Reverse / cross-flow hydrogenation reaction device and application thereof

Abstract

The invention discloses a reverse / cross-flow hydrogenation reaction device and application thereof. The reverse / cross-flow hydrogenation reaction device comprises a hydrogenation reactor I and a hydrogenation reactor II; the hydrogenation reactor I is of a gas-liquid reverse / cross-flow reactor structure and comprises a gas-liquid removal section, a gas-liquid reverse / cross-flow mass transfer strengthening section and a liquid degassing section which are sequentially communicated from top to bottom; the gas-liquid reverse / cross-flow mass transfer strengthening section is filled with one or more layers of integral modular catalysts, and each layer of integral modular catalyst comprises a catalyst unit module body and an outer frame for fixing and framing the catalyst unit module body; the outer frame is of a segmental structure, so that catalyst unit module bodies in the outer frame are not fully distributed on the cross section of the hydrogenation reactor I, an arch-shaped notch is reserved on one side of the outer frame to serve as a liquid descending channel, and the arch-shaped notches of the upper and lower adjacent layers of integral modular catalysts are arranged in a central symmetry manner; and the hydrogenation reactor II is of a gas-liquid countercurrent reactor structure.

Description

Technical Field

[0001] The invention relates to the technical field of hydrogenation, and in particular to a reverse / cross-flow hydrogenation reaction device and application thereof. Background Art

[0002] Hydrogenation technology is widely used in the fields of oil refining, chemical industry, biochemical industry, food and medicine. It is a process in which certain components containing unsaturated groups in the raw materials undergo hydrogenation reaction to produce the desired product in an atmosphere of hydrogen and catalyst.

[0003] Fixed bed catalytic hydrogenation can be divided into two forms according to the overall feeding direction of the materials: upflow (downward feeding) and downflow (upward feeding). Downflow (upward feeding) is widely used because of its wide range of applications, that is, most fixed bed hydrogenation uses the traditional trickle bed hydrogenation process of gas-liquid co-current. During the reaction process, the gas and liquid generally flow downward through the fixed catalyst bed to complete the catalytic hydrogenation reaction. Since in the fixed bed gas-liquid co-current hydrogenation process, the liquid passes through the catalyst bed in the form of a liquid film, which easily leads to uneven liquid distribution, channeling and short-circuiting, thereby reducing the utilization rate and reaction rate of the catalyst. Therefore, in order to ensure the reaction conversion rate and selectivity, it is generally necessary to adopt more stringent reaction conditions, such as a higher hydrogen-to-liquid ratio, a longer reaction residence time, a higher temperature and hydrogen partial pressure, etc., which not only has high equipment investment and energy consumption, but also has problems such as low reaction efficiency, low catalyst utilization, uneven reaction, and many side reactions. As the demand for high efficiency and energy saving in hydrogenation equipment continues to increase, higher requirements are placed on the fixed-bed hydrogenation reaction process. Here, gas-liquid countercurrent hydrogenation can not only improve the efficiency of hydrogenation reaction, increase catalyst utilization, and reduce energy consumption and investment, but also become an important development direction of fixed-bed hydrogenation reaction technology.

[0004] Patent CN102041063B proposes a method for deep desulfurization of diesel, in which the diesel feedstock and hydrogen first pass through a gas-liquid countercurrent hydrogenation reaction zone, and the effluent of the gas-liquid countercurrent hydrogenation reaction zone enters a gas-liquid parallel current hydrogenation reaction zone, and the gas-liquid parallel current hydrogenation reaction zone adopts a gas-liquid parallel current downward flow operation mode, wherein the gas-liquid countercurrent hydrogenation reaction zone uses a Mo-Co type hydrogenation refining catalyst, and the gas-liquid parallel current hydrogenation reaction zone uses a Mo-Ni type hydrogenation refining catalyst or a W-Mo-Ni type hydrogenation refining catalyst. Patent CN101343563B proposes a method for hydrogenating light hydrocarbons, which uses a countercurrent hydrogenation reactor and a conventional parallel current hydrogenation reactor in series. The raw material enters the flash zone of the countercurrent hydrogenation reactor at a relatively low temperature, and the gaseous hydrocarbon flows upward to react with diolefins and mercaptans to form sulfide and diolefin hydrogenation in the upper part of the countercurrent reactor. The high-boiling sulfide produced by the upper reaction and the liquid hydrocarbon after the raw material flash evaporate flow downward together, and thiophene sulfur reacts with olefins for alkylation; hydrogen enters from the bottom of the countercurrent reactor and flows upward; the liquid phase discharged from the bottom of the countercurrent reactor is mixed with new hydrogen and heated to enter the parallel flow hydrogenation reactor for deep hydrodesulfurization, selective cracking or isomerization. Patent CN103805240B proposes a low-cost combined hydrorefining method for oil products, including: first, hydrogen is mixed into the liquid phase material, the liquid phase material mixed with hydrogen dissolving enters the liquid phase hydrogenation reactor for reaction, the material after the liquid phase hydrogenation reaction enters the countercurrent reactor from the upper part of the reactor, and further reacts with a small amount of new hydrogen entering from the bottom of the reactor in the countercurrent reactor, and the liquid product after the reaction is partially circulated to the front of the liquid phase hydrogenation reactor, and the rest is used as a hydrogenation product. The above-mentioned invention methods simply change the first hydrogenation reactor in the hydrogenation process from a conventional gas-liquid co-current reactor to a gas-liquid counter-current reactor, without improving the substantial contents such as the internal structure of the reactor and the catalyst loading method. In fact, the internal structure, material contact method and catalyst loading method of the counter-current hydrogenation reactor are essentially different from those of the co-current hydrogenation reactor. It is difficult to achieve the application effect of the gas-liquid counter-current reactor by simply modifying the parts.

