A hydrogenation reaction device and hydrogenation method using a combined catalyst bed

Abstract

The present invention discloses a hydrogenation reaction device and hydrogenation method using a combined catalyst bed. The hydrogenation reaction device includes a gas deliquidation zone, a hydrogenation reaction zone, and a liquid degassing zone, which are sequentially connected from top to bottom. The hydrogenation reaction zone is provided with multiple combined catalyst beds distributed longitudinally. A liquid raw material feed port is provided between the gas deliquidation zone and the uppermost combined catalyst bed, and a hydrogen feed port is provided 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 loaded 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 material to pass through but prevent the catalyst particles from passing through.

Description

Technical Field

[0001] The present 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 involves the catalytic action of a catalyst to hydrogenate raw materials and hydrogen under specific reaction conditions (temperature and pressure), thereby improving oil quality. Hydrogenation technology is widely used in various fields, including petroleum refining, chemical engineering, biochemical engineering, food and medicine.

[0003] The most widely used fixed-bed hydrogenation technology in industry is the gas-liquid co-current trickle bed hydrogenation process, in which the gas and liquid phases flow co-currently downward through a fixed catalyst bed, completing the hydrogenation reaction. Generally speaking, the fixed-bed gas-liquid co-current hydrogenation process is a trickle bed hydrogenation process, in which the liquid flows downward as a liquid film over the solid catalyst. Under these flow conditions, especially in large fixed-bed gas-liquid co-current units, significant problems exist: The low-speed, low-turbulence state of the liquid leads to uneven distribution, channeling, and short-circuiting, which prevents complete catalyst wetting, reducing catalyst utilization and reaction conversion. It also easily leads to uneven radial temperature distribution within the reactor, forming local hot spots, accelerating catalyst deactivation, and directly affecting the efficiency of the catalytic hydrogenation reaction. To address these issues, fixed-bed gas-liquid countercurrent hydrogenation, with its advantages of improving material turbulence, mass and heat transfer efficiency, and increasing catalyst utilization, has become a research hotspot and an important development direction for fixed-bed hydrogenation reaction processes. However, the conventional fixed-bed countercurrent hydrogenation process is based on the gas phase passing through the catalyst bed in an upflowing high-speed manner, which is prone to catalyst particle floating and breakage, local liquid retention or low turbulence or uneven reaction, resulting in local hot spots and catalyst coking. Therefore, there is an urgent need for technological progress 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 aromatics saturation. Under diesel fraction hydrotreating conditions, hydrogen and diesel feedstock are passed through a catalyst bed in a countercurrent manner. The reactor is divided into at least two reaction zones, each consisting 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 provided at the junction of at least one reaction zone, and a liquid accumulation outlet pipeline is provided at the bottom or side of the liquid accumulation zone to direct liquid from the liquid accumulation zone to the lower reaction zone of the reactor as a cooling stream. This patent, on the one hand, varies the gas velocity by varying the reactor diameter to prevent flooding and maintain stable operation within the reactor. On the other hand, a cooling stream is introduced to remove heat from the bed. However, problems such as floating and breakage of catalyst particles, local hot spots, and catalyst coking still exist.

[0005] Patent application CN116948701A proposes a bio-oil hydrogenation process. Hydrogen enters the gas-liquid contact zone, partially flows upward through the gas-liquid contact zone, the gas-liquid countercurrent zone, the gas-liquid separation zone, and the gas-phase reaction zone. Part of the hydrogen is then heat-exchanged with the liquid-phase material flowing out of the gas-liquid countercurrent zone and mixed with the liquid-phase material flowing into the liquid-phase reaction zone. The bio-oil feedstock enters the gas-liquid separation zone, partially converts to the gas phase, and enters the gas-phase reaction zone along with the gas-phase material from the gas-liquid countercurrent zone for hydrogenation. The gas-phase reaction product flows out of the top of the reactor. The liquid-phase feedstock in the gas-liquid separation zone enters the gas-liquid countercurrent zone, where it reacts with the hydrogen in a countercurrent fashion and enters the gas-liquid contact zone. The liquid-phase material then flows downward into the gas-liquid contact zone for liquid-phase hydrogenation. The liquid-phase reaction product flows out of the bottom of the reactor. This patent utilizes zoned liquid flow patterns to control reaction temperature rise and promptly remove moisture generated during bio-oil hydrogenation. However, it still fails to address issues such as catalyst particle floating and breakage, local hot spots, and catalyst coking, which impact hydrogenation efficiency and long-term operation.

