Cascade hydrogen supply reverse / cross flow hydrogenation reaction device and application thereof

Abstract

The invention discloses a cascade hydrogen supply reverse / cross flow hydrogenation reaction device and application thereof in hydrogenation reaction. The cascade hydrogen supply reverse / cross flow hydrogenation reaction device comprises a gas-liquid removal area, an upper reaction area, a lower reaction area and a liquid degassing area which are sequentially communicated from top to bottom. The upper reaction zone comprises an inner cylinder I and an annular space I located outside the inner cylinder I, the top end of the inner cylinder I is communicated with a hydrogen-containing fluid I, the bottom end is closed, a through hole I is formed in the cylinder wall and used for communicating the inner cylinder I and the annular space I, the bottom end of the annular space I is communicated with a hydrogen-containing fluid II, and the top end is closed; the lower reaction area comprises an inner cylinder II and an annular space II located on the outer side of the inner cylinder II, the top end of the annular space II is communicated with a hydrogen-containing fluid II, the bottom end of the annular space II is closed, the bottom end of the inner cylinder II is communicated with a hydrogen-containing fluid III, the top end of the inner cylinder II is closed, and a through hole II is formed in the cylinder wall and used for communicating the inner cylinder II and the annular space II; the inner cylinder I and the annular space II are filled with a monolithic catalyst; and the annular space I and the inner cylinder II are filled with a non-monolithic catalyst.

Description

Technical Field

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

[0002] Hydrogenation technology is an important process technology. Under a certain temperature and pressure, raw materials and hydrogen react through the catalytic action of catalysts to improve the quality of oil or produce specific products. It is widely used in the fields of petroleum refining, chemical industry, biochemical industry, food and medicine. Generally speaking, fixed-bed catalytic hydrogenation mostly adopts the traditional trickle bed hydrogenation process with gas-liquid co-current. During the reaction process, gas and liquid co-currently flow downward through a fixed catalyst bed to complete the catalytic hydrogenation reaction. The conventional fixed-bed gas-liquid co-current hydrogenation process has problems such as low mass transfer and heat transfer efficiency, low catalyst utilization, uneven reaction, and easy coking of catalysts. Therefore, more stringent reaction conditions are required, such as higher hydrogen-liquid ratio, longer reaction residence time, lower space velocity, higher temperature and hydrogen partial pressure, etc., resulting in high device investment and energy consumption. Fixed-bed gas-liquid countercurrent hydrogenation has the advantages of improving mass transfer and heat transfer efficiency and increasing catalyst utilization, and has become a research hotspot and important development direction for fixed-bed hydrogenation reaction technology.

[0003] Patent CN103805240B proposes a low-cost combined hydrorefining method for oil products. In this method, hydrogen is first mixed into liquid phase materials, and the liquid phase materials mixed with hydrogen are introduced into a liquid phase hydrogenation reactor for reaction. The materials after the liquid phase hydrogenation reaction enter the countercurrent reactor from the upper part of the reactor, and further react with a small amount of new hydrogen entering from the bottom of the reactor in the countercurrent reactor. 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. 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 at the junction of at least one reaction zone, and a liquid accumulation outlet pipeline is set at the bottom or side of the liquid accumulation zone to introduce the liquid in the liquid accumulation zone into the lower reaction zone of the reactor as a cooling stream. Patent application CN116948701A proposes a hydrogenation process for blended bio-oil, wherein hydrogen enters from a gas-liquid contact zone, partially passes through the gas-liquid contact zone, the gas-liquid countercurrent zone, the gas-liquid separation zone and the gas phase reaction zone in sequence, and partially exchanges heat with the liquid phase material discharged from the gas-liquid countercurrent zone and is mixed into the liquid phase reaction zone; the raw material for blending bio-oil enters from the gas-liquid separation zone, partially converts into gas phase, and enters the gas phase reaction zone together with the gas phase material from the gas-liquid countercurrent zone for hydrogenation reaction, and the gas phase reaction product flows out from the top of the reactor; the liquid phase raw material in the gas-liquid separation zone enters the gas-liquid countercurrent zone, countercurrently contacts with hydrogen and enters the gas-liquid contact zone for reaction, and the liquid phase material enters the gas-liquid contact zone downward for liquid phase hydrogenation reaction, and the liquid phase reaction product flows out from the bottom of the reactor. The overall design concept of the countercurrent hydrogenation process and reactor used in the above invention method is to simply change the feed of the conventional fixed bed hydrogenation reactor from a parallel flow state to a countercurrent flow state, without adaptively designing the internal structure of the countercurrent reactor, the catalyst loading method and the intensification of the mass transfer process, so that the countercurrent process and reactor still have problems such as low mass and heat transfer efficiency, uneven reaction, and low catalyst utilization.

[0004] Therefore, for the fixed-bed hydrogenation process, it is of great significance to develop new countercurrent hydrogenation processes and reactor structures to enhance heat transfer in the hydrogenation process, improve the hydrogenation reaction rate, reaction conversion depth and catalyst utilization, and solve problems such as concentrated heat release, uneven temperature rise, and easy coking of catalysts. Summary of the invention

[0005] In view of the above technical problems and the shortcomings in the art, the present invention provides a reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply and its application. The present invention controls the contact and mass transfer of hydrogen-containing fluid I, hydrogen-containing fluid II, and hydrogen-containing fluid III with different types of catalysts at different reaction stages by designing a special structure of the hydrogenation reaction device, so as to enhance the mass and heat transfer of the hydrogenation reaction process. On the one hand, the problems of intense heat release, uneven reaction, and easy coking of catalysts in the early stage of the hydrogenation reaction are solved, and on the other hand, the reaction rate, depth of hydrogenation reaction, and product selectivity in the later stage of the hydrogenation reaction are improved, thereby improving the overall hydrogenation reaction effect.

