A reverse / cross flow hydrogenation reaction device and application thereof

Abstract

The application discloses a reverse / staggered flow hydrogenation reaction device and application thereof. The reverse / staggered flow hydrogenation reaction device comprises a hydrogenation reactor I and a hydrogenation reactor II; the hydrogenation reactor I is a gas-liquid reverse / staggered flow reactor structure, and comprises a gas liquid separation section, a gas-liquid reverse / staggered flow mass transfer intensification section and a liquid gas separation section which are sequentially and communicatively arranged from top to bottom; the gas-liquid reverse / staggered flow mass transfer intensification section is filled with one or more layers of integral modular catalysts, each layer of the integral modular catalysts comprises a catalyst unit module body and an outer frame for fixing and surrounding the catalyst unit module body; the outer frame is a circular gap structure, so that the catalyst unit module body in the outer frame is not completely filled on the cross section of the hydrogenation reactor I, and an arc-shaped gap is left on one side as a liquid descending channel, and the arc-shaped gap position centers of two adjacent layers of the integral modular catalysts are symmetrically arranged; and the hydrogenation reactor II is a gas-liquid reverse flow reactor structure.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogenation, in particular to a reverse / staggered flow hydrogenation reaction device and application thereof. BACKGROUND

[0002] Hydrogenation technology is widely used in the fields of oil refining, chemical industry, bio-chemical industry, food and medicine, etc. It is a process in which certain components containing unsaturated groups in raw materials are made to generate target products through hydrogenation reaction under the atmosphere of hydrogen and catalyst.

[0003] Fixed-bed catalytic hydrogenation can be divided into upflow (downward feeding) and downflow (upward feeding) according to the overall feeding direction of the material, and the downflow (upward feeding) is widely used due to its wide application range, that is, the traditional gas-liquid co-current trickle bed hydrogenation process is generally used in fixed-bed hydrogenation, and the gas-liquid co-current passes through the fixed catalyst bed during the reaction process, and the catalytic hydrogenation reaction is completed. Due to the gas-liquid co-current hydrogenation process in the fixed bed, the liquid passes through the catalyst bed in the form of liquid film, which easily leads to uneven liquid distribution, channeling and short circuiting, thereby reducing the utilization rate of the catalyst and the reaction rate. Therefore, in order to ensure the reaction conversion rate and selectivity, relatively harsh reaction conditions such as high hydrogen liquid ratio, long reaction residence time, high temperature and hydrogen partial pressure are generally required, which not only increases the investment and energy consumption of the device, but also has problems such as low reaction efficiency, low catalyst utilization rate, uneven reaction, and many side reactions. With the further improvement of the demand for high efficiency and energy saving of hydrogenation devices, higher requirements are put forward for the fixed-bed hydrogenation reaction process. Here, the gas-liquid countercurrent hydrogenation not only can improve the hydrogenation reaction efficiency, increase the catalyst utilization rate, and reduce the energy consumption and investment, but also becomes an important development direction of the fixed-bed hydrogenation reaction process.

[0004] Patent CN102041063B proposes a method for deep desulfurization of diesel, which is diesel feedstock and hydrogen first through gas-liquid countercurrent hydrogenation reaction zone, gas-liquid countercurrent hydrogenation reaction zone effluent into gas-liquid co-current hydrogenation reaction zone, gas-liquid co-current hydrogenation reaction zone using gas-liquid co-current downward flow operation mode, wherein the gas-liquid countercurrent hydrogenation reaction zone uses Mo-Co type hydrogenation catalyst, gas-liquid co-current hydrogenation reaction zone using Mo-Ni type hydrogenation catalyst or W-Mo-Ni type hydrogenation catalyst. Patent CN101343563B proposes a method for hydrogenation of light hydrocarbons, which adopts a series connection of a countercurrent hydrogenation reactor and a conventional co-current hydrogenation reactor. The feedstock enters the flash zone of the countercurrent hydrogenation reactor at a lower temperature, the gas-phase hydrocarbons flow upward to perform diene and mercaptan to sulfide reaction and diene hydrogenation reaction in the upper part of the countercurrent reactor, the high-boiling sulfides generated in the upper part of the reaction and the liquid-phase hydrocarbons after flashing of the feedstock flow downward together, and the thiophene sulfur and olefins perform alkylation reaction; hydrogen gas 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, heated and then enters the co-current hydrogenation reactor to perform deep hydrogenation desulfurization, selective cracking or isomerization reaction. Patent CN103805240B proposes a low-cost combined hydrofining method for oil products, which includes: first, mixing hydrogen into liquid-phase material, mixing the hydrogen-dissolved liquid-phase material into a liquid-phase hydrogenation reactor to perform reaction, the material after the liquid-phase hydrogenation reaction enters a 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 part of the liquid product after the reaction is recycled to the front of the liquid-phase hydrogenation reactor, and the rest is used as hydrogenation product. The above-mentioned invention methods are all simple changes of the first hydrogenation reactor in the hydrogenation process from the conventional gas-liquid co-current reactor to the gas-liquid countercurrent reactor, without improving the internal structure of the reactor and the catalyst loading mode, etc. In fact, the internal structure, material contact mode and catalyst loading mode of the countercurrent hydrogenation reactor and the co-current hydrogenation reactor are essentially different, and only simple changes cannot achieve the application effect of the gas-liquid countercurrent reactor.