[0006] Therefore, for the fixed-bed gas-liquid countercurrent hydrogenation process, the development of new countercurrent hydrogenation processes, catalyst forms and reactor structures 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 shortcomings 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 deliquescence zone, a hydrogenation reaction zone, and a liquid degassing zone connected in sequence from top to bottom, wherein a plurality of combined catalyst beds are arranged longitudinally in the hydrogenation reaction zone, a liquid raw material feed port is provided between the gas deliquescence zone and the uppermost combined catalyst bed, and a hydrogen feed port is provided 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 feedstock inlet is connected to the top of the uppermost modular catalyst bed. The hydrogen feed inlet is connected to the bottom of the lowermost modular catalyst bed. The structures of the modular catalyst beds can be entirely identical, partially identical, or entirely different, preferably different. The diameters of the gas degassing zone, hydrogenation reaction zone, and liquid degassing zone can be identical or different, preferably identical.

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

[0012] The shapes of the modular catalyst units loaded in the fixed layer and the supporting layer can be any one or more combinations of cylindrical, rectangular, square, rhombus, polygonal, etc., preferably rectangular. The shapes of the modular catalyst units loaded in the fixed layer and the supporting layer can be the same or different. The modular catalyst units loaded in 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 1mm×1mm to 10mm×10mm, preferably 3mm×3mm to 8mm×8mm, such as 6mm×6mm, etc. The opening size of the modular catalyst units loaded in 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, a liquid reaction product outlet may be provided at the bottom of the liquid degassing zone of the hydrogenation reaction device.

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

[0016] In some embodiments, a liquid material distributor may be provided on the upper portion of the combined catalyst bed for uniformly distributing the liquid material from above, and the liquid material flowing downward is in communication with the liquid material distributor.

[0017] In some embodiments, a gas material distributor may be provided below the combined catalyst bed to uniformly distribute the gas material from below. The upwardly flowing gas material such as hydrogen is connected to the gas material distributor.

[0018] In some preferred embodiments, a pulse hydrogen feed port is provided between adjacent modular catalyst beds in the hydrogenation reaction apparatus. 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 modular catalyst bed adjacent thereto. Hydrogen and other gaseous materials from the modular catalyst bed below adjacent to the pulse hydrogen feed port rise together with the hydrogen introduced from the pulse hydrogen feed port, merge, and then be connected through the gas material distributor to enter the modular catalyst bed above 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 tube type, plate type, bubble type, nozzle type, jet type, trough type, disc type, metal membrane tube, ceramic membrane tube, and microchannel.