[0006] [1] The reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply of the present invention is a fixed bed hydrogenation reactor. Specifically:

[0007] A reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, comprising a gas deliquidation zone, an upper reaction zone, a lower reaction zone and a liquid degassing zone which are sequentially connected from top to bottom;

[0008] The upper reaction zone includes an inner tube I and an annular space I located outside the inner tube I. The top end of the inner tube I is connected to the hydrogen-containing fluid I, the bottom end is closed, and a through hole I is provided on the tube wall for connecting the inner tube I and the annular space I. The bottom end of the annular space I is connected to the hydrogen-containing fluid II, and the top end is closed;

[0009] The lower reaction zone includes an inner cylinder II and an annular space II located outside the inner cylinder II. The top of the annular space II is connected to the hydrogen-containing fluid II and the bottom is closed. The bottom of the inner cylinder II is connected to the hydrogen-containing fluid III, the top is closed, and a through hole II is provided on the cylinder wall for connecting the inner cylinder II and the annular space II.

[0010] The average density of hydrogen-containing fluid I is ≥ the average density of hydrogen-containing fluid II ≥ the average density of hydrogen-containing fluid III; the average density is defined as the sum of the mass of the gas phase and the liquid in the fluid divided by the sum of the standard volume of the gas phase and the standard volume of the liquid;

[0011] The inner cylinder I and the annular space II are filled with a monolithic catalyst; the annular space I and the inner cylinder II are filled with a non-monolithic catalyst.

[0012] In the counter / cross-flow hydrogenation reaction device with stepped hydrogen supply, a feed port for hydrogen-containing fluid I can be set between the gas deliquidation zone and the upper reaction zone, and the feed port for hydrogen-containing fluid I is connected to the top of the inner tube I and is not connected to the annular space I.

[0013] In the counter / cross-flow hydrogenation reaction device with step-wise hydrogen supply, a feed port for hydrogen-containing fluid II can be provided between the upper reaction zone and the lower reaction zone, and the feed port for hydrogen-containing fluid II is connected to the annular space I and the annular space II, but not to the inner tube I and the inner tube II.

[0014] In the counter / cross-flow hydrogenation reaction device with step-wise hydrogen supply, a feed port for hydrogen-containing fluid III can be provided between the lower reaction zone and the liquid degassing zone, and the feed port for hydrogen-containing fluid III is connected to the inner cylinder II but not to the annular space II.

[0015] In the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, a residual gas outlet can be provided at the top of the gas deliquidation zone.

[0016] In the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, a liquid reaction product outlet can be provided at the bottom of the liquid degassing zone.

[0017] In the counter / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the diameters of the gas deliquid zone, the upper reaction zone, the lower reaction zone and the liquid degassing zone may be the same or different, preferably the same.

[0018] The height-to-diameter ratio of the counter-current / cross-current hydrogenation reaction device with step-wise hydrogen supply may be 0.5 to 10:1, preferably 1 to 5:1, such as 2.5:1.

[0019] In the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the inner cylinder I and the inner cylinder II can both be cylindrical cylinders.

[0020] In the counter-flow / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the height-to-diameter ratio of the inner cylinder I can be 0.1 to 5:1, preferably 0.2 to 2:1, such as 1:1, 2:1, 3:1, etc.

[0021] In the counter / cross-flow hydrogenation reaction device with cascade hydrogen supply, the ratio of the diameter of the inner cylinder I to the diameter of the counter / cross-flow hydrogenation reaction device with cascade hydrogen supply can be 1:1.05-4, preferably 1:1.2-3, for example 1:1.5, 1:2, etc.

[0022] In the counter-current / cross-current hydrogenation reaction device with step-wise hydrogen supply, the height-to-diameter ratio of the inner cylinder II can be 1 to 20:1, preferably 2 to 8:1, such as 2:1, 4:1, etc.

[0023] For the counter / cross-flow hydrogenation reaction device with cascade hydrogen supply, the ratio of the diameter of the inner cylinder II to the diameter of the counter / cross-flow hydrogenation reaction device with cascade hydrogen supply can be 1:2-20, preferably 1:3-8, such as 1:3, 1:4, etc.

[0024] In some embodiments, in the counter-flow / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the diameter of the inner cylinder I is not less than the diameter of the inner cylinder II.

[0025] In the reverse / cross-flow hydrogenation reaction device with stepped hydrogen supply, through holes I and II realize the diffusion of materials between inner cylinder I or inner cylinder II and annular space I or annular space II. The shapes of through holes I and II can be independently circular, elliptical, teardrop-shaped, Ω-shaped, ∞-shaped, triangular, rectangular, pentagonal and above polygons, and any one or more combinations thereof, preferably circular. The apertures of through holes I and through holes II can be independently changed or not changed along the axial direction of inner cylinder I and inner cylinder II, and the change mode may include one or more combinations of increasing, decreasing, alternating large and small settings, irregular changes, and partial area closure.

[0026] In the counter / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the ratio of the area of ​​the through hole I opened in the wall of the inner cylinder I to the side area of ​​the wall of the inner cylinder I can be 1:1.5-20, preferably 1:2-10, for example 1:4.

[0027] In the counter-current / cross-current hydrogenation reaction device with step-wise hydrogen supply, the through hole I provided on the wall of the inner cylinder I may have a diameter of 0.1 to 100 mm, preferably 2 to 8 mm, such as 4 mm, 6 mm, etc.

[0028] In the counter / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the ratio of the area of ​​the through hole II opened in the wall of the inner cylinder II to the side area of ​​the wall of the inner cylinder II can be 1:1.01-50, preferably 1:1.2-5, for example 1:2, 1:3, 1:4, etc.

[0029] In the counter / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the through hole II provided on the wall of the inner cylinder II may have a diameter of 1 to 100 mm, preferably 5 to 20 mm, such as 10 mm, 12 mm, 14 mm, etc.

[0030] In some embodiments, in the counter / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the aperture of the through hole II opened in the wall of the inner cylinder II is not smaller than the aperture of the through hole I opened in the wall of the inner cylinder I.

[0031] In the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the wall between the inner cylinder I and the annular space I, and the wall between the inner cylinder II and the annular space II can be independently provided with isolation screens to prevent the non-monolithic catalyst from running away. Furthermore, the apertures of the isolation screens can be independently 10 to 100 meshes, such as 12 meshes.

[0032] In the counter / cross-flow hydrogenation reaction device with stepped hydrogen supply, the lower and upper parts of the integral catalyst bed filled with the inner cylinder I and the annular space II and the non-integrated catalyst bed filled with the annular space I and the inner cylinder II can be respectively provided with a supporting grid and a pressing grid, wherein the supporting grid of the integral catalyst bed can be a flat plate closed structure and the pressing grid can be an open structure, and the supporting grid of the non-integrated catalyst bed can be an open structure and the pressing grid can be a flat plate closed structure.