[0005] Patent CN102041069B proposes a gas-liquid countercurrent hydrogenation method for diesel desulfurization, denitrification and aromatic saturation, which passes hydrogen and diesel feedstock through the catalyst bed in a countercurrent manner under diesel fraction hydroprocessing conditions. The reactor is divided into at least two reaction zones, each reaction zone is composed of at least one hydrogenation catalyst bed; the diameter of the reactor increases from the lower reaction zone to the upper reaction zone; a liquid accumulation zone is arranged at the junction of at least one reaction zone, and a liquid accumulation outlet pipeline is arranged at the bottom or side of the liquid accumulation zone to guide the liquid in the liquid accumulation zone into the lower reaction zone of the reactor as a cooling stream. The invention method only improves the internal structure of the countercurrent reactor from the perspective of adjusting the flow state of the material, and does not fully consider the catalyst loading mode and mass transfer process strengthening in the countercurrent reactor.

[0006] In summary, the gas-liquid countercurrent hydrogenation reactor and the gas-liquid cocurrent hydrogenation reactor are different in essence in terms of gas-liquid contact mass transfer forms, reactor structures and catalyst loading modes and the like, and most of the existing gas-liquid countercurrent hydrogenation processes are focused on process flow improvement, and only a few are slightly improved in the internal structure of the reactor. On the one hand, the hydrogenation reaction process is not effectively strengthened, and on the other hand, the problems of local hot spots and easy coking of catalysts in the conventional reaction process are not solved. 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 to the process intensification of the gas-liquid countercurrent hydrogenation process. SUMMARY

[0007] In view of the above technical problems and the deficiencies in the field, the present application provides an inverse / misalignment flow hydrogenation reaction device and its application. The present application greatly strengthens the mass transfer and heat transfer of the hydrogenation reaction process through the two-stage special structure hydrogenation reactor and the series coupling between them, can realize continuous and efficient hydrogenation conversion under more moderate conditions, solve the problems of uneven reaction, easy to produce local hot spots, catalyst easy to coking and other problems in the conventional hydrogenation reaction process, improve the hydrogenation reaction conversion rate and selectivity, prolong the service life of the catalyst, and reduce the energy consumption of the device.

[0008] [1] An inverse / misalignment flow hydrogenation reaction device, comprising a hydrogenation reactor I and a hydrogenation reactor II;

[0009] The hydrogenation reactor I is a gas-liquid countercurrent / misalignment flow reactor structure, comprising a gas-liquid separation section, a gas-liquid countercurrent / misalignment flow mass transfer intensification section and a liquid-gas separation section which are sequentially and communicatively arranged from top to bottom; a liquid inlet I is arranged between the gas-liquid separation section and the gas-liquid countercurrent / misalignment flow mass transfer intensification section; a gas inlet I is arranged between the gas-liquid countercurrent / misalignment flow mass transfer intensification section and the liquid-gas separation section; a gas outlet I is arranged above the gas-liquid separation section; a liquid outlet I is arranged below the liquid-gas separation section; the gas-liquid countercurrent / misalignment flow mass transfer intensification section is filled with one or more layers of integral modular catalyst, each layer of integral modular catalyst comprises a catalyst unit module body and an outer frame for fixing and enclosing the catalyst unit module body; the outer frame is a circular gap structure, so that the catalyst unit module body in the outer frame does not completely fill the cross section of the hydrogenation reactor I, but leaves an arc-shaped gap on one side as a liquid descending channel, and the arc-shaped gap positions of the upper and lower adjacent two layers of integral modular catalyst are centrally symmetrically arranged, so that the special structure is arranged to guide the path of the gas-liquid mass transfer process, so that the gas-liquid contact in the hydrogenation reactor I simultaneously performs countercurrent and misalignment flow mass transfer, and plays a role in intensifying mass transfer and heat transfer;

[0010] The hydrogenation reactor II is a gas-liquid countercurrent reactor structure, comprising a gas-liquid separation zone, a fast mass transfer reaction zone and a liquid degassing zone which are sequentially connected from top to bottom; a liquid inlet II connected with the liquid outlet I is arranged between the gas-liquid separation zone and the fast mass transfer reaction zone; a gas inlet II connected with the gas outlet I is arranged between the fast mass transfer reaction zone and the liquid degassing zone; the gas outlet II is arranged above the gas-liquid separation zone; and the liquid outlet II is arranged below the liquid degassing zone.

[0011] The diameter of the gas-liquid separation zone, the fast mass transfer reaction zone and the liquid degassing zone of the reverse / staggered flow hydrogenation reaction device can be the same or different, preferably the same.

[0012] The height-diameter ratio of the hydrogenation reactor I of the reverse / staggered flow hydrogenation reaction device can be 0.5-5:1, preferably 1-3:1, for example 2:1, 2.5:1, 3:1, etc.

[0013] The diameter of the gas-liquid separation zone, the fast mass transfer reaction zone and the liquid degassing zone of the reverse / staggered flow hydrogenation reaction device can be the same or different, preferably the same.

[0014] The height-diameter ratio of the hydrogenation reactor II of the reverse / staggered flow hydrogenation reaction device can be 1-15:1, preferably 3-8:1, for example 6:1, 5:1, etc.

[0015] In some embodiments, the height-diameter ratio of the hydrogenation reactor I of the reverse / staggered flow hydrogenation reaction device is less than the height-diameter ratio of the hydrogenation reactor II.

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

[0017] The fast mass transfer reaction zone of the reverse / staggered flow hydrogenation reaction device can be filled with catalyst. Further, the catalyst filled in the fast mass transfer reaction zone can be a non-integral modular catalyst, the void fraction of the catalyst bed can be 50%-95%, preferably 60%-90%, for example 76.2%, 78.2%, 81.5%, etc., the catalyst particle size can be 1-3 mm, for example 1.2-1.5 mm, 2.5-3.0 mm, etc., and the catalyst bulk density can be 0.8-1.1 g / mL, for example 0.88-1.00 g / mL, 0.82-1.03 g / mL, etc.