[0005] Patent CN102041069B proposes a gas-liquid countercurrent hydrogenation method for diesel desulfurization, denitrogenation and aromatic saturation. Under the conditions of diesel fraction hydrotreatment, hydrogen and diesel feedstock pass through the catalyst bed in a countercurrent manner. The reactor is divided into at least two reaction zones, each of which is composed of at least one hydrogenation catalyst bed; the diameter of the reactor increases successively 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 junction, 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 logistics. This invention method only makes a slight improvement to the internal structure of the countercurrent reactor from the perspective of adjusting the material flow state, and does not fully consider the catalyst loading method and the enhancement of the mass transfer process in the countercurrent reactor.

[0006] In summary, the gas-liquid countercurrent hydrogenation reactor and the gas-liquid parallel current hydrogenation reactor are essentially different in terms of gas-liquid contact mass transfer form, reactor structure, and catalyst loading method. Most of the existing gas-liquid countercurrent hydrogenation processes focus on process flow improvements, and very few are slight improvements in the internal structure of the reactor. On the one hand, they have not effectively achieved a significant enhancement of the hydrogenation reaction process, and on the other hand, they have not solved problems such as local hot spots and easy coking of catalysts in conventional reactions. Therefore, how to design a more efficient gas-liquid countercurrent hydrogenation process and a gas-liquid countercurrent hydrogenation reactor structure according to the characteristics of the gas-liquid countercurrent hydrogenation reaction mass transfer process is of great significance for the actual gas-liquid countercurrent hydrogenation process enhancement. Summary of the invention

[0007] In view of the above technical problems and the shortcomings in the art, the present invention provides a reverse / cross-flow hydrogenation reaction device and its application. The present invention greatly enhances the mass transfer and heat transfer in the hydrogenation reaction process through two-stage special structure hydrogenation reactors and the series coupling between them, and can achieve continuous and efficient hydrogenation conversion under more moderate conditions, solve the problems of uneven reaction, easy generation of local hot spots, easy coking of catalysts, etc. in conventional hydrogenation reactions, improve the conversion rate and selectivity of hydrogenation reactions, extend the service life of catalysts, and reduce the energy consumption of the device.

[0008] [1] A reverse / cross-flow hydrogenation reaction device, comprising a hydrogenation reactor I and a hydrogenation reactor II;

[0009] The hydrogenation reactor I is a gas-liquid counter / cross flow reactor structure, comprising a gas deliquid section, a gas-liquid counter / cross flow mass flow enhancement section and a liquid degassing section which are sequentially connected from top to bottom; a liquid feed port I is arranged between the gas deliquid section and the gas-liquid counter / cross flow mass flow enhancement section; a gas feed port I is arranged between the gas-liquid counter / cross flow mass flow enhancement section and the liquid degassing section; a gas discharge port I is arranged above the gas deliquid section; a liquid discharge port I is arranged below the liquid degassing section; the gas-liquid counter / cross flow mass flow enhancement section is filled with one or more layers of integral modular catalysts, and each layer of the integral modular catalyst comprises a catalyst The catalyst unit module body and the outer frame for fixing the catalyst unit module body; the outer frame is a circular structure, so that the catalyst unit module body inside is not completely covered on the cross section of the hydrogenation reactor I, but an arched gap is left on one side as a liquid descending channel, and the arched gap positions of the upper and lower adjacent layers of the integral modular catalyst are arranged symmetrically. Such a special structural arrangement is to guide the path of the gas-liquid mass transfer process, so that the gas and liquid in the hydrogenation reactor I are in contact with each other and simultaneously carry out countercurrent and cross-current mass transfer, thereby enhancing the mass transfer and heat transfer;

[0010] The hydrogenation reactor II is a gas-liquid countercurrent reactor structure, including a gas deliquidation zone, a rapid mass transfer reaction zone and a liquid degassing zone which are sequentially connected from top to bottom; a liquid feed port II connected to the liquid discharge port I is arranged between the gas deliquidation zone and the rapid mass transfer reaction zone; a gas feed port II connected to the gas discharge port I is arranged between the rapid mass transfer reaction zone and the liquid degassing zone; a gas discharge port II is arranged above the gas deliquidation zone; and a liquid discharge port II is arranged below the liquid degassing zone.

[0011] In the counter / cross flow hydrogenation reaction device, the diameters of the gas deliquid section, the gas-liquid counter / cross flow mass transfer enhancement section and the liquid degassing section may be the same or different, preferably the same.

[0012] In the counter / cross-flow hydrogenation reaction device, the height-to-diameter ratio of the hydrogenation reactor I can be 0.5 to 5:1, preferably 1 to 3:1, such as 2:1, 2.5:1, 3:1, etc.

[0013] In the reverse / cross-flow hydrogenation reaction device, the diameters of the gas deliquid zone, the fast mass transfer reaction zone and the liquid degassing zone may be the same or different, preferably the same.

[0014] In the counter-current / cross-current hydrogenation reaction device, the height-to-diameter ratio of the hydrogenation reactor II can be 1 to 15:1, preferably 3 to 8:1, such as 6:1, 5:1, etc.

[0015] In some embodiments, in the counter / cross flow hydrogenation reaction apparatus, the height-to-diameter ratio of hydrogenation reactor I is smaller than the height-to-diameter ratio of hydrogenation reactor II.

[0016] In some embodiments, in the reverse / cross-flow hydrogenation reaction device, the effective volume of hydrogenation reactor I is greater than the effective volume of hydrogenation reactor II. Further, the ratio of the effective volume of hydrogenation reactor I to hydrogenation reactor II may be greater than 1:1 and not more than 100:1, preferably 2 to 20:1, such as 10:1, 12.5:1, 15:1, etc. The effective volume is defined as the volume of the catalyst loaded in the reactor.