[0033] In the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the catalyst unit in the monolithic catalyst may have a shape of any one or more combinations of cylindrical, rectangular, square, rhombus, polygonal, etc., preferably rectangular.

[0034] In the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the monolithic catalyst is provided with an array-arranged, mutually interpenetrating honeycomb pore structure.

[0035] In the counter / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the through-hole sizes of the surface of the monolithic catalyst filled in the inner cylinder I and the annular space II can be independently 1mm×1mm to 10mm×10mm, preferably 3mm×3mm to 8mm×8mm.

[0036] In the counter / cross-flow hydrogenation reaction device with cascade hydrogen supply, the monolithic catalyst single layer heights filled in the inner cylinder I and the annular space II can be independently 50 to 1500 mm, preferably independently 100 to 600 mm, such as 450 mm.

[0037] In the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the porosity of the monolithic catalyst bed filled in the inner cylinder I and the annular space II can be independently 60% to 90%, preferably 70% to 80%.

[0038] The catalyst unit in the monolithic catalyst is generally composed of a monolithic honeycomb substrate, a coating material and an active component; during the preparation process, a monolithic honeycomb monomer 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 modular catalyst unit can use commercially available products as needed, or improve commercially available products as needed, or it can be prepared according to conventional knowledge in the field.

[0039] In the reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply, the inner cylinder I and the annular space II can be independently loaded with 2 to 100 layers, preferably 5 to 60 layers (e.g. 15 layers, 20 layers, 25 layers, etc.) of monolithic catalysts, which can be adjusted according to the type of hydrogenation reaction, reaction effect, etc.

[0040] In the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the ratio of the number of monolithic catalyst layers loaded in the inner cylinder I and the annular space II can be (1:10) to (10:1), preferably (1:5) to (5:1), which can be adjusted according to the type of hydrogenation reaction, reaction effect, etc.

[0041] In the counter / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the porosity of the non-integral catalyst bed filled in the annular space I and the inner cylinder II can be independently 60% to 95%, preferably 65% ​​to 85%.

[0042] In the counter / cross-flow hydrogenation reaction device with cascade hydrogen supply, the shapes of the non-monolithic catalysts loaded in the annular space I and the inner cylinder II can be independently spherical, toothed spherical, sheet-shaped, strip-shaped, clover-shaped, four-leaf clover-shaped, hollow ring, multi-hole columnar, or a combination of one or more stacking shapes.

[0043] In the counter / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the radial dimension of the cross section of the non-integral catalyst filled in the annular space I and the inner cylinder II can be 0.5 to 10 mm, preferably 1 to 6 mm.

[0044] In the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the non-integral catalyst filled in the annular space I and the inner cylinder II is generally a supported catalyst, wherein the catalyst carrier can be SiO 2 、Al 2 O 3 、SiO 2 -Al 2 O 3 、TiO 2 , activated carbon, MgO, molecular sieve, etc. The non-monolithic catalyst filled in the annular space I and the inner cylinder II can be a commercially available product as needed, or can be prepared according to conventional knowledge in the art.

[0045] In the counter / cross-flow hydrogenation reaction device with stepped hydrogen supply, material distributors can be set at the top of the inner cylinder I and the annular space II, and at the bottom of the inner cylinder II and the annular space I, wherein the material distributor at the top of the inner cylinder I can be connected to the hydrogen-containing fluid I, the material distributors at the bottom of the annular space I and the top of the annular space II can be connected to the hydrogen-containing fluid II, and the material distributor at the bottom of the inner cylinder II can be connected to the hydrogen-containing fluid III.

[0046] In the counter / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the material distributors at the top of the inner cylinder I and the annular space II, and at the bottom of the inner cylinder II and the annular space I can be independently any one or more combinations of tubular, plate, bubble, nozzle, jet, trough, disc, metal membrane tube, ceramic membrane tube, and microchannel.

[0047] In the reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply, the gas-liquid separation zone can be provided with a component with a gas-liquid separation function to perform gas-liquid separation; the component with the gas-liquid separation function can be one or more of a baffle structure, a cyclone / centrifugal structure, a filler and a wire mesh structure; the liquid degassing zone can be provided with a liquid level control and a certain liquid level height to keep the liquid for a sufficient residence time to achieve liquid degassing, and a component with a liquid degassing function can be provided inside or not.

[0048] The monolithic catalyst and the non-monolithic catalyst used in the present invention can both be catalysts with hydrogenation function, and the hydrogenation active component can be selected according to the type of hydrogenation reaction, such as any one or more of a hydrogenation saturation catalyst, a hydrodesulfurization catalyst, a hydrodenitrogenation catalyst, a hydrodemetallization catalyst, a hydrodeoxygenation catalyst, a hydrocracking catalyst, an aromatics hydrogenation saturation catalyst, etc.; the catalyst active component includes but is not limited to one or more combinations of precious metals, Co, Mo, Ni, W, Mg, Zn, rare earth elements, etc.

[0049] The active components in the monolithic catalyst and the non-monolithic catalyst used in the present invention may be the same or different; the active components and catalytic activity of the monolithic catalyst loaded in the inner cylinder I and the annular space II may be the same or different, preferably the same; similarly, the active components and catalytic activity of the non-monolithic catalyst loaded in the inner cylinder II and the annular space I may be the same or different. Here, the catalytic activity of the catalyst can be regulated during the preparation process by the size of the specific surface area of ​​the catalyst carrier, the properties of the active centers on the surface, and the number of active centers per unit surface area.

[0050] In the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, hydrogen-containing fluid I, hydrogen-containing fluid II, and hydrogen-containing fluid III can be a mixture of hydrogen-containing gas and liquid reaction raw materials. Further, hydrogen-containing fluid I, hydrogen-containing fluid II, and hydrogen-containing fluid III can be a gas-liquid mixed fluid containing nano / micron hydrogen bubbles, so that the required hydrogen source can be provided according to different stages of the reaction during the reaction, and efficient hydrogenation can be maintained throughout the process. The material flow state is not a pure liquid phase or a pure gas phase, but a gas-liquid mixture containing a small amount or a large amount of nano / micro bubbles, which is conducive to maintaining a suitable residence time and efficient contact, reducing problems such as biased flow back mixing, thereby strengthening reverse / cross-flow contact mass transfer and heat transfer. Further, the size of the nano / micron hydrogen bubble can be 10nm to 1000μm.