[0018] The outer frame can comprise a support grid, a compression grid, an outer frame and an interconnecting part; the support grid and the compression grid can be horizontally arranged and located at the lower part and the upper part of the catalyst unit module body respectively; the outer frame can be vertically arranged and located outside the catalyst unit module body; the support grid and the hydrogenation reactor I can be fixedly welded; the support grid, the compression grid and the outer frame can be movably connected.

[0019] The smaller the circular defect rate is, the longer the gas-liquid countercurrent mass transfer path is, the higher the mass transfer intensity is, but the greater the pressure drop is; the greater the circular defect rate is, the shorter the gas-liquid countercurrent mass transfer path is, the lower the mass transfer intensity is, but the smaller the pressure drop is. The circular defect rate of the whole modularized catalyst circular defect structure of the countercurrent / crossflow hydrogenation reaction device is preferably 0.5% to 50%, and more preferably 1% to 10%, for example, 5.0%, 6.2%, 7.5% and the like. The circular defect rate is defined as the ratio of the area of the notch on the unit circle to the total area of the circle.

[0020] The gas-liquid countercurrent / crossflow mass transfer intensification section of the countercurrent / crossflow hydrogenation reaction device can be filled with 2 to 100 layers, preferably 10 to 50 layers (for example, 18 layers, 25 layers, 35 layers and the like) of the whole modularized catalyst.

[0021] The height of the single layer of the whole modularized catalyst can be 50 to 1500 mm, and preferably 100 to 600 mm, for example, 450 mm and the like.

[0022] The size of the through hole on the surface of the whole modularized catalyst can be 1 mm x 1 mm to 10 mm x 10 mm, and preferably 3 mm x 3 mm to 8 mm x 8 mm.

[0023] Each layer of the whole modularized catalyst can comprise one or more catalyst unit module bodies.

[0024] The shape of the catalyst unit module body can be any one of a cylindrical shape, a rectangular shape, a square shape, a diamond shape, a polygonal shape and the like, and is preferably a rectangular shape.

[0025] The catalyst unit module body can be provided with an array of honeycomb hole structures, which are interconnected, so as to increase the gas-liquid mass transfer contact area and facilitate the diffusion flow and mass transfer of the material.

[0026] The bulk density of the catalyst unit module body can be 0.6 to 0.9 g / mL, for example, 0.68 to 0.82 g / mL, 0.73 to 0.85 g / mL and the like.

[0027] The catalyst unit module body of the reverse / staggered flow hydrogenation reaction device is generally composed of a monolithic honeycomb matrix, a coating material and an active component; in the preparation process, a monolithic honeycomb is used as the matrix, a high specific surface coating and an active component are loaded by a step-by-step impregnation method, and the impregnation thickness of the active component can be controlled by adjusting the coating amount; the monolithic modular catalyst can generally be a commercially available product or prepared according to the conventional knowledge in the field.

[0028] In the hydrogenation reactor II, the rapid mass transfer reaction zone is generally filled with a supported catalyst, wherein the catalyst carrier can be one or more of SiO2, Al2O3, SiO2-Al2O3, TiO2, activated carbon, MgO, molecular sieve, etc.; the catalyst shape can be one or more of spherical, strip-shaped, trilobal, tooth spherical, etc.; the catalyst can be a commercially available product or prepared according to the conventional knowledge in the field.

[0029] The gas-liquid separation section and the gas-liquid separation zone of the reverse / staggered flow hydrogenation reaction device can be independently provided with a component having a gas-liquid separation function for gas-liquid separation; the component having a gas-liquid separation function can be one or more of a baffle structure, a cyclone / centrifugal structure, a packing and a wire mesh structure.

[0030] The liquid-gas separation section and the liquid-gas separation zone of the reverse / staggered flow hydrogenation reaction device can be independently provided with a liquid level control and a certain liquid level height to maintain sufficient residence time of the liquid to realize liquid-gas separation, and can be internally provided with or without a component having a liquid-gas separation function.

[0031] The reverse / staggered flow hydrogenation reaction device can include a heat removal device between the hydrogenation reactor I and the hydrogenation reactor II for removing heat from the reaction liquid product of the hydrogenation reactor I and adjusting the required reaction temperature of the material entering the hydrogenation reactor II; the heat removal device can be a heat exchanger, an air cooler or a water cooler, etc.

[0032] The remaining hydrogen of the hydrogenation reactor I of the reverse / staggered flow hydrogenation reaction device can be all or part of the hydrogen source of the hydrogenation reactor II, or a supplemental hydrogen pipeline can be provided in the hydrogenation reactor II to supplement the hydrogen required by the hydrogenation reactor II.

[0033] The catalysts loaded in the gas-liquid reverse / staggered flow mass transfer enhancement section of the hydrogenation reactor I and the rapid mass transfer reaction zone of the hydrogenation reactor II can be catalysts with hydrogenation function; the hydrogenation catalysts can be selected according to the type of hydrogenation reaction, such as any one or more of hydrogenation saturation catalyst, hydrogenation desulfurization catalyst, hydrogenation denitrification catalyst, hydrogenation demetallization catalyst, hydrogenation deoxygenation catalyst, hydrogenation cracking catalyst, aromatic hydrocarbon hydrogenation saturation catalyst, etc.

[0034] [2] The use of the reverse / staggered flow hydrogenation reaction device according to [1] in a hydrogenation reaction.