[0020] In some embodiments, the height of the catalyst package in each sandwich layer of the hydrogenation reaction device 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 apparatus, for any two adjacent combined catalyst beds, the volume of catalyst particles loaded in the sandwich layer of the lower combined catalyst bed (volume of the catalyst package) can be independently less than or equal to the volume of catalyst particles loaded in the sandwich layer of the upper combined catalyst bed. Furthermore, for any two adjacent combined catalyst beds, the volume of catalyst particles loaded in the sandwich layer of the lower combined catalyst bed can be independently 80% to 99% of the volume of catalyst particles loaded in the sandwich layer of the upper combined catalyst bed. Furthermore, the volume of catalyst particles loaded in the sandwich layer of the lower combined catalyst bed can be independently 85% to 97% (e.g., 90%) of the volume of catalyst particles loaded in the sandwich layer of 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 heights of the modular catalyst units loaded in the fixed layer and the supporting layer of the hydrogenation reaction apparatus can each independently 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, the hydrogenation reaction device, for any two adjacent combined catalyst beds, the volume of catalyst loaded in the fixed layer of the lower combined catalyst bed can be independently greater than or equal to the volume of catalyst loaded in the fixed layer of the upper combined catalyst bed. Further, for any two adjacent combined catalyst beds, the volume of catalyst loaded in the fixed layer of the lower combined catalyst bed can be independently 100% to 800% of the volume of catalyst loaded in the fixed layer of the upper combined catalyst bed. Further, the volume of catalyst loaded in the fixed layer of 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 of 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 apparatus, for any two adjacent combined catalyst beds, the volume of catalyst loaded in the support layer of the lower combined catalyst bed can be independently greater than or equal to the volume of catalyst loaded in the support layer of the upper combined catalyst bed. Further, for any two adjacent combined catalyst beds, the volume of catalyst loaded in the support layer of the lower combined catalyst bed can be independently 100% to 800% of the volume of catalyst loaded in the support layer of the upper combined catalyst bed. Furthermore, the volume of catalyst loaded in the support layer of 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 of 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 modular catalyst bed in the hydrogenation reaction apparatus, the porosity of the catalyst loaded in the fixed layer can be independently less than or equal to (preferably less than) the porosity of the catalyst loaded in the support layer. This is primarily due to the fact that the fixed layer, located above the catalyst bed, has a slightly lower porosity that facilitates uniform material distribution and prevents accumulation of material in the catalyst bed, while the support layer, located below the catalyst bed, has a slightly higher porosity that facilitates material flow and heat diffusion, thereby preventing reaction heat accumulation and localized hot spots.

[0026] In some embodiments, for any combined catalyst bed of the hydrogenation reaction device, 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 set at the bottom of the fixed layer, sandwich layer and support layer to support and fix the catalyst loaded in the corresponding layer. The two sides of the grid can be used for material circulation, making the combined catalyst bed a cage structure with internal support.

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

[0030] In the hydrogenation reaction apparatus, the catalyst packages can be stacked. The wrapping assembly can be a flexible mesh. Each catalyst package comprises catalyst particles and a flexible mesh wrapping the catalyst particles. The flexible mesh acts as an isolation device, preventing the catalyst particles from floating or moving around, which could cause breakage. Furthermore, the flexible mesh can be appropriately squeezed and deformed by the catalyst particles.

[0031] The hole size of the wrapping component of the hydrogenation reaction device 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 one or more combinations of sphere, toothed sphere, sheet, strip, clover, four-leaf clover, hollow ring, and multi-hole column.

[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 sieve, etc.

[0035] The hydrogenation reaction unit described above can be equipped 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, and an aromatics hydrogenation saturation catalyst; the catalyst active component includes but is not limited to one or more combinations of precious metals, Co, Mo, Ni, W, Mg, Zn, and rare earth elements; 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 centers on the surface, and the number of active centers per unit surface area.

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

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

[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. After the hydrogenation reaction, the liquid material enters the liquid degassing zone for degassing, and the gaseous material enters the gas deliquid zone for deliquescence.

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

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

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

[0044] In the hydrogenation method, the ratio of the single pulse hydrogen flow rate to the liquid raw material feed rate between adjacent combined catalyst beds 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. Furthermore, 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 fixed layer and the supporting layer are loaded with modular catalyst units with a space velocity of 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, the total hydrogen (the sum of the main reaction hydrogen feed and each pulse hydrogen) and the liquid reaction raw material (m 3The ratio of total hydrogen to liquid raw material can be adjusted according to the requirements of various hydrogenation reactions, 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 to 600 Nm 3 / h:1m 3 / h.