[0017] In the reverse / cross-flow hydrogenation reaction device, the rapid mass transfer reaction zone can be loaded with a catalyst. Further, the catalyst loaded in the rapid mass transfer reaction zone can be a non-integrated modular catalyst, the catalyst bed void ratio can be 50% to 95%, preferably 60% to 90%, such as 76.2%, 78.2%, 81.5%, etc., the catalyst particle size can be 1 to 3 mm, such as 1.2 to 1.5 mm, 2.5 to 3.0 mm, etc., and the catalyst bulk density can be 0.8 to 1.1 g / mL, such as 0.88 to 1.00 g / mL, 0.82 to 1.03 g / mL, etc.

[0018] The reverse / cross-flow hydrogenation reaction device, the outer frame may include a supporting grid, a pressing grid, an external frame and interconnected parts; the supporting grid and the pressing grid may be arranged horizontally, respectively located at the lower part and the upper part of the catalyst unit module body; the external frame may be arranged vertically, located outside the catalyst unit module body; the supporting grid and the hydrogenation reactor I may be a fixed welding structure, and the supporting grid, the pressing grid and the external frame may be a movable connection structure.

[0019] The smaller the roundness ratio, the longer the gas-liquid cross-flow mass transfer path, the higher the mass transfer intensity, but the greater the pressure drop; the larger the roundness ratio, the shorter the gas-liquid cross-flow mass transfer path, the lower the mass transfer intensity, but the smaller the pressure drop. In the reverse / cross-flow hydrogenation reaction device, the roundness ratio of the overall modular catalyst roundness structure is preferably 0.5% to 50%, more preferably 1% to 10%, such as 5.0%, 6.2%, 7.5%, etc. The roundness ratio is defined as the ratio of the area of ​​the notch on the unit circle to the total area of ​​the circle.

[0020] In the counter / cross flow hydrogenation reaction device, the gas-liquid counter / cross flow mass transfer enhancement section can be loaded with 2 to 100 layers, preferably 10 to 50 layers (eg 18 layers, 25 layers, 35 layers, etc.) of integral modular catalyst.

[0021] In the counter-flow / cross-flow hydrogenation reaction device, the height of the single-layer integral modular catalyst can be 50 to 1500 mm, preferably 100 to 600 mm, such as 450 mm.

[0022] In the counter-flow / cross-flow hydrogenation reaction device, the through-hole size of the surface of the overall modular catalyst can be 1mm×1mm~10mm×10mm, preferably 3mm×3mm~8mm×8mm.

[0023] In the reverse / cross-flow hydrogenation reaction device, each layer of the integral modular catalyst may include one or more catalyst unit module bodies.

[0024] In the reverse / cross-flow hydrogenation reaction device, the shape of the catalyst unit module body can be any one of cylindrical, rectangular, square, rhombus, polygonal, etc., preferably rectangular.

[0025] In the reverse / cross-flow hydrogenation reaction device, a honeycomb pore structure arranged in an array may be provided in the catalyst unit module body. The honeycomb pore structure is interconnected, which can increase the gas-liquid mass transfer contact area and is also beneficial to material diffusion flow and mass transfer and heat transfer.

[0026] In the counter-flow / cross-flow hydrogenation reaction device, the bulk density of the catalyst unit module body can be 0.6-0.9 g / mL, such as 0.68-0.82 g / mL, 0.73-0.85 g / mL, etc.

[0027] In the reverse / cross-flow hydrogenation reaction device, the catalyst unit module body is generally composed of an integral honeycomb substrate, a coating material and an active component; during the preparation process, an integral honeycomb is used as a substrate, and a step-by-step impregnation method is adopted to load a high specific surface area coating and active components, and the thickness of the active component impregnation can be controlled by adjusting the coating amount; the integral modular catalyst can generally use commercially available products as needed, or it can be prepared according to conventional knowledge in the field.

[0028] In the hydrogenation reactor II, the rapid mass transfer reaction zone is generally loaded with a supported catalyst, wherein the catalyst carrier may be one or more of SiO2, Al2O3, SiO2-Al2O3, TiO2, activated carbon, MgO, molecular sieve, etc.; the catalyst shape may be one or more of sphere, bar, clover-shaped, toothed ball, etc.; the catalyst may be a commercially available product as needed, or may be prepared according to conventional knowledge in the art.

[0029] In the reverse / cross-flow hydrogenation reaction device, the gas-liquid separation section and the gas-liquid separation zone can be independently provided with components with gas-liquid separation function to perform gas-liquid separation; the components with gas-liquid separation function can be one or more of a baffle structure, a cyclone / centrifugal structure, a filler and a wire mesh structure.

[0030] In the reverse / cross-flow hydrogenation reaction device, the liquid degassing section and the liquid degassing zone can be independently set with liquid level control and a certain liquid level height to keep the liquid with sufficient residence time to achieve liquid degassing, and components with liquid degassing function can be set or not set inside.

[0031] The reverse / cross-flow hydrogenation reaction device may include a heat extraction device between the hydrogenation reactor I and the hydrogenation reactor II, which is used to extract heat from the reaction liquid product of the hydrogenation reactor I and adjust the reaction temperature required for the material entering the hydrogenation reactor II. The heat extraction device may be a heat exchanger, an air cooler or a water cooler.

[0032] In the reverse / cross-flow hydrogenation reaction device, the remaining hydrogen in the hydrogenation reactor I can be used in whole or in part as the hydrogen source for the hydrogenation reactor II, or a supplementary hydrogen pipeline can be set in the hydrogenation reactor II to supplement the hydrogen required by the hydrogenation reactor II.

