Biomass sugar (glucose) solution hydrogenation catalyst properties

[0080]

[0081] Comparative Example 1

[0082] A conventional gas, liquid, and solid three-phase fixed bed countercurrent hydrogenation reactor and hydrogenation method were used. The height-to-diameter ratio of the hydrogenation reactor was 2.5, and two catalyst beds were used. The two beds had the same height and were filled with conventional catalyst particles corresponding to the respective reactions. The device was used to investigate the reaction effects of maleic anhydride hydrogenation and biomass sugar (glucose) hydrogenation under different conditions.

[0083] First, the liquid reaction raw materials are temperature-adjusted to the inlet temperature of the hydrogenation reactor and then enter from the top of the hydrogenation reactor. The hydrogen gas is temperature-adjusted to the inlet temperature of the hydrogenation reactor and then enters from the bottom of the hydrogenation reactor. The two undergo a countercurrent hydrogenation reaction in the catalyst bed and leave after the hydrogenation reaction is completed.

[0084] Note: In the maleic anhydride hydrogenation process, maleic anhydride is the solute and γ-butyrolactone is the solvent. The maleic anhydride concentration in the hydrogenation reaction feed is 10wt%.

[0085] The operating conditions of the hydrogenation reactor are shown in Table 6, and the reaction results are shown in Table 7.

[0086] Comparative Example 2

[0087] A conventional gas, liquid, and solid three-phase fixed bed countercurrent hydrogenation reactor and hydrogenation method were used. The height-to-diameter ratio of the hydrogenation reactor was 2.5, and two catalyst beds were used. The two beds had the same height and were filled with catalyst unit modules corresponding to their respective reactions. The device was used to investigate the reaction effects of maleic anhydride hydrogenation and biomass sugar (glucose) hydrogenation under different conditions.

[0088] First, the liquid reaction raw materials are temperature-adjusted to the inlet temperature of the hydrogenation reactor and then enter from the top of the hydrogenation reactor. The hydrogen gas is temperature-adjusted to the inlet temperature of the hydrogenation reactor and then enters from the bottom of the hydrogenation reactor. The two undergo a countercurrent hydrogenation reaction in the catalyst bed and leave after the hydrogenation reaction is completed.

[0089] Note: In the maleic anhydride hydrogenation process, maleic anhydride is the solute and γ-butyrolactone is the solvent. The maleic anhydride concentration in the hydrogenation reaction feed is 10wt%.

[0090] The operating conditions of the hydrogenation reactor are shown in Table 6, and the reaction results are shown in Table 7.

[0091] Comparative Example 3

[0092] A conventional gas, liquid, solid three-phase fixed bed countercurrent hydrogenation reactor and hydrogenation method were used. The height-to-diameter ratio of the hydrogenation reactor was 2.5. Two catalyst beds were used. The upper bed was made of catalyst particles, and the lower bed was made of catalyst unit modules. The ratio of the bed height of catalyst particles to that of catalyst unit modules was 1:2. The reaction effects of maleic anhydride hydrogenation and biomass sugar (glucose) hydrogenation were investigated under different conditions using this device.

[0093] First, the liquid reaction raw materials are temperature-adjusted to the inlet temperature of the hydrogenation reactor and then enter from the top of the hydrogenation reactor. The hydrogen gas is temperature-adjusted to the inlet temperature of the hydrogenation reactor and then enters from the bottom of the hydrogenation reactor. The two undergo a countercurrent hydrogenation reaction in the catalyst bed and leave after the hydrogenation reaction is completed.

[0094] Note: In the maleic anhydride hydrogenation process, maleic anhydride is the solute and γ-butyrolactone is the solvent. The maleic anhydride concentration in the hydrogenation reaction feed is 10wt%.

[0095] The operating conditions of the hydrogenation reactor are shown in Table 6, and the reaction results are shown in Table 7.

[0096] Example 1

[0097] A hydrogenation reaction device (hydrogenation reactor) and a hydrogenation method using a combined catalyst bed are introduced in the specific embodiment of the present invention.