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

[0051] The hydrogenation reaction device and hydrogenation method using a combined catalyst bed of the present invention are applicable to various raw materials capable of undergoing hydrogenation reactions with hydrogen in the fields of petrochemical industry, medicine, food, etc., and can be crude oil and secondary processed oils 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.; and can also be various raw materials containing carbon-carbon double bonds, carbon-carbon triple bonds and organic functional groups that can undergo hydrogenation reactions in the fields of chemical industry, 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, and controls the intermittent action of pulsed hydrogen on the combined catalyst bed. This can greatly enhance the material turbulence and mass and heat transfer in the countercurrent hydrogenation process, and solve the problems of uneven material distribution, local hot spots, catalyst coking, etc. in large countercurrent hydrogenation reactors. At the same time, it 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 operating cycle of the device.

[0053] Although conventional fixed-bed countercurrent hydrogenation has more advantages and broad application prospects compared with cocurrent hydrogenation, there are still many problems in its actual application process. For example, 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. 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 the heat release is large. Especially when the hydrogenation reaction rate is fast, a large 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 will coke and become inactivated, thereby reducing the service life of the catalyst; on the other hand, it will further aggravate the 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, by coupling the combined catalyst bed with the countercurrent hydrogenation reaction process, material turbulence and mass and heat transfer enhancement are achieved, thereby solving the problems of uneven material distribution, local hot spots, catalyst coking, etc. in large hydrogenation reactors, 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 up in the hydrogenation reaction zone. Each combined catalyst bed layer includes a fixed layer, a sandwich layer, and a support layer. 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 ensure that the particle catalyst in the countercurrent reactor can only move appropriately within the limited space of the catalyst package, thereby avoiding serious collision and breakage of the catalyst. It can also ensure that modular catalyst units (catalyst unit modules) with different porosities are loaded in the fixed layer and the support layer respectively, ensuring 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) 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 (top layer) to the nth layer (bottom 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) filled in the sandwich layer gradually decreases, while the filling amount (volume) or filling height of the modular catalyst units filled 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 improving material circulation and heat diffusion becomes very important. The design of the combined catalyst bed of the 1st layer to the nth layer of the present invention can not only ensure a higher hydrogenation reaction efficiency, but also maintain good mass transfer and heat transfer capabilities.

[0058] 3) The present invention adopts a combined catalyst bed hydrogenation reaction device, by introducing a pulse of hydrogen between each section of the combined catalyst bed, and along the direction of the raw material hydrogenation reaction, the amount of each pulse of hydrogen gradually increases. This setting is, on the one hand, through the instantaneous impact of the pulsed hydrogen, the catalyst particles are brought into a micro-suspension state, and the scale and coking precursors between the catalyst particles are quickly removed, thereby avoiding the coking precursor from further developing into a coke that is difficult to remove, and extending the service life of the catalyst; on the other hand, the introduction of the pulsed hydrogen can also make the catalyst particles move in a limited catalyst package, constantly updating the exposed 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 figure is a schematic structural diagram of a hydrogenation reaction device using a combined catalyst bed according to the present invention. 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 intended to illustrate the present invention and are not intended to limit the scope of the invention. The operating methods in the following examples where no specific conditions are specified are generally performed under conventional conditions or as 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 connected in sequence from top to bottom. The hydrogenation reaction zone 11 includes a multi-layer combined catalyst bed 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 an orderly manner. The sandwich layer 17 is composed of a number of catalyst packages 2 stacked together. 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 feed inlet 1 is located between the degassing zone 10 and the hydrogenation reaction zone 11. This inlet communicates with a liquid distributor 13, located above the topmost modular catalyst bed. Liquid distributors are also located above the remaining modular catalyst beds to evenly distribute the liquid feed from above. Downward-flowing liquid feed communicates with the liquid distributors.

[0063] A main hydrogen feed port 3 is located between the hydrogenation reaction zone 11 and the liquid degassing zone 12. This port is connected to a hydrogen distributor 14, located below the lowest modular catalyst bed, to ensure uniform distribution of the hydrogen feed. Gas material distributors are also located below the remaining modular catalyst beds to evenly distribute the gas materials flowing from below. Upward-flowing hydrogen and other gas materials are connected to the gas material distributors.