[0035] The reverse / staggered flow hydrogenation reaction device of the present application is suitable for a variety of raw materials in the fields of petroleum chemical industry, medicine, food, etc. that can undergo hydrogenation reaction with hydrogen, such as crude oil, gasoline, kerosene, diesel, residual oil, heavy oil, wax oil, lubricating oil, deasphalted oil, biodiesel, animal or vegetable oil, coal tar, anthracene oil, etc. and secondary processed oil; and a variety of raw materials in the fields of chemical industry, medicine, food, etc. that can undergo hydrogenation reaction, such as olefin hydrogenation, alkyne hydrogenation, aldehyde compound hydrogenation, ketone compound hydrogenation, ester compound hydrogenation, nitro compound hydrogenation, carbonyl compound hydrogenation, nitrile compound hydrogenation, etc.

[0036] [3] A hydrogenation method using the reverse / staggered flow hydrogenation reaction device according to [1].

[0037] In some embodiments, in the hydrogenation method, the raw material liquid enters the hydrogenation reactor I from the liquid feed port I, hydrogen enters the hydrogenation reactor I from the gas feed port I, the raw material liquid and hydrogen undergo reverse / staggered flow hydrogenation reaction in the hydrogenation reactor I, the remaining hydrogen after the reaction is completed exits from the gas discharge port I, part or all of which enters the hydrogenation reactor II, and the reaction liquid after the reaction is completed exits from the liquid discharge port I, part or all of which enters the hydrogenation reactor II.

[0038] Part or all of the remaining hydrogen discharged from the gas discharge port I of the hydrogenation reactor I enters the hydrogenation reactor II through the gas feed port II with or without additional hydrogen, and part or all of the reaction liquid discharged from the liquid discharge port I of the hydrogenation reactor I enters the hydrogenation reactor II through the liquid feed port II, and the two undergo reverse flow hydrogenation reaction in the hydrogenation reactor II, the remaining hydrogen after the reaction is completed exits from the gas discharge port II, and the reaction liquid after the reaction is completed exits from the liquid discharge port II.

[0039] In the hydrogenation method, the hydrogen 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, and in principle, the total hydrogen 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 the hydrogenation reactor I and the hydrogenation reactor II is 100%, wherein the hydrogenation reaction conversion rate of the hydrogenation reactor I can be 50% to 99%, preferably 60% to 90%, the hydrogenation reaction conversion rate of the hydrogenation reactor II can be 1% to 50%, preferably 10% to 40%, and the hydrogenation reaction conversion rate of the hydrogenation reactor I is higher than that of the hydrogenation reactor II.

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

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

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

[0044] The process conditions of hydrogenation reactor I and hydrogenation reactor II in the hydrogenation method can independently include: reaction temperature of normal temperature-500℃, reaction pressure of 0.1-20 MPaG, liquid hourly space velocity of 0.1-20 h -1 .

[0045] In the present application, the liquid feed in hydrogenation reactor I is the pre-reaction material, which has high raw material concentration, and is prone to cause problems such as uneven reaction, concentrated heat release, poor selectivity, etc.; the liquid feed in hydrogenation reactor II is the post-reaction material, which has low raw material concentration and slow reaction rate, so more severe reaction conditions (such as higher temperature and pressure, lower space velocity) are needed to achieve ideal conversion rate, and it is more prone to problems such as catalyst coking and more side reactions caused by long local residence time. (Note: The pre-reaction stage described herein refers to the stage in which the concentration of the reaction substrate in the raw material liquid in the reactor is ≥ the concentration of the target product, and the post-reaction stage refers to the reaction stage in which the concentration of the reaction substrate in the raw material liquid in the reactor is < the concentration of the target product.)

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

[0047] (1) By setting the special structure and reaction mass transfer path guide of hydrogenation reactor I, on the one hand, the hydrogenation reactor I can simultaneously perform continuous gas-liquid countercurrent and gas-liquid cross-flow contact mass transfer, which greatly enhances the mass transfer, on the other hand, the use of integrated modular catalyst, catalyst loading method and the through hole set in the catalyst is more conducive to the diffusion flow of the material, thereby achieving better mass and heat transfer effect, especially suitable for the system with high concentration of raw material substrate in the pre-reaction stage, which can achieve high conversion rate and selectivity under mild conditions.

[0048] (2) Hydrogenation reactor I is compared with hydrogenation reactor II, and a proper smaller height-diameter ratio is arranged, so that liquid material has a longer radial flow distance in each catalyst bed, and the advantages of gas-liquid cross flow mass transfer are fully exerted, that is, sufficient radial flow of liquid material and gas-liquid cross flow contact can make the reactor temperature be more evenly distributed along the radial direction, so that the reaction rate is faster, and problems such as concentrated reaction heat release, local hot spots, many side reactions, and catalyst coking are solved.

[0049] (3) Hydrogenation reactor II is compared with hydrogenation reactor I, and a proper larger height-diameter ratio is arranged, mainly based on the fact that the material in hydrogenation reactor II is the post-reaction material, the concentration of the raw material substrate is low, and the reaction rate is slow, and harsh reaction conditions (such as higher temperature) are generally required to achieve an ideal conversion rate. Here, by arranging a large height-diameter ratio reactor, on the one hand, the passing rate of the material on the catalyst surface can be improved, and the formed liquid film can be thinner, thereby playing a role in strengthening mass transfer, and on the other hand, high-voidage catalyst is arranged, which maximizes the reduction or even elimination of local residence of liquid on the catalyst surface, prevents the occurrence of phenomena such as partial flow and channeling, and thereby solves problems such as catalyst bed coking and easy deactivation.