[0098] The design structure of the hydrogenation reactor is as follows:

[0099] The height-to-diameter ratio of the hydrogenation reactor is 2.5, and a total of two combined catalyst beds are arranged, the upper part is the first combined catalyst bed, and the lower part is the second combined catalyst bed;

[0100] The first layer of combined catalyst bed: fixed layer height 150mm, 1 layer of catalyst unit module, bed void ratio 65%; support layer height 150mm, 1 layer of catalyst unit module, bed void ratio 80%; sandwich layer filled with catalyst height 300mm, 50% of the first layer of combined catalyst bed height, the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

[0101] The second layer of combined catalyst bed: fixed layer height 150mm, 1 layer of catalyst unit module, bed void ratio 65%; support layer height 150mm, 1 layer of catalyst unit module, bed void ratio 80%, the height of the catalyst package filled in the sandwich layer is 260mm, which is 46.4% of the height of the second layer of combined catalyst bed, and the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

[0102] A pulse of hydrogen gas is passed between the first and second combined catalyst beds, with a single injection time of 60 seconds and a time interval of 600 seconds.

[0103] The device was used to investigate the reaction effects of maleic anhydride hydrogenation and biomass sugar (glucose) hydrogenation under different conditions. First, the liquid reaction raw material was temperature-adjusted to the inlet temperature of the hydrogenation reactor and then entered from the top of the hydrogenation reactor. The main reaction hydrogen was temperature-adjusted to the inlet temperature of the hydrogenation reactor and then entered from the bottom of the hydrogenation reactor. The two reacted in a countercurrent hydrogenation reaction in the catalyst bed and left after the hydrogenation reaction was completed. During the hydrogenation reaction, pulsed hydrogen was intermittently introduced between the first and second combined catalyst beds.

[0104] Note: In the maleic anhydride hydrogenation process, maleic anhydride is the solute and γ-butyrolactone is the solvent. The maleic anhydride concentration in the hydrogenation reaction feed is 10wt%.

[0105] The operating conditions of the hydrogenation reaction unit are shown in Table 6, and the reaction results are shown in Table 7.

[0106] Example 2

[0107] A hydrogenation reaction device (hydrogenation reactor) and a hydrogenation method using a combined catalyst bed are introduced in the specific embodiment of the present invention.

[0108] The design structure of the hydrogenation reactor is as follows:

[0109] The height-to-diameter ratio of the hydrogenation reactor is 2.0, and a total of three combined catalyst beds are arranged, the upper part is the first combined catalyst bed, the middle part is the second combined catalyst bed, and the lower part is the third combined catalyst bed;

[0110] The first layer of combined catalyst bed: fixed layer height 150mm, 1 layer of catalyst unit module, bed void ratio 55%; support layer height 150mm, 1 layer of catalyst unit module, bed void ratio 70%; sandwich layer filled with catalyst height 200mm, 40% of the first layer of combined catalyst bed height, the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

[0111] The second layer of combined catalyst bed: fixed layer height 300mm, 2 layers of catalyst unit modules, bed void ratio 55%; support layer height 300mm, 2 layers of catalyst unit modules, bed void ratio 75%, the height of the catalyst package filled in the sandwich layer is 180mm, which is 23% of the height of the second layer of combined catalyst bed, and the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

[0112] The third combined catalyst bed: fixed layer height 450mm, 3 layers of catalyst unit modules, bed void ratio 55%; support layer height 600mm, 4 layers of catalyst unit modules, bed void ratio 80%, the height of the catalyst package filled in the sandwich layer is 155mm, which is 12.8% of the height of the third combined catalyst bed, and the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

[0113] A pulse of hydrogen gas is passed between the first and second combined catalyst beds, with a single injection time of 30 seconds and a time interval of 600 seconds.

[0114] A pulse of hydrogen gas is passed between the second and third combined catalyst beds, with a single injection time of 60 seconds and a time interval of 600 seconds.

[0115] The device was used to investigate the reaction effects of maleic anhydride hydrogenation and biomass sugar (glucose) hydrogenation under different conditions. First, the liquid reaction raw material was temperature-adjusted to the inlet temperature of the hydrogenation reactor and then entered from the top of the hydrogenation reactor. The main reaction hydrogen was temperature-adjusted to the inlet temperature of the hydrogenation reactor and then entered from the bottom of the hydrogenation reactor. The two reacted in a countercurrent hydrogenation reaction in the catalyst bed and left after the hydrogenation reaction was completed. During the hydrogenation reaction, pulsed hydrogen was intermittently introduced between the first and second combined catalyst beds and between the second and third combined catalyst beds.