[0051] The average density of the hydrogen-containing fluid I in the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply can be 400-1000 kg / m 3 .

[0052] The average density of the hydrogen-containing fluid II in the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply can be 100-400 kg / m 3 .

[0053] In the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply, the average density of the hydrogen-containing fluid III can be 5 to 100 kg / m 3 .

[0054] In the reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply, the mass fraction of hydrogen in the hydrogen-containing fluid I can be 0.01wt% to 0.5wt%, preferably 0.1wt% to 0.3wt%.

[0055] In the reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply, the mass fraction of hydrogen in the hydrogen-containing fluid II can be 0.5wt% to 10wt%, preferably 1wt% to 5wt%.

[0056] In the reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply, the mass fraction of hydrogen in the hydrogen-containing fluid III can be 80wt% to 100wt%, preferably 85wt% to 95wt%.

[0057] In the reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply, the hydrogen-containing fluid I, hydrogen-containing fluid II, and hydrogen-containing fluid III can be formed by mixing the gas-liquid mixing device I, gas-liquid mixing device II, and gas-liquid mixing device III, respectively. Further, the gas-liquid mixing device I, gas-liquid mixing device II, and gas-liquid mixing device III can be independently static mixers, dissolved air pumps, colloid mills, microporous plate nano / micro hydrogen dispersion components, ceramic membrane nano / micro hydrogen dispersion components, or one or more combinations thereof.

[0058] [2] Application of the reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply described in [1] in hydrogenation reaction.

[0059] The reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply can be used as the main hydrogenation reaction, pre-hydrogenation reaction or post-hydrogenation reaction in the hydrogenation process, and can also be connected in series or in parallel with processes such as gas-liquid co-current fixed bed hydrogenation, upflow or downflow liquid phase hydrogenation, ebullating bed hydrogenation, and suspended bed hydrogenation.

[0060] [3] A hydrogenation method, using the counter-current / cross-current hydrogenation reaction device with cascade hydrogen supply as described in [1].

[0061] In some embodiments, the hydrogenation method comprises:

[0062] In the upper reaction zone, the hydrogen-containing fluid I enters the inner cylinder I, and gradually diffuses through the cylinder wall of the inner cylinder I to the annular space I, and undergoes a hydrogenation reaction with the material from the annular space I from bottom to top. The liquid reaction material after completing the hydrogenation reaction in the upper reaction zone enters the lower reaction zone to continue to react;

[0063] In the lower reaction zone, the hydrogen-containing fluid II and the liquid reaction materials after the reaction in the upper reaction zone enter the annular space II together, and gradually diffuse through the wall of the inner tube II to the inner tube II, and undergo a hydrogenation reaction with the hydrogen-containing fluid III coming from the inner tube II from bottom to top. After the hydrogenation reaction is completed in the lower reaction zone, the remaining hydrogen leaves from the top of the lower reaction zone and enters the upper reaction zone.

[0064] In some embodiments, the hydrogenation method is mainly carried out in the upper reaction zone in the early stage of the reaction, and in the lower reaction zone in the late stage of the reaction; the early stage of the reaction refers to the stage when the conversion rate of the key components of the hydrogenation reaction is lower than 70%, and the late stage of the reaction refers to the stage when the conversion rate of the key components of the hydrogenation reaction is above 70%.

[0065] In the hydrogenation method, the space velocity of the integral modular catalyst unit loaded in the inner cylinder I can be 2 to 30 h -1 , preferably 5 to 20 hours -1 , for example 8h -1 , 10h -1 , 12h -1 , 16h -1 wait.

[0066] In the hydrogenation method, the space velocity of the non-monolithic catalyst filled in the annular space I can be 0.1 to 10 h -1 , preferably 0.5 to 4 hours -1 , for example 0.5h -1 , 0.6h -1 、0.8h -1 , 1h -1 , 2h -1 wait.

[0067] In the hydrogenation method, the space velocity of the non-monolithic catalyst loaded in the inner cylinder II can be 0.1 to 10 h -1 , preferably 1 to 5 hours -1 , for example 1h -1 , 1.5h -1 , 2h -1 , 4h -1 wait.

[0068] In the hydrogenation method, the space velocity of the integral modular catalyst unit filled in the annular space II can be 1 to 20 h -1 , preferably 3 to 15 hours -1 , for example 4h -1 , 5h -1 , 6h -1 wait.

[0069] In some embodiments, in the hydrogenation method, the space velocity of the integral modular catalyst unit loaded in the inner cylinder I is not less than the space velocity of the integral modular catalyst unit loaded in the annular space II.

[0070] In some embodiments, in the hydrogenation method, the space velocity of the non-integral catalyst loaded in the inner cylinder II is not less than the space velocity of the non-integral catalyst loaded in the annular space I.

[0071] Hydrogen added to hydrogen-containing fluid I, hydrogen-containing fluid II, and hydrogen-containing fluid III (Nm 3 / h) and the liquid reaction raw material (m 3 / h) can be adjusted according to various hydrogenation 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. In some embodiments, the feed ratio of hydrogen to liquid reaction raw material in the hydrogenation method can be 1 to 1500 Nm 3 / h:1m 3 / h, preferably 5 to 500 Nm 3 / h:1m 3 / h.

[0072] The hydrogenation method and the hydrogenation reaction process conditions are generally determined by those skilled in the art according to the properties of the raw materials, the quality requirements of the final product, etc. In some embodiments, the process conditions of the internally and externally coupled reverse / cross-flow hydrogenation reactor may include: a reaction temperature of room temperature to 500°C, and a reaction pressure of 0.1 to 20 MPaG.