[0050] (4) By arranging the structure of hydrogenation reactor I and reactor II for the pre-reaction material and the post-reaction material respectively, and the material flow mode suitable for the reaction characteristics of each material, the reactor I and reactor II are connected in series, and the hydrogenation reaction occurs in turn, the two-stage reactions are coupled with each other, which ensures the efficient conversion of the entire hydrogenation reaction, and makes the reaction more uniform, and greatly reduces the side reactions. BRIEF DESCRIPTION OF DRAWINGS

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

[0052] The application will be further described below in conjunction with the drawings and specific embodiments. It should be understood that these embodiments are only used to illustrate the application and not to limit the scope of the application. The operation methods not specified in the following examples are usually carried out according to the conventional conditions or the conditions recommended by the manufacturers.

[0053] Reference Figure 1 A reverse / cross flow hydrogenation reaction device includes hydrogenation reactor I 5 and hydrogenation reactor II 15 connected in series and pipelines connected thereto.

[0054] The hydrogenation reactor I 5 is a gas-liquid counter / cross flow reactor structure, comprising a gas-liquid separation section 8, a gas-liquid counter / cross flow mass transfer enhancement section and a liquid-gas separation section 9 arranged in sequence from top to bottom. The gas-liquid separation section 8, the gas-liquid counter / cross flow mass transfer enhancement section and the liquid-gas separation section 9 have the same diameter. A liquid inlet I is arranged between the gas-liquid separation section 8 and the gas-liquid counter / cross flow mass transfer enhancement section. A gas inlet I is arranged between the gas-liquid counter / cross flow mass transfer enhancement section and the liquid-gas separation section 9. A gas outlet I is arranged above the gas-liquid separation section 8. A liquid outlet I is arranged below the liquid-gas separation section 9. The gas-liquid counter / cross flow mass transfer enhancement section is filled with one or more layers of the integral modular catalyst 10. Each layer of the integral modular catalyst 10 comprises a catalyst unit module body 11 and an outer frame for fixing and enclosing the catalyst unit module body 11. The outer frame comprises a support grid 12, a compression grid 13, an outer frame 14 and an interconnecting component. The support grid 12 and the compression grid 13 are arranged horizontally and are located at the lower part and the upper part of the catalyst unit module body 11 respectively. The outer frame 14 is arranged vertically and is located outside the catalyst unit module body 11. The support grid 12 is fixedly welded with the hydrogenation reactor I, and the support grid 12, the compression grid 13 and the outer frame 14 are movably connected. The outer frame is a circular segment structure, so that the catalyst unit module bodies 11 in the outer frame do not completely fill the cross section of the hydrogenation reactor I, but leave an arc-shaped gap on one side as a liquid descending channel, and the arc-shaped gap positions of the upper and lower adjacent two layers of the integral modular catalyst 10 are arranged in a center-symmetrical manner.

[0055] The hydrogenation reactor II 15 is a gas-liquid counter flow reactor structure, comprising a gas-liquid separation zone 21, a rapid mass transfer reaction zone and a liquid-gas separation zone 22 arranged in sequence from top to bottom. The gas-liquid separation zone 21, the rapid mass transfer reaction zone and the liquid-gas separation zone 22 have the same diameter. A liquid inlet II connected with the liquid outlet I is arranged between the gas-liquid separation zone 21 and the rapid mass transfer reaction zone. A gas inlet II connected with the gas outlet I is arranged between the rapid mass transfer reaction zone and the liquid-gas separation zone 22. A gas outlet II is arranged above the gas-liquid separation zone 21. A liquid outlet II is arranged below the liquid-gas separation zone 22. The rapid mass transfer reaction zone is filled with the catalyst 20. The effective volume of the hydrogenation reactor I 5 is greater than that of the hydrogenation reactor II 15.

[0056] A hydrogenation method, which uses the counter / cross flow hydrogenation reaction device as shown in Figure 1 The hydrogenation method comprises the following steps:

[0057] Firstly, liquid feed 1 and hydrogen 2 are introduced into liquid feed inlet I and gas feed inlet I of hydrogenation reactor I 5 respectively, liquid feed 1 is uniformly distributed by liquid feed distributor 6 and then enters the whole modular catalyst 10 to carry out reverse / cross flow hydrogenation reaction with the gas rising from the lower part, the remaining hydrogen after the reaction is removed from hydrogenation reactor I 5 after being removed from liquid by gas-liquid separation section 8, and the remaining gas 3 of hydrogenation reactor I 5 enters hydrogenation reactor I 15; hydrogen 2 is uniformly distributed by hydrogen distributor 7 and then enters the whole modular catalyst 10 to carry out reverse / cross flow hydrogenation reaction with the liquid descending from the upper part, the reaction product is removed from hydrogenation reactor I 5 after being removed from liquid by liquid-gas separation section 9, and the reaction liquid product 4 of hydrogenation reactor I 5 enters hydrogenation reactor II 15.

[0058] In hydrogenation reactor II 15, liquid feed 1 and hydrogen 2 are introduced into liquid feed inlet II and gas feed inlet II of hydrogenation reactor II 15 respectively, the top feed is uniformly distributed by liquid feed distributor 18 and then enters catalyst 20 bed to carry out reverse flow hydrogenation reaction with the gas rising from the lower part, the remaining hydrogen after the reaction is removed from hydrogenation reactor II 15 after being removed from liquid by gas-liquid separation section 21, and the remaining gas 16 of hydrogenation reactor II 15 is removed; the remaining gas 3 is uniformly distributed by hydrogen distributor 19 and then enters catalyst 20 bed to carry out reverse flow hydrogenation reaction with the liquid descending from the upper part, and the reaction product 17 is removed after being removed from liquid by liquid-gas separation section 22.