[0116] Note: In the maleic anhydride hydrogenation process, maleic anhydride is the solute and γ-butyrolactone is the solvent. The maleic anhydride concentration in the hydrogenation reaction feed is 10wt%.

[0117] The operating conditions of the hydrogenation reaction unit are shown in Table 6, and the reaction results are shown in Table 7.

[0118] Example 3

[0119] A hydrogenation reaction device (hydrogenation reactor) and a hydrogenation method using a combined catalyst bed are introduced in the specific embodiment of the present invention.

[0120] The design structure of the hydrogenation reactor is as follows:

[0121] The height-to-diameter ratio of the hydrogenation reactor is 2.0, and a total of 4 combined catalyst beds are arranged, from the 1st layer to the 4th layer from top to bottom;

[0122] The first layer of combined catalyst bed: fixed layer height 150mm, 1 layer of catalyst unit module, bed void ratio 55%; support layer height 150mm, 1 layer of catalyst unit module, bed void ratio 70%; sandwich layer filled with catalyst height 150mm, 33.3% of the first layer of combined catalyst bed height, the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

[0123] The second combined catalyst bed: fixed layer height 300mm, 2 layers of catalyst unit modules, bed void ratio 65%; support layer height 300mm, 2 layers of catalyst unit modules, bed void ratio 80%, the height of the catalyst package filled in the sandwich layer is 130mm, which is 17.8% of the height of the second combined catalyst bed, and the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

[0124] The third combined catalyst bed: fixed layer height 450mm, 3 layers of catalyst unit modules, bed void ratio 65%; support layer height 450mm, 3 layers of catalyst unit modules, bed void ratio 80%, the height of the catalyst package filled in the sandwich layer is 115mm, which is 11.3% of the height of the third combined catalyst bed, and the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

[0125] The 4th combined catalyst bed: fixed layer height 600mm, 1 layer of catalyst unit modules, bed void ratio 75%; support layer height 600mm, 1 layer of catalyst unit modules, bed void ratio 90%, the height of the catalyst package filled in the sandwich layer is 100mm, which is 7.7% of the height of the 4th combined catalyst bed, and the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

[0126] A pulse of hydrogen is passed between the first and second combined catalyst beds, with a single introduction time of 20 s and a time interval of 600 s; a pulse of hydrogen is passed between the second and third combined catalyst beds, with a single introduction time of 40 s and a time interval of 600 s; a pulse of hydrogen is passed between the third and fourth combined catalyst beds, with a single introduction time of 60 s and a time interval of 600 s.

[0127] The device was used to investigate the reaction effects of maleic anhydride hydrogenation and biomass sugar (glucose) hydrogenation under different conditions. First, the liquid reaction raw material was temperature-adjusted to the inlet temperature of the hydrogenation reactor and then entered from the top of the hydrogenation reactor. The main reaction hydrogen was temperature-adjusted to the inlet temperature of the hydrogenation reactor and then entered from the bottom of the hydrogenation reactor. The two reacted in a countercurrent hydrogenation reaction in the catalyst bed and left after the hydrogenation reaction was completed. During the hydrogenation reaction, pulsed hydrogen was intermittently introduced between the 1st and 2nd layers and the 2nd and 3rd layers, and between the 3rd and 4th combined catalyst beds.

[0128] Note: In the maleic anhydride hydrogenation process, maleic anhydride is the solute and γ-butyrolactone is the solvent. The maleic anhydride concentration in the hydrogenation reaction feed is 10wt%.

[0129] The operating conditions of the hydrogenation reaction unit are shown in Table 6, and the reaction results are shown in Table 7.

[0130] Table 6 Operating conditions of hydrogenation reactor (device)

[0131]

[0132] Table 7 Hydrogenation reaction results

[0133]

[0134] Note 1: Average radial temperature difference refers to the average radial temperature difference of each bed from top to bottom in the hydrogenation reaction unit; Note 2: The coking amount of conventional catalyst (g / 100g): refers to the amount of coke formed on the catalyst surface due to the deposition of reactants during the use of the catalyst. Catalyst coking will reduce its activity and selectivity, affect the reaction efficiency and product yield, and is an important indicator for measuring catalyst performance and life. That is, the greater the amount of catalyst coking, the worse the reaction effect and the shorter the life. Here, the grams of coke per 100g catalyst surface are measured by thermogravimetric analysis (TGA) after 8h of hydrogenation reaction.