[0033] The counter / cross-flow hydrogenation reaction device, the gas-liquid counter / cross-flow mass transfer enhancement section of the hydrogenation reactor I and the rapid mass transfer reaction zone of the hydrogenation reactor II, can be loaded with a catalyst having a hydrogenation function. The hydrogenation catalyst can be selected according to the reaction type, generally according to the type of hydrogenation reaction, and the best type of catalyst can be selected, 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.

[0034] [2] Application of the counter-current / cross-current hydrogenation reaction apparatus described in [1] in hydrogenation reaction.

[0035] The reverse / cross-flow hydrogenation reaction device of the present invention is suitable for 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.

[0036] [3] A hydrogenation method, using the counter-current / cross-current hydrogenation reaction device described in [1].

[0037] In some embodiments, in the hydrogenation method, the raw material liquid enters the hydrogenation reactor I from the liquid feed port I, the hydrogen enters the hydrogenation reactor I from the gas feed port I, the raw material liquid and the hydrogen undergo a reverse / cross-flow hydrogenation reaction in the hydrogenation reactor I, the remaining hydrogen after the reaction is completed leaves from the gas discharge port I, and partially or completely enters the hydrogenation reactor II, and the reaction liquid after the reaction is completed leaves from the liquid discharge port I, and partially or completely enters the hydrogenation reactor II;

[0038] Part or all of the remaining hydrogen discharged from the gas outlet I of the hydrogenation reactor I enters the hydrogenation reactor II through the gas feed port II with or without additional hydrogen supplementation, and part or all of the reaction liquid discharged from the liquid outlet I of the hydrogenation reactor I enters the hydrogenation reactor II through the liquid feed port II. The two undergo a countercurrent hydrogenation reaction in the hydrogenation reactor II, and the remaining hydrogen after the reaction is completed leaves from the gas outlet II, and the reaction liquid after the reaction is completed leaves from the liquid outlet II.

[0039] In the hydrogenation method, the hydrogen-to-liquid ratio of the hydrogenation reactor I and the hydrogenation reactor II can be adjusted according to the reaction requirements, hydrogen consumption, conversion rate and selectivity. In principle, the total hydrogen-to-liquid ratio is the lowest and the energy consumption is the lowest under the premise of ensuring the best reaction effect.

[0040] In some embodiments, the sum of the hydrogenation reaction conversion rates of hydrogenation reactor I and hydrogenation reactor II is 100%, wherein the hydrogenation reaction conversion rate of hydrogenation reactor I may be 50% to 99%, preferably 60% to 90%, and the hydrogenation reaction conversion rate of hydrogenation reactor II may be 1% to 50%, preferably 10% to 40%, and the hydrogenation reaction conversion rate of hydrogenation reactor I is higher than the hydrogenation reaction conversion rate of hydrogenation reactor II.

[0041] In the hydrogenation method, the feed ratio of hydrogen to raw liquid in the hydrogenation reactor I can be 1 to 1500 Nm 3 / h:1m 3 / h, preferably 50 to 500 Nm 3 / h:1m 3 / h.

[0042] In the hydrogenation method, the feed ratio of hydrogen to reaction liquid in the hydrogenation reactor II can be 1 to 500 Nm 3 / h:1m 3 / h, preferably 2 to 200 Nm 3 / h:1m 3 / h.

[0043] The hydrogenation method may use hydrogen with a purity greater than 90 vol%, preferably pure hydrogen greater than 99.9 vol%.

[0044] The process conditions of the hydrogenation reactor I and the hydrogenation reactor II can be independently as follows: the reaction temperature is room temperature to 500°C, the reaction pressure is 0.1 to 20 MPaG, the liquid hourly volume space velocity is 0.1 to 20 h -1 .

[0045] In the present invention, the liquid feed in hydrogenation reactor I is the material in the early stage of hydrogenation reaction. Due to the high raw material concentration, it is easy to cause problems such as uneven reaction, concentrated heat release, and poor selectivity; the liquid feed in hydrogenation reactor II is the material in the late stage of reaction. The raw material concentration is low and the reaction rate is slow. Therefore, more stringent reaction conditions (such as higher temperature and pressure, lower space velocity) are required to achieve the ideal conversion rate. It is more likely to cause problems such as catalyst coking and many side reactions due to long local residence time. (Note: The early stage of reaction described herein refers to the stage where the reaction substrate concentration in the raw material liquid in the reactor is ≥ the target product concentration, and the late stage of reaction refers to the reaction stage where the reaction substrate concentration in the raw material liquid in the reactor is < the target product concentration.)

[0046] In order to solve the above problems, the reverse / cross-flow hydrogenation reaction device and hydrogenation method of the present invention have the following technical advantages:

[0047] (1) By setting up the special structure of the hydrogenation reactor I and guiding the reaction mass transfer path, on the one hand, continuous gas-liquid countercurrent and gas-liquid cross-current contact mass transfer can be carried out simultaneously in the hydrogenation reactor I, which greatly enhances the mass transfer. On the other hand, the use of an overall modular catalyst, a catalyst loading method and through holes arranged inside the catalyst are more conducive to the diffusion flow of materials, thereby achieving better mass transfer and heat transfer effects. It is particularly suitable for systems with high raw material substrate concentrations in the early stage of the reaction, and can achieve higher conversion rates and selectivity under mild conditions.

[0048] (2) Compared with hydrogenation reactor II, hydrogenation reactor I is set with a smaller aspect ratio in order to allow the liquid material to have a longer radial flow distance in each catalyst bed layer and give full play to the advantages of gas-liquid cross-flow mass transfer. That is, sufficient radial flow of liquid material and gas-liquid cross-flow contact can make the reactor temperature more uniform along the radial direction, making the reaction rate faster while solving problems such as concentrated reaction exotherm, local hot spots, many side reactions, and catalyst coking.