[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 in 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 in 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 includes:

[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 the combined catalyst beds 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 the combined catalyst beds according to the reaction time program; the liquid material after the hydrogenation reaction is completed enters the liquid degassing zone 12 for degassing, and then leaves the bottom of the hydrogenation reaction device as a liquid reaction product 9; the gas material after the hydrogenation reaction is completed enters the gas deliquidation zone 10 for deliquidation, and then 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 the maleic anhydride feedstock and γ-butyrolactone solvent are shown in Tables 1 and 2, and the properties of the maleic anhydride hydrogenation catalyst are shown in Table 3. The properties of the biomass sugar (glucose) hydrogenation feedstock are shown in Table 4, and the properties of the biomass sugar (glucose) solution hydrogenation catalyst are shown in Table 5. All of the above raw materials were commercially available, and all hydrogenation catalysts were 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 Traits 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 three-phase fixed-bed countercurrent hydrogenation reactor with a gas-liquid-solid ratio and hydrogenation method was used. The reactor had a height-to-diameter ratio of 2.5 and two catalyst beds of equal height, each filled with conventional catalyst particles corresponding to the respective reaction. This apparatus was used to investigate the hydrogenation of maleic anhydride and biomass sugar (glucose) under different conditions.

[0083] First, the liquid reaction raw materials are temperature-controlled to the hydrogenation reactor inlet temperature and then enter from the top of the hydrogenation reactor. The hydrogen gas is temperature-controlled to the hydrogenation reactor inlet temperature 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 10 wt%.

[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 three-phase fixed-bed countercurrent hydrogenation reactor with a gas-liquid-solid ratio and hydrogenation method was used. The reactor had a height-to-diameter ratio of 2.5 and two catalyst beds of equal height, each filled with catalyst modules corresponding to the respective reaction. This device was used to investigate the hydrogenation of maleic anhydride and biomass sugar (glucose) under different conditions.

[0088] First, the liquid reaction raw materials are temperature-controlled to the hydrogenation reactor inlet temperature and then enter from the top of the hydrogenation reactor. The hydrogen gas is temperature-controlled to the hydrogenation reactor inlet temperature 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 10 wt%.

[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 reactor had a height-to-diameter ratio of 2.5 and employed two catalyst beds: an upper bed of catalyst granules and a lower bed of catalyst modules. The bed height ratio of catalyst granules to catalyst modules was 1:2. The hydrogenation of maleic anhydride and biomass sugar (glucose) was investigated using this device under different conditions.

[0093] First, the liquid reaction raw materials are temperature-controlled to the hydrogenation reactor inlet temperature and then enter from the top of the hydrogenation reactor. The hydrogen gas is temperature-controlled to the hydrogenation reactor inlet temperature 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 10 wt%.

[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] The present invention discloses a hydrogenation reaction device (hydrogenation reactor) and a hydrogenation method using a combined catalyst bed.

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

[0099] The hydrogenation reactor has a height-to-diameter ratio of 2.5 and is equipped with two combined catalyst beds, the upper one being the first combined catalyst bed and the lower one being the second combined catalyst bed.

[0100] The first layer of combined catalyst bed: the fixed layer height is 150mm, there is one layer of catalyst unit modules, and the bed void ratio is 65%; the support layer height is 150mm, there is one layer of catalyst unit modules, and the bed void ratio is 80%; the height of the catalyst loaded in the sandwich layer is 300mm, which is 50% of the height of the first layer of combined catalyst bed, and the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

[0101] The second layer of combined catalyst bed: the fixed layer height is 150mm, there is 1 layer of catalyst unit modules, and the bed void ratio is 65%; the support layer height is 150mm, there is 1 layer of catalyst unit modules, and the bed void ratio is 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. The aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

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

[0103] This device was used to investigate the hydrogenation of maleic anhydride and biomass sugar (glucose) under different conditions. The liquid feedstock was first temperature-controlled to the hydrogenation reactor inlet temperature and then introduced from the top. The main reaction hydrogen, then temperature-controlled to the reactor inlet temperature, then introduced from the bottom. The two reacted in a countercurrent hydrogenation process within the catalyst bed, exiting the reactor after completion. During the hydrogenation process, 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 10 wt%.