[0073] The reverse / cross-flow hydrogenation reaction device and hydrogenation method for cascade hydrogen supply of the present invention are applicable to various raw materials that can undergo hydrogenation reaction with hydrogen in the fields of petrochemical, medicine, food, etc., and can be crude oil and secondary processed oil such as crude oil, gasoline, kerosene, diesel, residual oil, heavy oil, wax oil, lubricating oil, deasphalted oil, biodiesel, animal oil or vegetable oil, coal tar, anthracene oil, etc.; it can also be various raw materials containing carbon-carbon double bonds, carbon-carbon triple bonds and organic functional groups that can undergo hydrogenation reaction in the fields of chemical, medicine, food, etc., such as olefin hydrogenation, alkyne hydrogenation, aldehyde compound hydrogenation, ketone compound hydrogenation, ester compound hydrogenation, nitro compound hydrogenation, carbonyl compound hydrogenation, nitrile compound hydrogenation and the like.

[0074] For the conventional fixed bed countercurrent hydrogenation process, there are mainly the following problems:

[0075] (1) The contact between the liquid reaction raw materials and hydrogen is completely reversed, which is prone to problems such as liquid overflow, biased flow, gas phase centering and short-circuit flow. There are problems such as low gas-liquid contact mass transfer efficiency and low catalyst utilization.

[0076] (2) When conventional granular catalysts are generally loaded into a hydrogenation reactor, on the one hand, the pure gas-liquid reverse contact flow will cause collision and wear between catalyst particles due to the upward lift of the gas. In severe cases, a large number of catalyst particles will be broken and block the bed, increasing the pressure drop and causing the hydrogenation reactor to be unable to operate normally.

[0077] (3) The problem of gas-liquid countercurrent contact mass transfer is that the gas phase has low relative heat and low viscosity. On the one hand, a higher gas-liquid ratio is required to uniformly release heat during the hydrogenation reaction. Especially for hydrogenation reactions with large heat release, serious local hot spots still exist even with a higher gas-liquid ratio. On the other hand, compared with liquid-liquid contact, the mutual viscosity of gas-liquid contact is smaller, which is not conducive to deep hydrogenation reaction and mass and heat transfer.

[0078] (4) Generally speaking, in the early stage of the reaction, the reaction substrate concentration is high, the mass transfer driving force is high, and the hydrogenation reaction rate is fast, but it is easy to cause problems such as concentrated heat release, local hot spots, uneven reaction, and catalyst coking. In the later stage of the reaction, the reaction substrate concentration is low, the mass transfer driving force is low, and the hydrogenation reaction rate is low. More stringent conditions such as higher pressure and temperature and longer residence time are required to achieve the ideal reaction effect.

[0079] The present invention uses a special hydrogenation reaction device and hydrogenation method to divide the hydrogenation reaction process into an upper reaction zone and a lower reaction zone, so that the early stage and late stage of the hydrogenation reaction respectively occur in the upper reaction zone and the lower reaction zone, which can greatly enhance the mass transfer and heat transfer in the hydrogenation reaction process, effectively improve the efficiency of the hydrogenation reaction, and solve the problems of concentrated heat release, local hot spots, uneven reaction, catalyst coking, etc. in the conventional countercurrent hydrogenation reaction zone, making the entire hydrogenation reaction process more uniform, efficient and easy to control. The main technical effects and advantages of the present invention are as follows:

[0080] 1) In the hydrogenation reaction process of the present invention, hydrogen-containing fluid I, hydrogen-containing fluid II, and hydrogen-containing fluid III are introduced into the upper, middle, and lower parts of the reactor in sequence, and the hydrogen contents of hydrogen-containing fluid I, hydrogen-containing fluid II, and hydrogen-containing fluid III are increased in sequence, and the average density is decreased in sequence. On the one hand, by stepwise supplying nano / micro hydrogen sources along the reaction process direction according to the difficulty of the reaction, the hydrogenation reaction rate can be increased while preventing catalyst coking. On the other hand, compared with the conventional hydrogenation process, the material contact mode is biased towards liquid-liquid mass transfer reaction, which is beneficial to improve the problems of gas phase centering, short-circuit flow, local hydrogen deficiency, etc., thereby improving the catalyst utilization rate and hydrogenation reaction efficiency.

[0081] 2) In the hydrogenation reactor structure of the present invention, an upper reaction zone and a lower reaction zone are provided. The reaction mainly occurs in the upper reaction zone in the early stage of the hydrogenation reaction, and mainly occurs in the lower reaction zone in the later stage of the hydrogenation reaction. Both the upper reaction zone and the lower reaction zone adopt a structural mode of a combination of an inner cylinder and an annular space. The difference is that the main reaction substrate of the upper reaction zone diffuses from the inner cylinder (modular catalyst unit) to the annular space (conventional catalyst), while the main reaction substrate of the lower reaction zone diffuses from the annular space (modular catalyst unit) to the inner cylinder (conventional catalyst). This process of alternating diffusion between the modular catalyst unit and the conventional catalyst and changing the flow path can not only effectively even out the reaction heat and prevent the accumulation of reaction heat, but also regulate the progress of the hydrogenation reaction, making the reaction process very controllable and easy to control.

[0082] 3) In the process of hydrogenation reaction, the present invention designs a novel structure of the upper reaction zone and the lower reaction zone of the hydrogenation reactor to guide the flow direction of the material to enhance the mass transfer and heat transfer. In the whole process of hydrogenation reaction, the material contact mass transfer mode is cross-flow and counter-flow at the same time, which is particularly beneficial to improve the depth of hydrogenation conversion for liquid-liquid contact mass transfer.