[0049] (3) Compared with hydrogenation reactor I, hydrogenation reactor II is set with a larger aspect ratio. This is mainly because hydrogenation reactor II contains materials in the late stage of reaction, with low raw material substrate concentration and slow reaction rate. Generally, more stringent reaction conditions (such as higher temperature) are required to achieve the desired conversion rate. Here, by setting a large aspect ratio reactor, on the one hand, the rate of material passing through the catalyst surface can be increased, and the liquid film formed can be thinner, which plays a role in enhancing mass transfer. On the other hand, a high-porosity catalyst is set to minimize or even eliminate the local retention of liquid on the catalyst surface, prevent the occurrence of deviation flow, channeling and other phenomena, thereby solving the problems of coking and clogging of the catalyst bed and easy deactivation.

[0050] (4) By setting the early-stage materials and the late-stage materials of the reaction to adopt the structural forms of hydrogenation reactor I and reactor II respectively and the material flow mode adapted to the respective reaction characteristics, reactor I and reactor II are connected in series, and hydrogenation reactions occur in sequence. The two-stage reactions are coupled with each other, which ensures the efficient conversion of the entire hydrogenation reaction while making the reaction more uniform and greatly reducing side reactions. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 It is a schematic structural diagram of a reverse / cross-flow hydrogenation reaction device of the present invention. DETAILED DESCRIPTION

[0052] 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.

[0053] See also Figure 1 A reverse / cross-flow hydrogenation reaction device comprises a hydrogenation reactor I 5 and a hydrogenation reactor II15 connected in series and their connected pipelines.

[0054] The hydrogenation reactor 15 is a gas-liquid counter / cross flow reactor structure, including a gas deliquid section 8, a gas-liquid counter / cross flow mass transfer enhancement section and a liquid degassing section 9 which are sequentially connected from top to bottom. The diameters of the gas deliquid section 8, the gas-liquid counter / cross flow mass transfer enhancement section and the liquid degassing section 9 are the same. A liquid feed port I is arranged between the gas deliquid section 8 and the gas-liquid counter / cross flow mass transfer enhancement section. A gas feed port I is arranged between the gas-liquid counter / cross flow mass transfer enhancement section and the liquid degassing section 9. A gas discharge port I is arranged above the gas deliquid section 8. A liquid discharge port I is arranged below the liquid degassing section 9. The gas-liquid counter / cross flow mass transfer enhancement section is filled with one or more layers of an integral modular catalyst 10, and each layer of the integral modular catalyst 10 comprises a catalyst unit module body 11 and an outer frame for fixing and framing the catalyst unit module body 11. The outer frame includes a support grid 12, a compression grid 13, an external frame 14 and interconnected parts; the support grid 12 and the compression grid 13 are arranged horizontally, respectively located at the lower part and the upper part of the catalyst unit module body 11; the external frame 14 is arranged vertically, and is located outside the catalyst unit module body 11; the support grid 12 and the hydrogenation reactor 1 are fixed welding structures, and the support grid 12, the compression grid 13 and the external frame 14 are movable connection structures. The outer frame is a circular structure, so that the catalyst unit module body 11 inside it is not completely covered on the cross section of the hydrogenation reactor 1, but an arched gap is left on one side as a liquid descending channel, and the arched gap positions of the upper and lower adjacent layers of the integral modular catalyst 10 are arranged symmetrically.

[0055] The hydrogenation reactor II 15 is a gas-liquid countercurrent reactor structure, including a gas deliquidation zone 21, a rapid mass transfer reaction zone and a liquid degassing zone 22 which are sequentially connected from top to bottom. The diameters of the gas deliquidation zone 21, the rapid mass transfer reaction zone and the liquid degassing zone 22 are the same. A liquid feed port II connected to the liquid discharge port I is provided between the gas deliquidation zone 21 and the rapid mass transfer reaction zone. A gas feed port II connected to the gas discharge port I is provided between the rapid mass transfer reaction zone and the liquid degassing zone 22. A gas discharge port II is provided above the gas deliquidation zone 21. A liquid discharge port II is provided below the liquid degassing zone 22. The rapid mass transfer reaction zone is loaded with a catalyst 20. The effective volume of the hydrogenation reactor I 5 is greater than the effective volume of the hydrogenation reactor II 15.

[0056] A hydrogenation method, using the above Figure 1 The reverse / cross-flow hydrogenation reaction device shown comprises:

[0057] First, the liquid feed 1 and the hydrogen 2 are respectively introduced into the liquid feed port I and the gas feed port I of the hydrogenation reactor I 5. After the liquid feed 1 is evenly distributed by the liquid feed distributor 6, it enters the integral modular catalyst 10 to undergo a counter-current / cross-current hydrogenation reaction with the gas rising from the bottom. The remaining hydrogen after the reaction is deliquidated by the gas deliquid section 8 and leaves the hydrogenation reactor I5, and enters the hydrogenation reactor I15 as the remaining gas 3 of the hydrogenation reactor I5; the hydrogen 2 is evenly distributed by the hydrogen distributor 7, and then enters the integral modular catalyst 10 to undergo a counter-current / cross-current hydrogenation reaction with the liquid descending from the top. The reaction product is degassed by the liquid degassing zone 9 and leaves the hydrogenation reactor I 5, and enters the hydrogenation reactor II 15 as the reaction liquid product 4 of the hydrogenation reactor I5.