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

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

[0061] Item Feed oil Density, g / cm 3 ]]> 0.836 Viscosity, mm 2 / s]] 764.7 Sulfur, wt% 0.62 Nitrogen, pg / g 103 Distillation range, °C IBP / 5% 202 / 238 10％ / 30％ 258 / 269 50％ / 70％ 290 / 301 90％ / 95％ 322 / 334 EBP 353

[0062] Table 2 Physicochemical indexes of straight-run diesel hydrogenation catalyst

[0063]

[0064] Table 3 Biomass sugar (glucose) solution feedstock

[0065] Item Indicator Property Colorless transparent liquid Concentration, mol / L 1.5

[0066] Table 4 Properties of biomass sugar (glucose) solution hydrogenation catalyst

[0067]

[0068] Comparative Example 1

[0069] A conventional fixed bed series hydrogenation process was adopted, and hydrogenation reactor I and hydrogenation reactor II were both gas-liquid countercurrent hydrogenation reactors; the height-diameter ratio of hydrogenation reactor I was 2.0, and the height-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 by using the device respectively. Hydrogenation reactor I and hydrogenation reactor II were both filled with non-integral modular catalysts corresponding to their respective reactions.

[0070] First, the raw material was introduced into the top of hydrogenation reactor I after being adjusted to the inlet temperature of hydrogenation reactor I, and hydrogen was introduced into the bottom of hydrogenation reactor I after being adjusted to the inlet temperature of hydrogenation reactor I, and the countercurrent hydrogenation reaction occurred in hydrogenation reactor I to obtain liquid product and residual gas; the liquid product was introduced into the top of hydrogenation reactor II after being adjusted to the inlet temperature of hydrogenation reactor II, and the residual gas was introduced into the bottom of hydrogenation reactor II after being adjusted to the inlet temperature of hydrogenation reactor II, and the countercurrent hydrogenation reaction continued to occur, and then the hydrogenation reaction was completed and the reaction product was discharged.

[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 hereinafter.

[0072] Comparative Example 2

[0073] A conventional fixed bed series hydrogenation process was adopted, and hydrogenation reactor I and hydrogenation reactor II were both gas-liquid countercurrent hydrogenation reactors; the height-diameter ratio of hydrogenation reactor I was 2.0, and the height-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 by using the device respectively. Hydrogenation reactor I and hydrogenation reactor II were both filled with non-integral modular catalysts corresponding to their respective reactions.

[0074] First, the raw material was introduced into the top of hydrogenation reactor I after being adjusted to the inlet temperature of hydrogenation reactor I, and hydrogen was introduced into the bottom of hydrogenation reactor I after being adjusted to the inlet temperature of hydrogenation reactor I, and the countercurrent hydrogenation reaction occurred in hydrogenation reactor I to obtain liquid product and residual gas; the liquid product was introduced into the top of hydrogenation reactor II after being adjusted to the inlet temperature of hydrogenation reactor II, and the residual gas was introduced into the bottom of hydrogenation reactor II after being adjusted to the inlet temperature of hydrogenation reactor II, and the countercurrent hydrogenation reaction continued to occur, and then the hydrogenation reaction was completed and the reaction product was discharged.

[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 is adopted, and the hydrogenation reactor I and the hydrogenation reactor II are both gas-liquid countercurrent hydrogenation reactors; the height-diameter ratio of the hydrogenation reactor I is 4.0, and the height-diameter ratio of the hydrogenation reactor II is 2.0. The reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation are respectively investigated under different conditions by using the device. The hydrogenation reactor I and the hydrogenation reactor II are both filled with respective non-integral modular catalysts corresponding to reactions.

[0078] Firstly, the raw material is introduced into the top of the hydrogenation reactor I after being adjusted to the inlet temperature of the hydrogenation reactor I, and hydrogen is introduced into the bottom of the hydrogenation reactor I after being adjusted to the inlet temperature of the hydrogenation reactor I, and the countercurrent hydrogenation reaction occurs in the hydrogenation reactor I, so that liquid products and residual gas are obtained; the liquid products are introduced into the top of the hydrogenation reactor II after being adjusted to the inlet temperature of the hydrogenation reactor II, and the residual gas is introduced into the bottom of the hydrogenation reactor II after being adjusted to the inlet temperature of the hydrogenation reactor II, and the countercurrent hydrogenation reaction continues to occur, and the hydrogenation reaction is completed and then the hydrogenation reaction is exited.

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

[0080] Example 1

[0081] The device and the method introduced in the specific embodiment of the present application are adopted. The height-diameter ratio of the hydrogenation reactor I is 2.5; the gas-liquid countercurrent / cross-flow mass transfer intensification section is filled with 25 layers of integral modular catalysts; the circular gap rate of the circular gap structure of the integral modular catalysts is 7.5%. The height-diameter ratio of the hydrogenation reactor II is 6:1, and the void fraction of the catalyst bed layer filled in the rapid mass transfer zone is 81.5%. The reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation are respectively investigated under different conditions by using the device.