[0083] 4) The present invention couples the special structure of the upper and lower reaction zones of the hydrogenation reactor with the catalyst loading method: in the upper reaction zone, the material is first subjected to hydrogenation reaction in the modular catalyst unit of the inner tube, and then diffused to the conventional catalyst in the annular space for hydrogenation reaction. This is mainly based on the high concentration of fresh reaction substrates, fast reaction rate, and large heat release, which are prone to cause local hot spots and catalyst coking and deactivation. The modular catalyst unit not only has a small pressure drop and a high air velocity, but also its surface through holes can effectively improve the flow of materials, prevent material accumulation, and reduce the residence time of materials on the catalyst surface, thereby uniformizing the reaction heat and preventing the catalyst from coking and deactivation. As the reaction proceeds, the hydrogenation reaction gradually tends to be stable and gentle. At this time, the gradual diffusion to the annular space can not only improve mass transfer through counter / cross-current contact, but also can be used in conventional catalyst systems. A slightly longer residence time (slightly lower space velocity) is further coupled to improve the hydrogenation reaction rate; in the lower reaction zone, the reactants first enter the modular catalyst unit in the annular space for hydrogenation reaction, and then diffuse to the conventional catalyst in the inner tube for hydrogenation reaction. This is mainly based on the low concentration of the reaction substrate in the later stage of the reaction and the slow reaction rate, especially when the reaction conversion rate is close to 100%. The reaction rate is even lower. Therefore, improving the rate in the later stage of the hydrogenation reaction is an issue that needs to be focused on. Therefore, the unreacted substrate in the upper reaction zone first enters the modular catalyst unit in the annular space. From the perspective of adjusting the material flow state, the reaction heat is further uniformed by improving the material flow and strengthening the turbulent flow state. In this way, when the material diffuses into the conventional catalyst in the inner tube, not only the mass transfer is improved through counter / cross-current contact, but also the high conversion rate in the later stage of the reaction is guaranteed with high selectivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] Figure 1 It is a schematic structural diagram of a reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply according to the present invention. DETAILED DESCRIPTION

[0085] 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.

[0086] See also Figure 1A reverse / cross-flow hydrogenation reaction device 6 with step-wise hydrogen supply includes a gas deliquidation zone 7, an upper reaction zone 8, a lower reaction zone 9 and a liquid degassing zone 10 which are sequentially connected from top to bottom. The upper reaction zone 8 includes an inner cylinder I11 and an annular space I12 located outside the inner cylinder I11. The top end of the inner cylinder I11 is connected to a hydrogen-containing fluid I1, the bottom end is a closed support plate I16, and the cylinder wall 20 is provided with a through hole I for connecting the inner cylinder I11 and the annular space I12. The bottom end of the annular space I12 is connected to a hydrogen-containing fluid II 2, and the top end is a closed compression plate I19. The lower reaction zone 9 includes an inner cylinder II 22 and an annular space II 23 located outside the inner cylinder II 22. The top of the annular space II 23 is connected to the hydrogen-containing fluid II 2, and the bottom is a closed support plate II 27. The bottom of the inner cylinder II 22 is connected to the hydrogen-containing fluid III3, the top is a closed pressing plate II 29, and the cylinder wall 31 is provided with a through hole II for connecting the inner cylinder II 22 and the annular space II 23. A feed port for hydrogen-containing fluid I1 is set between the gas deliquid zone 7 and the upper reaction zone 8. The feed port for hydrogen-containing fluid I1 is connected to the top of the inner cylinder I11 and is not connected to the annular space I12. A feed port for hydrogen-containing fluid II 2 is set between the upper reaction zone 8 and the lower reaction zone 9. The feed port for hydrogen-containing fluid II2 is connected to the annular space I12 and the annular space II 23, and is not connected to the inner cylinder I11 and the inner cylinder II 22. A feed port for hydrogen-containing fluid III 3 is provided between the lower reaction zone 9 and the liquid degassing zone 10, and the feed port for hydrogen-containing fluid III 3 is connected to the inner cylinder II 22, and is not connected to the annular space II 23. A residual gas outlet is provided at the top of the gas deliquid zone 7; and a liquid reaction product outlet is provided at the bottom of the liquid degassing zone 10. The diameters of the gas deliquid zone 7, the upper reaction zone 8, the lower reaction zone 9 and the liquid degassing zone 10 are the same. The average density of hydrogen-containing fluid I1 ≥ the average density of hydrogen-containing fluid II 2 ≥ the average density of hydrogen-containing fluid III 3. The inner cylinder I11 is filled with a monolithic catalyst A14, and the annular space II 23 is filled with a monolithic catalyst B 26; the annular space I12 is filled with a non-monolithic catalyst C15 (conventional catalyst), and the inner cylinder II 22 is filled with a non-monolithic catalyst D 25 (conventional catalyst). The inner cylinder I11 and the inner cylinder II 22 are both cylindrical cylinders. An isolation wire mesh I 33 is provided on the surface of the cylinder wall 20 between the inner cylinder I11 and the annular space I12, and an isolation wire mesh II 34 is provided on the surface of the cylinder wall between the inner cylinder II 22 and the annular space II 23, respectively, to prevent the non-integrated catalysts C15 and D 25 from running away. A support grid A and a compression grid A 18 are provided at the lower and upper parts of the bed of the integral catalyst A14 loaded in the inner cylinder I11. A support grid B and a compression grid B 30 are provided at the lower and upper parts of the bed of the integral catalyst B 26 loaded in the annular space II23. A support grid C17 and a compression grid C are provided at the lower and upper parts of the bed of the non-integrated catalyst C15 loaded in the annular space I12.The lower and upper parts of the non-monolithic catalyst D 25 bed loaded in the inner cylinder II 22 are respectively provided with a support grid D 28 and a compression grid D. The support grids A and B of the monolithic catalyst A14 and B 26 beds are flat closed structures, and the compression grids A 18 and B 30 are open structures. The support grids C17 and D 28 of the non-monolithic catalyst C15 and D 25 beds are open structures, and the compression grids C and D are flat closed structures. Monolithic catalysts A 14 and B 26 are provided with an array-arranged mutually interpenetrating honeycomb pore structure. The through hole sizes on the surfaces of monolithic catalysts A14 and B 26 are independently 1mm×1mm~10mm×10mm, preferably independently 3mm×3mm~8mm×8mm. A material distributor A13 is arranged at the top of the inner cylinder I11, a material distributor B 24 is arranged at the top of the annular space II 23, a material distributor C 32 is arranged at the bottom of the inner cylinder II 22, and a material distributor D 21 is arranged at the bottom of the annular space I12, wherein the material distributor A13 at the top of the inner cylinder I11 is in communication with the hydrogen-containing fluid I1, the material distributors D 21 and B 24 at the bottom of the annular space I12 and the top of the annular space II 23 are in communication with the hydrogen-containing fluid II 2, and the material distributor C 32 at the bottom of the inner cylinder II 22 is in communication with the hydrogen-containing fluid III 3. The hydrogen-containing fluid I1, the hydrogen-containing fluid II 2, and the hydrogen-containing fluid III 3 are mixtures of hydrogen-containing gas and liquid reaction raw materials, specifically gas-liquid mixed fluids containing nano / micron hydrogen bubbles, so that the required hydrogen source is provided according to different stages of the reaction during the reaction, and the size of the nano / micron hydrogen bubbles is 10nm to 1000μm. The hydrogen-containing fluid I1, hydrogen-containing fluid II2, and hydrogen-containing fluid III3 can be obtained by mixing gas-liquid mixing equipment I, gas-liquid mixing equipment II, and gas-liquid mixing equipment III, respectively; gas-liquid mixing equipment I, gas-liquid mixing equipment II, and gas-liquid mixing equipment III can respectively independently use one or more combinations of static mixers, dissolved air pumps, colloid mills, microporous plate nano / micron hydrogen dispersion components, and ceramic membrane nano / micron hydrogen dispersion components. The average density of hydrogen-containing fluid I1 is 400-1000 kg / m. 3 The average density of hydrogen-containing fluid II 2 is 100 to 400 kg / m 3 The average density of the hydrogen-containing fluid III 3 is 5 to 100 kg / m 3 .