[0135] It can be seen from the effects of the embodiments of the present invention and the comparative examples that the hydrogenation reaction device and hydrogenation method using a combined catalyst bed of the present invention, by designing a combined catalyst bed with a special structure and applying pulsed hydrogen to the combined catalyst bed, can greatly improve the hydrogenation reaction rate, and the temperature distribution of each combined catalyst bed in the hydrogenation reactor is very uniform, and the radial temperature difference is ≤3°C, which solves the problems of uneven reaction, local hot spots, catalyst coking, etc. in large countercurrent hydrogenation reactors, thereby greatly improving the reaction efficiency of the fixed bed gas-liquid countercurrent hydrogenation reaction process, and extending the service life of the catalyst and the overall operation cycle of the device.

[0136] In addition, it should be understood that after reading the above description of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. A hydrogenation reaction device using a combined catalyst bed, characterized in that: It comprises a gas deliquidation zone, a hydrogenation reaction zone and a liquid degassing zone which are sequentially connected from top to bottom, a plurality of combined catalyst beds distributed vertically are arranged in the hydrogenation reaction zone, a liquid raw material feed port is arranged between the gas deliquidation zone and the uppermost combined catalyst bed, and a hydrogen feed port is arranged between the liquid degassing zone and the lowermost combined catalyst bed; The combined catalyst bed includes an upper fixed layer, a middle sandwich layer and a lower support layer. The fixed layer and the support layer are filled with modular catalyst units. The sandwich layer contains one or more catalyst packages. The catalyst packages contain catalyst particles and a wrapping assembly for wrapping the catalyst particles. The wrapping assembly has holes that allow materials to pass through but prevent catalyst particles from passing through.

2. The hydrogenation reaction device according to claim 1, characterized in that: The number of combined catalyst beds in the hydrogenation reaction zone is 2 to 6; A pulse hydrogen feed port is provided between adjacent combined catalyst beds; A liquid material distributor is arranged on the upper part of the combined catalyst bed to evenly distribute the liquid material from above; A gas material distributor is arranged at the lower part of the combined catalyst bed layer to evenly distribute the gas material from below; The pulse hydrogen feed port is communicated with the gas material distributor of the adjacent upper combined catalyst bed.

3. The hydrogenation reaction device according to claim 1, characterized in that: The height of the catalyst package in each sandwich layer is independently 50 to 1500 mm, preferably independently 50 to 1000 mm; For any two adjacent combined catalyst beds, the volume of catalyst particles loaded in the sandwich layer of the lower combined catalyst bed is independently less than or equal to the volume of catalyst particles loaded in the sandwich layer of the upper combined catalyst bed; The heights of the modular catalyst units loaded in the fixed layer and the supporting layer are independently 50 to 1500 mm, preferably independently 100 to 900 mm; For any two adjacent combined catalyst beds, the volume of catalyst loaded in the fixed layer of the lower combined catalyst bed is independently greater than or equal to the volume of catalyst loaded in the fixed layer of the upper combined catalyst bed; For any two adjacent combined catalyst beds, the volume of catalyst loaded in the support layer in the lower combined catalyst bed is independently greater than or equal to the volume of catalyst loaded in the support layer in the upper combined catalyst bed; For any combined catalyst bed, the void fraction of the catalyst loaded in the fixed layer is independently less than or equal to the void fraction of the catalyst loaded in the supporting layer.