[0082] Firstly, the raw material is introduced into the top of the hydrogenation reactor I after being adjusted to the inlet temperature of the hydrogenation reactor I, and hydrogen is introduced into the bottom of the hydrogenation reactor I after being adjusted to the inlet temperature of the hydrogenation reactor I, and the countercurrent / cross-flow hydrogenation reaction occurs in the hydrogenation reactor I, so that liquid products and residual gas are obtained; the liquid products are introduced into the top of the hydrogenation reactor II after being adjusted to the inlet temperature of the hydrogenation reactor II, and the residual gas is introduced into the bottom of the hydrogenation reactor II after being adjusted to the inlet temperature of the hydrogenation reactor II, and the countercurrent hydrogenation reaction continues to occur, and the hydrogenation reaction is completed and then the hydrogenation reaction is exited.

[0083] The operation conditions of the hydrogenation reactor I and the 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 introduced in the embodiment of the present application are used, the process flow is same as example 1, and the difference lies in that the height-diameter ratio of the hydrogenation reactor I is 2.0; 35 layers of the integral modular catalyst are filled in the mass transfer enhancement zone; the circular notch rate of the circular notch structure of the integral modular catalyst is 5.0%. The height-diameter ratio of the hydrogenation reactor II is 6:1, and the catalyst bed layer porosity filled in the rapid mass transfer zone is 76.2%. The reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation are respectively investigated under different conditions by using the device.

[0086] The operation conditions of the hydrogenation reactor I and the 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 introduced in the embodiment of the present application are used, the process flow is same as example 1, and the difference lies in that the height-diameter ratio of the hydrogenation reactor I is 2.0; 35 layers of the integral modular catalyst are filled in the mass transfer enhancement zone; the circular notch rate of the circular notch structure of the integral modular catalyst is 5.0%. The height-diameter ratio of the hydrogenation reactor II is 6:1, and the catalyst bed layer porosity filled in the rapid mass transfer zone is 76.2%. The reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation are respectively investigated under different conditions by using the device.

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

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

[0091]

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

[0093]

[0094] Δt11, Δt12, Δt13: the average radial temperature difference of the upper, middle and lower in the hydrogenation reactor I;

[0095] Δt21, Δt22, Δt23: the average radial temperature difference of the upper, middle and lower in the hydrogenation reactor II.

[0096] From the effects of the embodiments and the comparative examples of the present application, it can be seen that, by using the hydrogenation reaction device and the hydrogenation method of the present application, the hydrogenation reactor I and the hydrogenation reactor II are coupled in series, the material before the reaction is reacted in the hydrogenation reactor I, and the material after the reaction is reacted in the hydrogenation reactor II. It can be seen that the average radial temperature difference of the two hydrogenation reactors is greatly reduced, the convection mass transfer and heat transfer diffusion of the material in the reaction process are effectively strengthened, the radial temperature distribution in the hydrogenation reaction process is more uniform, the problems of concentrated heat release, local hot spots and catalyst coking in the reaction process are solved, and the hydrogenation reaction conversion rate and selectivity are greatly improved.

[0097] Furthermore, it is to be understood that even though numerous characteristics and embodiments of the application have been set forth in the foregoing disclosure, the exact character it being understood that changes and modifications can be suggested to one skilled in the art, and it is intended that the application included all such changes and modifications as fall within the scope of the appended claims.

Claims

1. A reverse / cross flow hydroprocessing reactor apparatus, characterized by, The hydrogenation reactor I and the hydrogenation reactor II; the height-diameter ratio of the hydrogenation reactor I is less than that of the hydrogenation reactor II; The hydrogenation reactor I is a gas-liquid counterflow / reactive flow reactor structure, comprising a gas-liquid separation section, a gas-liquid counterflow / reactive flow mass transfer enhancement section and a liquid-gas separation section which are sequentially and communicatively arranged from top to bottom; a liquid inlet I is arranged between the gas-liquid separation section and the gas-liquid counterflow / reactive flow mass transfer enhancement section; a gas inlet I is arranged between the gas-liquid counterflow / reactive flow mass transfer enhancement section and the liquid-gas separation section; a gas outlet I is arranged above the gas-liquid separation section; a liquid outlet I is arranged below the liquid-gas separation section; the gas-liquid counterflow / reactive flow mass transfer enhancement section is filled with one or more layers of integral modular catalysts, each layer of the integral modular catalysts comprising a catalyst unit module body and an outer frame for fixing and enclosing the catalyst unit module body; the outer frame is a circular gap structure, so that the catalyst unit module body in the outer frame does not completely fill the cross section of the hydrogenation reactor I, but leaves an arc-shaped gap on one side as a liquid descending channel, and the arc-shaped gap positions of the upper and lower two layers of the integral modular catalysts are arranged in a center-symmetrical manner; The hydrogenation reactor II is a gas-liquid counterflow reactor structure, comprising a gas-liquid separation zone, a rapid mass transfer reaction zone and a liquid-gas separation zone which are sequentially and communicatively arranged from top to bottom; the rapid mass transfer reaction zone is filled with catalysts; the catalysts filled in the rapid mass transfer reaction zone are non-integral modular catalysts, and the catalyst bed porosity is 50% to 95%; a liquid inlet II connected with the liquid outlet I is arranged between the gas-liquid separation zone and the rapid mass transfer reaction zone; a gas inlet II connected with the gas outlet I is arranged between the rapid mass transfer reaction zone and the liquid-gas separation zone; a gas outlet II is arranged above the gas-liquid separation zone; a liquid outlet II is arranged below the liquid-gas separation zone.