[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] The present invention discloses a hydrogenation reaction device (hydrogenation reactor) and a hydrogenation method using a combined catalyst bed.

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

[0109] The hydrogenation reactor has a height-to-diameter ratio of 2.0 and is equipped with three combined catalyst beds: the first combined catalyst bed at the top, the second combined catalyst bed in the middle, and the third combined catalyst bed at the bottom.

[0110] The first layer of combined catalyst bed: the fixed layer height is 150mm, there is one layer of catalyst unit modules, and the bed void ratio is 55%; the support layer height is 150mm, there is one layer of catalyst unit modules, and the bed void ratio is 70%; the height of the catalyst loaded in the sandwich layer is 200mm, which is 40% of the height of the first layer of combined catalyst bed, and the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

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

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

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

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

[0115] This device was used to investigate the hydrogenation of maleic anhydride and biomass sugar (glucose) under different conditions. The liquid feedstock was first temperature-controlled to the hydrogenation reactor inlet temperature and then introduced from the top. The main reaction hydrogen, then temperature-controlled to the reactor inlet temperature, then introduced from the bottom. The two reacted in a countercurrent hydrogenation reaction within the catalyst bed, exiting after completion. During the hydrogenation process, 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 10 wt%.

[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] The present invention discloses a hydrogenation reaction device (hydrogenation reactor) and a hydrogenation method using a combined catalyst bed.

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

[0121] The hydrogenation reactor has a height-to-diameter ratio of 2.0 and is equipped with four modular catalyst beds, from top to bottom, from the first to the fourth layer;

[0122] The first layer of combined catalyst bed: the fixed layer height is 150mm, there is one layer of catalyst unit modules, and the bed void ratio is 55%; the support layer height is 150mm, there is one layer of catalyst unit modules, and the bed void ratio is 70%; the height of the catalyst loaded in the sandwich layer is 150mm, which is 33.3% of the height of the first layer of combined catalyst bed, and the aperture of the flexible isolation wire mesh outside the catalyst package is 12 mesh.

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

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

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

[0126] A pulse of hydrogen was 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 was 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 was 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] This device was used to investigate the hydrogenation of maleic anhydride and biomass sugar (glucose) under different conditions. The liquid feedstock was first temperature-controlled to the hydrogenation reactor inlet temperature and then introduced from the top. The main reaction hydrogen, then temperature-controlled to the reactor inlet temperature, then introduced from the bottom. The two reacted in a countercurrent hydrogenation reaction within the catalyst bed, exiting after completion. During the hydrogenation process, pulsed hydrogen was intermittently introduced between the first and second layers, the second and third layers, and the third and fourth layers of the combined catalyst bed.

[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 10 wt%.

[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 between the top and bottom layers of the hydrogenation reactor. Note 2: Coking amount of conventional catalyst (g / 100g): This refers to the amount of coke formed on the catalyst surface due to the deposition of reactants during use. Catalyst coking reduces its activity and selectivity, affecting reaction efficiency and product yield. It is an important indicator for measuring catalyst performance and lifespan. That is, the greater the amount of catalyst coking, the poorer the reaction effect and the shorter the lifespan. Here, the grams of coke per 100g of catalyst surface are measured using thermogravimetric analysis (TGA) after 8 hours 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, with a radial temperature difference of ≤3°C, thereby solving 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: The invention 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 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. 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 provided on the upper part of the combined catalyst bed to evenly distribute the liquid material from above; A gas material distributor is provided at the lower part of the combined catalyst bed 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; 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 height of the modular catalyst units filled in the fixed layer and the supporting layer are independently 50 to 1500 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 of the lower combined catalyst bed is independently greater than or equal to the volume of catalyst loaded in the support layer of the upper combined catalyst bed; For any combined catalyst bed, the voidage of the catalyst loaded in the fixed layer is independently less than or equal to the voidage of the catalyst loaded in the support layer.