4. The hydrogenation reaction device according to claim 3, characterized in that: For any two adjacent combined catalyst beds, the volume of the catalyst particles loaded in the sandwich layer of the lower combined catalyst bed is independently 80% to 99% of the volume of the catalyst particles loaded in the sandwich layer of the upper combined catalyst bed. Furthermore, the volume of the catalyst particles loaded in the sandwich layer of the lower combined catalyst bed is independently 85% to 97% of the volume of the catalyst particles loaded in the sandwich layer of the upper combined catalyst bed. For any two adjacent combined catalyst beds, the volume of the catalyst loaded in the fixed layer of the lower combined catalyst bed is independently 100% to 800% of the volume of the catalyst loaded in the fixed layer of the upper combined catalyst bed; further, the volume of the catalyst loaded in the fixed layer of the lower combined catalyst bed is independently 100% to 500% of the volume of the catalyst loaded in the fixed layer of the upper combined catalyst bed; For any two adjacent combined catalyst beds, the volume of the catalyst loaded in the support layer in the lower combined catalyst bed is independently 100% to 800% of the volume of the catalyst loaded in the support layer in the upper combined catalyst bed. Furthermore, the volume of the catalyst loaded in the support layer in the lower combined catalyst bed is independently 100% to 500% of the volume of the catalyst loaded in the support layer in the upper combined catalyst bed. For any combined catalyst bed, the void ratio of the catalyst loaded in the fixed layer is independently 50% to 75%, preferably independently 55% to 75%, and the void ratio of the catalyst loaded in the supporting layer is independently 60% to 95%, preferably independently 70% to 90%.

5. The hydrogenation reaction device according to claim 1, characterized in that: The height-to-diameter ratio of the hydrogenation reaction device is 0.5 to 10:1, preferably 1 to 5:

1.

6. The hydrogenation reaction device according to claim 1, characterized in that: The lower parts of the fixed layer, sandwich layer and supporting layer are independently provided with grids to support and fix the catalyst loaded in the corresponding layers. The two sides of the grids can be used for material flow, so that the combined catalyst bed becomes a cage structure with internal support. The fixed layer and the support layer are independently loaded with 1 to 20 layers, preferably 1 to 10 layers, of modular catalyst units; The wrapping component is a flexible wire mesh; The hole size of the package component is 10 to 100 mesh; The radial dimension of the cross section of the catalyst particles is 0.5 to 10 mm, preferably 1 to 6 mm.

7. Use of the hydrogenation reaction device according to any one of claims 1 to 6 in hydrogenation reactions.

8. A hydrogenation method, characterized in that: A hydrogenation reaction device as described in any one of claims 1 to 6 is used.

9. The hydrogenation method according to claim 8, characterized in that include: The liquid raw material enters the hydrogenation reaction device through the liquid raw material feed port, and the hydrogen enters the hydrogenation reaction device through the hydrogen feed port. The liquid raw material and the hydrogen undergo a countercurrent hydrogenation reaction in the combined catalyst bed. The liquid material after the hydrogenation reaction enters the liquid degassing zone for degassing, and the gas material after the hydrogenation reaction enters the gas deliquidation zone for deliquidation.

10. The hydrogenation method according to claim 8 or 9, characterized in that: The hydrogen gas from the hydrogen feed port is continuously introduced; Pulse hydrogen is intermittently introduced between adjacent combined catalyst beds; The duration of a single pulse of hydrogen between adjacent combined catalyst beds is independently 10 to 120 seconds, and the time interval between two adjacent pulses of hydrogen is independently 300 to 1200 seconds. The ratio of the single pulse hydrogen flow rate to the liquid raw material feed rate between each adjacent combined catalyst bed is independently 1 to 100 Nm 3 / h:1m 3 / h, preferably 5 to 50 Nm 3 / h:1m 3 / h; The single pulse hydrogen injection amount gradually increases along the flow direction of the liquid material, with an increasing rate of 1% to 80%, preferably 10% to 50%; The fixed layer and the supporting layer are loaded with modular catalyst units with a space velocity of 2 to 30 h -1 ; The space velocity of the catalyst particles filled in the sandwich layer is 0.1~10h -1 , preferably 0.5 to 4 hours -1 ; The space velocity of the modular catalyst units loaded in the fixed layer and the supporting layer is not less than the space velocity of the catalyst particles loaded in the sandwich layer; The feed ratio of total hydrogen to liquid raw material is 1~1500Nm 3 / h:1m 3 / h, preferably 5-600Nm 3 / h:1m 3 / h; The hydrogenation reaction temperature is from room temperature to 500°C; The hydrogenation reaction pressure is 0.1~20MpaG.

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