[0087] A hydrogenation method, using the above Figure 1 The reverse / cross-flow hydrogenation reaction device 6 with step-wise hydrogen supply shown comprises:

[0088] The hydrogen-containing fluid I1, the hydrogen-containing fluid II2, and the hydrogen-containing fluid III3 are respectively introduced into the upper part, the middle part, and the lower part of the counter-current / cross-current hydrogenation reaction device 6 with step-hydrogen supply; after the hydrogen-containing fluid I1 enters the counter-current / cross-current hydrogenation reaction device 6 with step-hydrogen supply, it is evenly distributed by the material distributor A13 of the inner cylinder I11 of the upper reaction zone 8, flows through the bed of the integral catalyst A14 loaded in the inner cylinder I11 of the upper reaction zone 8, and passes through the isolation wire mesh I33 between the inner cylinder I11 of the upper reaction zone 8 and the catalyst in the annular space I12 and the cylinder wall 20 of the inner cylinder I11 of the upper reaction zone 8 to enter the non-integral catalyst C15 loaded in the annular space I12 of the upper reaction zone 8, completes the counter-current / cross-current contact mass transfer with the material from bottom to top, and then enters the lower reaction zone 9 to continue the hydrogenation reaction;

[0089] The reaction liquid phase material and hydrogen-containing fluid II 2 of the upper reaction zone 8 are uniformly distributed through the material distributor B 24 of the monolithic catalyst B 26 bed in the annular space II 23 of the lower reaction zone 9, flow through the monolithic catalyst B 26 bed filled in the annular space II 23 of the lower reaction zone 9, and pass through the cylinder wall 31 of the inner cylinder II 22 of the lower reaction zone 9 and the isolation wire mesh II 34 between the inner cylinder II 22 of the lower reaction zone 9 and the catalyst in the annular space II 23 to enter the non-monolithic catalyst D 25 filled in the inner cylinder II 22 of the lower reaction zone 9, complete the counter-current / cross-current contact mass transfer with the materials from bottom to top, and then leave the lower reaction zone 9 and enter the liquid degassing zone 10 for degassing, and then leave from the bottom of the counter-current / cross-current hydrogenation reaction device 6 with cascade hydrogen supply as a liquid reaction product 5;

[0090] The hydrogen-containing fluid III 3 is introduced from the lower part of the lower reaction zone 9, and after being evenly distributed by the material distributor C 32 of the non-integrated catalyst bed D 25 in the inner cylinder II 22 of the lower reaction zone 9, enters the non-integrated catalyst D 25 loaded in the inner cylinder II 22 of the lower reaction zone 9, and passes through the isolation wire mesh II 34 between the inner cylinder II 22 of the lower reaction zone 9 and the catalyst in the annular space II 23 and the cylinder wall 31 of the inner cylinder II 22 of the lower reaction zone 9 to enter the integral catalyst B26 bed loaded in the annular space II 23 of the lower reaction zone 9, and enters the upper reaction zone 8 after completing the hydrogenation reaction in the lower reaction zone 9, and passes through the material distributor D 32 of the non-integrated catalyst bed C15 in the annular space I12 of the upper reaction zone 8. After being evenly distributed, the catalyst enters the non-integrated catalyst C15 loaded in the annular space I12 of the upper reaction zone 8, passes through the cylinder wall 20 of the inner cylinder I11 of the upper reaction zone 8 and the isolating wire mesh I 33 between the inner cylinder I11 of the upper reaction zone 8 and the catalyst in the annular space I12, enters the integral catalyst A14 loaded in the inner cylinder I11 of the upper reaction zone 8, leaves the upper reaction zone 8 and enters the gas deliquidation zone 7 after completing the hydrogenation reaction, and leaves the top of the counter / cross-flow hydrogenation reaction device 6 with step-wise hydrogen supply as the residual gas 4 of the hydrogenation reaction after completing the gas-liquid separation.

[0091] The above-mentioned reverse / cross-flow hydrogenation reaction device 6 with step-wise hydrogen supply and hydrogenation method are respectively applied to the hydrogenation of wax oil and the hydrogenation process of biomass sugar (glucose) solution. The properties of wax oil raw materials are shown in Table 1, and the properties of wax oil hydrogenation catalysts are shown in Table 2; the properties of biomass sugar (glucose) hydrogenation raw materials are shown in Table 3, and the properties of biomass sugar (glucose) solution hydrogenation catalysts are shown in Table 4. All the above raw materials are commercially available, and all hydrogenation catalysts are homemade.

[0092] Table 1 Wax oil raw material properties

[0093]

[0094] Table 2 Properties of Wax Oil Hydrogenation Catalyst

[0095]

[0096] Table 3 Biomass sugar (glucose) solution raw materials

[0097] project index Characteristics Colorless transparent liquid Concentration, mol / L 1.5

[0098] Table 4 Biomass sugar (glucose) solution hydrogenation catalyst properties

[0099]

[0100] Comparative Example 1

[0101] A conventional gas, liquid, and solid three-phase fixed bed parallel flow hydrogenation reactor and hydrogenation method were used. The height-to-diameter ratio of the hydrogenation reactor was 2.5. Two catalyst beds were used. The two beds had the same height. The first bed was filled with conventional catalysts B2 and B3 corresponding to the respective reaction processes, and the second bed was filled with conventional catalysts B1 and B4 corresponding to the respective reaction processes. The void ratios of the catalyst beds of B1, B2, B3, and B4 were 65.4%, 66.3%, 83.2%, and 80.5%, respectively. The device was used to investigate the reaction effects of hydrogenation of wax oil mixed feedstock and hydrogenation of biomass sugar (glucose) under different conditions.