[0058] In the hydrogenation reactor II 15, the residual gas 3 and the reaction liquid product 4 from the hydrogenation reactor I 5 are respectively introduced into the liquid feed port II and the gas feed port II of the hydrogenation reactor II 15. After the top feed is evenly distributed by the liquid feed distributor 18, it enters the catalyst bed 20 to undergo a countercurrent hydrogenation reaction with the gas rising from the bottom. The residual hydrogen after the reaction is deliquated in the gas deliquation zone 21 and leaves the hydrogenation reactor II 15 as the residual gas 16 of the hydrogenation reactor II 15. After the residual gas 3 is evenly distributed by the hydrogen distributor 19, it enters the catalyst bed 20 to undergo a countercurrent hydrogenation reaction with the liquid descending from the top. The reaction product 17 is degassed in the liquid degassing zone 22 and leaves.

[0059] The above-mentioned reverse / cross-flow hydrogenation reaction device and hydrogenation method are respectively applied to the hydrogenation of straight-run diesel and the hydrogenation of biomass sugar (glucose) solution. The properties of the straight-run diesel feedstock are shown in Table 1, and the properties of the straight-run diesel hydrogenation catalyst are shown in Table 2; the properties of the biomass sugar (glucose) hydrogenation feedstock are shown in Table 3, and the properties of the biomass sugar (glucose) solution hydrogenation catalyst are shown in Table 4. All the above-mentioned raw materials are commercially available, and all hydrogenation catalysts are homemade.

[0060] Table 1 Properties of straight-run diesel feedstock

[0061] project Crude oil <![CDATA[Density, g / cm 3 > 0.836 <![CDATA[Viscosity, mm 2 / s]]> 764.7 Sulfur, wt% 0.62 Nitrogen, μg / g 103 Distillation range, ℃ IBP / 5% 202 / 238 10％ / 30％ 258 / 269 50％ / 70％ 290 / 301 90％ / 95％ 322 / 334 EBP 353

[0062] Table 2 Physical and chemical indicators of straight-run diesel hydrogenation catalyst

[0063]

[0064] Table 3 Biomass sugar (glucose) solution raw materials

[0065] project index Characteristics Colorless transparent liquid Concentration, mol / L 1.5

[0066] Table 4 Biomass sugar (glucose) solution hydrogenation catalyst properties

[0067]

[0068] Comparative Example 1

[0069] The conventional fixed bed series hydrogenation process was adopted. Both hydrogenation reactor I and hydrogenation reactor II were gas-liquid countercurrent hydrogenation reactors; the height-to-diameter ratio of hydrogenation reactor I was 2.0, and the height-to-diameter ratio of hydrogenation reactor II was 2.0. The reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation were investigated under different conditions using this device. Both hydrogenation reactor I and hydrogenation reactor II were loaded with non-integrated modular catalysts corresponding to their respective reactions.

[0070] First, the raw material is temperature-adjusted to the inlet temperature of hydrogenation reactor I and then enters from the top of hydrogenation reactor I, and the hydrogen is temperature-adjusted to the inlet temperature of hydrogenation reactor I and then enters from the bottom of hydrogenation reactor I, and the two undergo a countercurrent hydrogenation reaction in hydrogenation reactor I to obtain liquid products and residual gas; the liquid product enters from the top of hydrogenation reactor II after temperature adjustment, and the residual gas enters from the bottom of hydrogenation reactor II after temperature adjustment, and the countercurrent hydrogenation reaction continues, and the hydrogenation reaction is completed and then leaves.

[0071] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 5, and the reaction results are shown in Table 6. The volume space velocity in Table 5 refers to the liquid volume space velocity, which will not be repeated below.

[0072] Comparative Example 2

[0073] The conventional fixed bed series hydrogenation process was adopted. Both hydrogenation reactor I and hydrogenation reactor II were gas-liquid countercurrent hydrogenation reactors; the height-to-diameter ratio of hydrogenation reactor I was 2.0, and the height-to-diameter ratio of hydrogenation reactor II was 4.0. The reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation were investigated under different conditions using this device. Both hydrogenation reactor I and hydrogenation reactor II were loaded with non-integrated modular catalysts corresponding to their respective reactions.

[0074] First, the raw material is temperature-adjusted to the inlet temperature of hydrogenation reactor I and then enters from the top of hydrogenation reactor I, and the hydrogen is temperature-adjusted to the inlet temperature of hydrogenation reactor I and then enters from the bottom of hydrogenation reactor I, and the two undergo a countercurrent hydrogenation reaction in hydrogenation reactor I to obtain liquid products and residual gas; the liquid product enters from the top of hydrogenation reactor II after temperature adjustment, and the residual gas enters from the bottom of hydrogenation reactor II after temperature adjustment, and the countercurrent hydrogenation reaction continues, and the hydrogenation reaction is completed and then leaves.

[0075] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 5, and the reaction results are shown in Table 6.

[0076] Comparative Example 3

[0077] The conventional fixed bed series hydrogenation process was adopted. Both hydrogenation reactor I and hydrogenation reactor II were gas-liquid countercurrent hydrogenation reactors; the height-to-diameter ratio of hydrogenation reactor I was 4.0, and the height-to-diameter ratio of hydrogenation reactor II was 2.0. The reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation were investigated under different conditions using this device. Both hydrogenation reactor I and hydrogenation reactor II were loaded with non-integrated modular catalysts corresponding to their respective reactions.

[0078] First, the raw material is temperature-adjusted to the inlet temperature of hydrogenation reactor I and then enters from the top of hydrogenation reactor I, and the hydrogen is temperature-adjusted to the inlet temperature of hydrogenation reactor I and then enters from the bottom of hydrogenation reactor I, and the two undergo a countercurrent hydrogenation reaction in hydrogenation reactor I to obtain liquid products and residual gas; the liquid product enters from the top of hydrogenation reactor II after temperature adjustment, and the residual gas enters from the bottom of hydrogenation reactor II after temperature adjustment, and the countercurrent hydrogenation reaction continues, and the hydrogenation reaction is completed and then leaves.