2. The reverse / staggered flow hydrogenation reaction apparatus according to claim 1, wherein The diameters of the gas-liquid separation section, the gas-liquid counterflow / reactive flow mass transfer enhancement section and the liquid-gas separation section are the same or different; The height-diameter ratio of the hydrogenation reactor I is 0.5 to 5:1; The diameters of the gas-liquid separation zone, the rapid mass transfer reaction zone and the liquid-gas separation zone are the same or different; The height-diameter ratio of the hydrogenation reactor II is 1 to 15:1; The effective volume of the hydrogenation reactor I is greater than that of the hydrogenation reactor II; the effective volume is defined as the volume of the reactor filled with catalysts; The catalyst bed porosity of the catalysts filled in the rapid mass transfer reaction zone is 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 / staggered flow hydrogenation reaction apparatus according to claim 2, wherein The height-diameter ratio of the hydrogenation reactor I is 1 to 3:1; The height-diameter ratio of the hydrogenation reactor II is 3 to 8:1; The ratio of the effective volume of the hydrogenation reactor I to that of the hydrogenation reactor II is greater than 1:1 and does not exceed 100:

1.

4. The reverse / staggered flow hydrogenation reaction apparatus according to claim 3, wherein The ratio of the effective volume of the hydrogenation reactor I to that of the hydrogenation reactor II is 2 to 20:

1.

5. The reverse / staggered flow hydrogenation reactor of claim 1, wherein, The outer frame comprises a support grid, a compression grid, an external frame and an interconnection component; the support grid and the compression grid are horizontally arranged and located at the lower part and the upper part of the catalyst unit module body, respectively; the external frame is vertically arranged and located outside the catalyst unit module body; the support grid and the hydrogenation reactor I are fixedly welded, and the support grid, the compression grid and the external frame are movably connected.

6. The reverse / staggered flow hydrogenation reaction apparatus as claimed in claim 1, wherein The ratio of the circular segment structure of the monolithic modular catalyst is 0.5% to 50%, and the ratio of the circular segment structure of the monolithic modular catalyst is defined as the ratio of the area of the notch on the unit circle to the total area of the circle.

7. The reverse / staggered flow hydrogenation reactor of claim 6, wherein, The ratio of the circular segment structure of the monolithic modular catalyst is 1% to 10%.

8. The reverse / staggered flow hydrogenation reaction apparatus of claim 1, wherein, The gas-liquid counterflow / misflow mass transfer enhancement section is filled with 2 to 100 layers of monolithic modular catalysts; The height of a single layer of monolithic modular catalyst is 50 to 1500 mm; The size of the through hole on the surface of the monolithic modular catalyst is 1 mm x 1 mm to 10 mm x 10 mm.

9. The reverse / staggered flow hydrogenation reactor of claim 8, wherein, The gas-liquid counterflow / misflow mass transfer enhancement section is filled with 10 to 50 layers of monolithic modular catalysts; The height of a single layer of monolithic modular catalyst is 100 to 600 mm; The size of the through hole on the surface of the monolithic modular catalyst is 3 mm x 3 mm to 8 mm x 8 mm.

10. The reverse / staggered flow hydrogenation reaction apparatus of claim 1, wherein, Each layer of monolithic modular catalyst comprises one or more catalyst unit module bodies; The catalyst unit module body is provided with an array of honeycomb hole structures that are interconnected; The bulk density of the catalyst unit module body is 0.6 to 0.9 g / mL.

11. The counterflow / misflow hydrogenation reaction device according to any one of claims 1 to 10 is used in a hydrogenation reaction.

12. A hydrogenation process characterized by, The counterflow / misflow hydrogenation reaction device according to any one of claims 1 to 10 is used.

13. The hydrogenation method according to claim 12, characterized by, The raw material liquid enters the hydrogenation reactor I from the liquid inlet I, and the hydrogen enters the hydrogenation reactor I from the gas inlet I, and the raw material liquid and the hydrogen undergo counterflow / misflow hydrogenation reaction in the hydrogenation reactor I, and the remaining hydrogen after the reaction is completed exits from the gas outlet I, part or all of which enters the hydrogenation reactor II, and the reaction liquid after the reaction is completed exits from the liquid outlet I, part or all of which 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 inlet II with or without additional hydrogen, 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 inlet II, and the two undergo counterflow hydrogenation reaction in the hydrogenation reactor II, and the remaining hydrogen after the reaction is completed exits from the gas outlet II, and the reaction liquid after the reaction is completed exits from the liquid outlet II.

14. The hydrogenation method according to claim 13, characterized by, 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%, the hydrogenation reaction conversion rate of the hydrogenation reactor II is 1% to 50%, and the hydrogenation reaction conversion rate of the hydrogenation reactor I is higher than that of the hydrogenation reactor II; The hydrogen to feedstock liquid feed ratio of hydrogenation reactor I is 1 to 1500 Nm 3 / h: 1 m 3 / h; The hydrogen to feed ratio of hydrogenation reactor II is 1-500 Nm 3 / h: 1 m 3 / h; The hydrogenation method uses hydrogen with a purity of greater than 90 vol%; The process conditions of the hydrogenation reactor I and the hydrogenation reactor II independently include: the reaction temperature is normal temperature to 500°C, the reaction pressure is 0.1 to 20 MPaG, the liquid hourly space velocity is 0.1 to 20 h -1 .

15. The hydrogenation method of claim 14, wherein, The hydrogenation reaction conversion rate of the hydrogenation reactor I is 60% to 90%, and the hydrogenation reaction conversion rate of the hydrogenation reactor II is 10% to 40%; The hydrogen to feedstock liquid feed ratio of hydrogenation reactor I is 50 to 500 Nm 3 / h: 1 m 3 / h; The hydrogen to feed ratio of hydrogenation reactor II is 2-200 Nm 3 / h: 1 m 3 / h; The hydrogenation method uses hydrogen with a purity of greater than 99.9 vol%.

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