4. The hydrogenation reaction device according to claim 3, characterized in that The height of the catalyst package in each sandwich layer is independently 50 to 1000 mm; The heights of the modular catalyst units filled in the fixed layer and the supporting layer are independently 100 to 900 mm.

5. The hydrogenation reaction device according to claim 3 or 4, 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; 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; For any two adjacent combined catalyst beds, the volume of the catalyst loaded in the support layer of the lower combined catalyst bed is independently 100% to 800% of the volume of the catalyst loaded in the support layer of the upper combined catalyst bed; For any combined catalyst bed, the void ratio of the catalyst filled in the fixed layer is independently 50% to 75%, and the void ratio of the catalyst filled in the supporting layer is independently 60% to 95%.

6. The hydrogenation reaction device according to claim 5, 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 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 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 of the lower combined catalyst bed is independently 100% to 500% of the volume of the catalyst loaded in the support layer of the upper combined catalyst bed; For any combined catalyst bed, the void ratio of the catalyst loaded in the fixed layer is independently 55% to 75%, and the void ratio of the catalyst loaded in the supporting layer is independently 70% to 90%.

7. 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.

8. The hydrogenation reaction device according to claim 7, characterized in that: The height-to-diameter ratio of the hydrogenation reaction device is 1 to 5:

1.

9. The hydrogenation reaction device according to claim 1, characterized in that: The fixed layer, sandwich layer and support layer are each provided with independent grids at the bottom to support and fix the catalysts loaded in the corresponding layers. The two sides of the grids are open for material flow, making the combined catalyst bed a cage structure with internal support. The fixed layer and the supporting layer are independently loaded with 1 to 20 layers of modular catalyst units; The wrapping component is a flexible wire mesh; The hole size of the package component is 10-100 mesh; The radial dimension of the cross section of the catalyst particles is 0.5 to 10 mm.

10. The hydrogenation reaction device according to claim 9, characterized in that: The fixed layer and the supporting layer are independently loaded with 1 to 10 layers of modular catalyst units; The radial dimension of the cross section of the catalyst particles is 1 to 6 mm.

11. Use of the hydrogenation reaction device according to any one of claims 1 to 10 in hydrogenation reaction.

12. A hydrogenation method, characterized in that: A hydrogenation reaction device according to any one of claims 1 to 10 is used.

13. The hydrogenation method according to claim 12, 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. After the hydrogenation reaction, the liquid material enters the liquid degassing zone for degassing, and the gaseous material enters the gas deliquid zone for deliquescence.

14. The hydrogenation method according to claim 12 or 13, characterized in that Hydrogen is continuously introduced into the hydrogen feed port; Pulsed hydrogen is intermittently introduced between adjacent combined catalyst beds; The duration of a single pulse of hydrogen gas between adjacent combined catalyst beds is independently 10 to 120 seconds, and the time interval between two adjacent pulses of hydrogen gas is independently 300 to 1200 seconds. The ratio of the single pulse hydrogen flow rate to the liquid raw material feed rate between adjacent combined catalyst beds is independently 1 to 100 Nm 3 / h:1m 3 / h; The single injection amount of pulse hydrogen gradually increases along the flow direction of the liquid material, with an increasing rate of 1% to 80%; The space velocity of the modular catalyst unit filled with fixed layer and support layer is 2~30h -1 ; The space velocity of the catalyst particles filled in the sandwich layer is 0.1~10h -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; The hydrogenation reaction temperature is room temperature to 500°C; The hydrogenation reaction pressure is 0.1 to 20 MPaG.

15. The hydrogenation method according to claim 14, characterized in that The ratio of the single pulse hydrogen flow rate to the liquid raw material feed rate between adjacent combined catalyst beds is 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 10% to 50%; The space velocity of the catalyst particles filled in the sandwich layer is 0.5~4h -1 ; The feed ratio of total hydrogen to liquid raw material is 5~600Nm 3 / h:1m 3 / h.

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