[0079] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 5, and the reaction results are shown in Table 6.

[0080] Example 1

[0081] The device and method described in the specific embodiment of the present invention are used. The height-to-diameter ratio of hydrogenation reactor I is 2.5; the gas-liquid counter / cross-flow mass transfer enhancement section is filled with 25 layers of integral modular catalyst; the integral modular catalyst round-slot structure has a round-slot ratio of 7.5%. The height-to-diameter ratio of hydrogenation reactor II is 6:1, and the void ratio of the catalyst bed filled in the rapid mass transfer zone is 81.5%. The device was used to investigate the reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation under different conditions.

[0082] First, the raw material is temperature-adjusted to the inlet temperature of hydrogenation reactor I and then enters from the top of hydrogenation reactor I, and the hydrogen is temperature-adjusted to the inlet temperature of hydrogenation reactor I and then enters from the bottom of hydrogenation reactor I, and the two undergo countercurrent / cross-current hydrogenation reaction in hydrogenation reactor I to obtain liquid products and residual gas; the liquid product enters from the top of hydrogenation reactor II after temperature adjustment, and the residual gas enters from the bottom of hydrogenation reactor II after temperature adjustment, and countercurrent hydrogenation reaction continues to occur, and leaves after the hydrogenation reaction is completed.

[0083] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 5, and the reaction results are shown in Table 6.

[0084] Example 2

[0085] The device and method described in the specific embodiment of the present invention are used, and the process flow is the same as that of Example 1, except that: the height-to-diameter ratio of hydrogenation reactor I is 2.0; 35 layers of integral modular catalyst are loaded in the mass transfer enhancement zone; the integral modular catalyst round-to-round structure has a round-to-round ratio of 5.0%. The height-to-diameter ratio of hydrogenation reactor II is 6:1, and the void ratio of the catalyst bed loaded in the rapid mass transfer zone is 76.2%. The device is used to investigate the reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation under different conditions.

[0086] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 5, and the reaction results are shown in Table 6.

[0087] Example 3

[0088] The device and method described in the specific embodiment of the present invention are used, and the process flow is the same as that of Example 1, except that: the height-to-diameter ratio of hydrogenation reactor I is 3.0; 18 layers of integral modular catalyst are loaded in the mass transfer enhancement zone; the integral modular catalyst round-to-round structure has a round-to-round ratio of 6.2%. The height-to-diameter ratio of hydrogenation reactor II is 5:1, and the void ratio of the catalyst bed loaded in the rapid mass transfer zone is 78.2%. The device is used to investigate the reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation under different conditions.

[0089] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 5, and the reaction results are shown in Table 6.

[0090] Table 5 Operating conditions of hydrogenation reactor I and hydrogenation reactor II

[0091]

[0092] Table 6 Reaction results of hydrogenation reactor I and hydrogenation reactor II

[0093]

[0094] Δt11\Δt12\Δt13: average radial temperature difference of top\middle\bottom in hydrogenation reactor I;

[0095] Δt21\Δt22\Δt23: Average radial temperature difference of top\middle\bottom in hydrogenation reactor II.

[0096] It can be seen from the effects of the embodiments and comparative examples of the present invention that the hydrogenation reaction device and hydrogenation method of the present invention are used, and the hydrogenation reactor I and the hydrogenation reactor II are coupled in series, so that the materials in the early stage of the reaction are reacted in the hydrogenation reactor I, and the materials in the late stage of the reaction are reacted in the hydrogenation reactor II. It can be seen that the average radial temperature difference of the two hydrogenation reactors is greatly reduced, which effectively enhances the convective mass transfer and heat transfer diffusion of the materials in the reaction process, makes the radial distribution of temperature in the hydrogenation reaction process more uniform, solves the problems of concentrated heat release, generation of local hot spots, easy coking of catalysts, etc. in the reaction process, and greatly improves the conversion rate and selectivity of the hydrogenation reaction.

[0097] 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 reverse / cross-flow hydrogenation reaction device, characterized in that: It includes a hydrogenation reactor I and a hydrogenation reactor II; The hydrogenation reactor I is a gas-liquid counter / cross flow reactor structure, including a gas deliquid section, a gas-liquid counter / cross flow mass flow enhancement section and a liquid degassing section which are sequentially connected from top to bottom; a liquid feed port I is arranged between the gas deliquid section and the gas-liquid counter / cross flow mass flow enhancement section; a gas feed port I is arranged between the gas-liquid counter / cross flow mass flow enhancement section and the liquid degassing section; a gas discharge port I is arranged above the gas deliquid section; a liquid discharge port I is arranged below the liquid degassing section; the gas-liquid counter / cross flow mass flow enhancement section is filled with one or more layers of integral modular catalysts, each layer of the integral modular catalyst comprises a catalyst unit module body and an outer frame for fixing the catalyst unit module body; the outer frame is a circular notch structure, so that the catalyst unit module body therein is not completely covered on the cross section of the hydrogenation reactor I, but an arched notch is left on one side as a liquid descending channel, and the positions of the arched notches of the upper and lower adjacent layers of the integral modular catalyst are arranged symmetrically; The hydrogenation reactor II is a gas-liquid countercurrent reactor structure, including a gas deliquidation zone, a rapid mass transfer reaction zone and a liquid degassing zone which are sequentially connected from top to bottom; a liquid feed port II connected to the liquid discharge port I is arranged between the gas deliquidation zone and the rapid mass transfer reaction zone; a gas feed port II connected to the gas discharge port I is arranged between the rapid mass transfer reaction zone and the liquid degassing zone; a gas discharge port II is arranged above the gas deliquidation zone; and a liquid discharge port II is arranged below the liquid degassing zone.

2. The reverse / cross-flow hydrogenation reaction device according to claim 1, characterized in that: The diameters of the gas-liquid degassing section, the gas-liquid counter / cross-flow mass transfer enhancement section and the liquid degassing section are the same or different; The height-to-diameter ratio of the hydrogenation reactor I is 0.5 to 5:1, preferably 1 to 3:1; The diameters of the gas deliquid zone, the rapid mass transfer reaction zone and the liquid degassing zone are the same or different; The height-to-diameter ratio of the hydrogenation reactor II is 1 to 15:1, preferably 3 to 8:1; The height-to-diameter ratio of the hydrogenation reactor I is smaller than the height-to-diameter ratio of the hydrogenation reactor II; The effective volume of the hydrogenation reactor I is greater than the effective volume of the hydrogenation reactor II. Furthermore, the ratio of the effective volume of the hydrogenation reactor I to the effective volume of the hydrogenation reactor II is greater than 1:1 and does not exceed 100:1, preferably 2 to 20:1; the effective volume is defined as the volume of the catalyst loaded in the reactor; The rapid mass transfer reaction zone is filled with catalyst; the catalyst filled in the rapid mass transfer reaction zone is a non-integrated modular catalyst, the catalyst bed void ratio is 50% to 95%, preferably 60% to 90%, the catalyst particle size is 1 to 3 mm, and the catalyst bulk density is 0.8 to 1.1 g / mL.

3. The reverse / cross-flow hydrogenation reaction device according to claim 1, characterized in that: The outer frame includes a supporting grid, a pressing grid, an external frame and interconnected parts; the supporting grid and the pressing grid are horizontally arranged, respectively located at the lower and upper parts of the catalyst unit module body; the external frame is vertically arranged, located outside the catalyst unit module body; the supporting grid and the hydrogenation reactor I are fixed welding structures, and the supporting grid, the pressing grid and the external frame are movable connection structures.

4. The reverse / cross-flow hydrogenation reaction device according to claim 1, characterized in that: The circular gap ratio of the integral modular catalyst circular gap structure is 0.5% to 50%, preferably 1% to 10%; the circular gap ratio is defined as the ratio of the area of ​​the gap on the unit circle to the total area of ​​the circle.

5. The reverse / cross-flow hydrogenation reaction device according to claim 1, characterized in that: The gas-liquid counter / cross mass transfer enhancement section is filled with 2 to 100 layers, preferably 10 to 50 layers, of integral modular catalyst; The height of the single-layer integral modular catalyst is 50 to 1500 mm, preferably 100 to 600 mm; The through hole size on the surface of the integral modular catalyst is 1 mm×1 mm to 10 mm×10 mm, preferably 3 mm×3 mm to 8 mm×8 mm.

6. The reverse / cross-flow hydrogenation reaction device according to claim 1, characterized in that: Each layer of the overall modular catalyst includes one or more catalyst unit module bodies; The catalyst unit module body is provided with an array of honeycomb pore structures, which are interconnected; The bulk density of the catalyst unit module body is 0.6 to 0.9 g / mL.

7. Use of the counter-current / cross-current hydrogenation reaction device according to any one of claims 1 to 6 in hydrogenation reactions.

8. A hydrogenation method, characterized in that: A reverse / cross-flow 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 The raw material liquid enters the hydrogenation reactor I from the liquid feed port I, and the hydrogen enters the hydrogenation reactor I from the gas feed port I. The raw material liquid and the hydrogen undergo a reverse / cross-flow hydrogenation reaction in the hydrogenation reactor I. After the reaction is completed, the remaining hydrogen leaves from the gas discharge port I and partially or completely enters the hydrogenation reactor II. After the reaction is completed, the reaction liquid leaves from the liquid discharge port I and partially or completely enters the hydrogenation reactor II. Part or all of the remaining hydrogen discharged from the gas outlet I of the hydrogenation reactor I enters the hydrogenation reactor II through the gas feed port II with or without additional hydrogen supplementation, and part or all of the reaction liquid discharged from the liquid outlet I of the hydrogenation reactor I enters the hydrogenation reactor II through the liquid feed port II. The two undergo a countercurrent hydrogenation reaction in the hydrogenation reactor II, and the remaining hydrogen after the reaction is completed leaves from the gas outlet II, and the reaction liquid after the reaction is completed leaves from the liquid outlet II.

10. The hydrogenation method according to claim 9, characterized in that: The sum of the hydrogenation reaction conversion rates of the hydrogenation reactor I and the hydrogenation reactor II is 100%, wherein the hydrogenation reaction conversion rate of the hydrogenation reactor I is 50% to 99%, preferably 60% to 90%, and the hydrogenation reaction conversion rate of the hydrogenation reactor II is 1% to 50%, preferably 10% to 40%, and the hydrogenation reaction conversion rate of the hydrogenation reactor I is higher than the hydrogenation reaction conversion rate of the hydrogenation reactor II; The feed ratio of hydrogen to raw liquid in hydrogenation reactor I is 1 to 1500 Nm 3 / h:1m 3 / h, preferably 50 to 500 Nm 3 / h:1m 3 / h; The feed ratio of hydrogen to reaction liquid in hydrogenation reactor II is 1 to 500 Nm 3 / h:1m 3 / h, preferably 2 to 200 Nm 3 / h:1m 3 / h; The hydrogenation method uses hydrogen with a purity greater than 90 vol%, preferably more than 99.9 vol% pure hydrogen; The process conditions of hydrogenation reactor I and hydrogenation reactor II are respectively and independently as follows: reaction temperature is room temperature to 500°C, reaction pressure is 0.1 to 20 MPaG, liquid hourly volume space velocity is 0.1 to 20 h -1 .

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