[0102] First, the mixture of raw materials and hydrogen is temperature-adjusted to the inlet temperature of the hydrogenation reactor, and then enters the hydrogenation reactor from the top and passes through the first and second catalyst beds from top to bottom to undergo hydrogenation reaction, and leaves the reactor after the hydrogenation reaction is completed.

[0103] The operating conditions of the hydrogenation reactor are shown in Table 5, and the results of the hydrogenation reaction are shown in Table 6.

[0104] Comparative Example 2

[0105] A conventional gas, liquid, and solid three-phase fixed bed co-current hydrogenation reactor and hydrogenation method were used. The height-to-diameter ratio of the hydrogenation reactor was 2.5. Two catalyst beds were used. The heights of the two beds were the same. The first bed was filled with 25 layers of modular catalyst units A1 and A3 corresponding to the respective reaction processes, and the second bed was filled with 25 layers of modular catalyst units A2 and A4 corresponding to the respective reaction processes. The void ratios of the catalyst beds of A1, A2, A3, and A4 were 72.8%, 73.1%, 77.2%, and 75.5%, respectively. The device was used to investigate the reaction effects of hydrogenation of wax oil mixed feedstock and hydrogenation of biomass sugar (glucose) under different conditions.

[0106] First, the mixture of raw materials and hydrogen is temperature-adjusted to the inlet temperature of the hydrogenation reactor, and then enters the hydrogenation reactor from the top and passes through the first and second catalyst beds from top to bottom to undergo hydrogenation reaction, and leaves the reactor after the hydrogenation reaction is completed.

[0107] The operating conditions of the hydrogenation reactor are shown in Table 5, and the results of the hydrogenation reaction are shown in Table 6.

[0108] Comparative Example 3

[0109] A conventional gas, liquid, solid three-phase fixed bed countercurrent hydrogenation reactor and hydrogenation method were used. The height-to-diameter ratio of the hydrogenation reactor was 2.5. Two catalyst beds were used. The two beds had the same height. The first bed was filled with conventional catalysts B2 and B4 corresponding to the respective reaction processes, and the second bed was filled with conventional catalysts B1 and B3 corresponding to the respective reaction processes. The void ratios of the catalyst beds of B1, B2, B3, and B4 were 65.4%, 66.3%, 83.2%, and 80.5%, respectively. The device was used to investigate the reaction effects of hydrogenation of wax oil mixed feedstock and hydrogenation of biomass sugar (glucose) under different conditions.

[0110] First, the crude oil is adjusted to the inlet temperature of the hydrogenation reactor and then enters from the top of the hydrogenation reactor. The hydrogen is adjusted to the inlet temperature of the hydrogenation reactor and then enters from the bottom of the hydrogenation reactor. The two undergo a hydrogenation reaction in the catalyst bed and leave after the hydrogenation reaction is completed.

[0111] The operating conditions of the hydrogenation reactor are shown in Table 5, and the reaction results are shown in Table 6.

[0112] Comparative Example 4

[0113] A conventional gas, liquid, solid three-phase fixed bed countercurrent hydrogenation reactor and hydrogenation method were used. The height-to-diameter ratio of the hydrogenation reactor was 2.5. Two catalyst beds were used. The heights of the two beds were the same. The first bed was filled with 25 layers of modular catalyst units A2 and A4 corresponding to the respective reaction processes, and the second bed was filled with 25 layers of modular catalyst units A1 and A3 corresponding to the respective reaction processes. The void ratios of the catalyst beds of A1, A2, A3, and A4 were 72.8%, 73.1%, 77.2%, and 75.5%, respectively. The device was used to investigate the reaction effects of hydrogenation of wax oil mixed feedstock and hydrogenation of biomass sugar (glucose) under different conditions.

[0114] First, the crude oil is adjusted to the inlet temperature of the hydrogenation reactor and then enters from the top of the hydrogenation reactor. The hydrogen is adjusted to the inlet temperature of the hydrogenation reactor and then enters from the bottom of the hydrogenation reactor. The two undergo a hydrogenation reaction in the catalyst bed and leave after the hydrogenation reaction is completed.

[0115] The operating conditions of the hydrogenation reactor are shown in Table 5, and the reaction results are shown in Table 6.

[0116] Example 1

[0117] A reverse / cross-flow hydrogenation reaction device and a hydrogenation method with step-wise hydrogen supply introduced in the specific embodiment of the present invention are used. The formation of hydrogen-containing fluid I / II / III is obtained by a dissolved air pump. The height-to-diameter ratio of the hydrogenation reaction device is 2.5:1, the height-to-diameter ratio of the inner cylinder I is 1:1, and the ratio of the diameter of the inner cylinder I to the diameter of the hydrogenation reaction device is 1:1.5; the height-to-diameter ratio of the inner cylinder II is 4:1, and the ratio of the diameter of the inner cylinder II to the diameter of the hydrogenation reaction device is 1:4; the through holes opened on the wall surfaces of the inner cylinders I and II are circular holes, and the hole size is evenly distributed along the surface of the inner cylinder I or II; the ratio of the opening area of ​​the inner cylinder I wall to the side area of ​​the inner cylinder I wall is 1:2, and the size of the opening of the inner cylinder I wall is 6mm; the ratio of the opening area of ​​the inner cylinder II wall to the side area of ​​the inner cylinder II wall is 1:4, and the size of the opening of the inner cylinder II wall is 14mm. The aperture of the isolation wire mesh between the inner cylinder I / II and the annular space I / II is 12 meshes.

[0118] The upper reaction zone and the lower reaction zone in the hydrogenation reaction device are filled with catalysts required for their respective reactions: the inner cylinder I of the upper reaction zone is filled with 15 layers of catalyst A2 / A3, the annular space I of the upper reaction zone is filled with catalyst B2 / B3, the annular space II of the lower reaction zone is filled with 15 catalysts A1 / A4, and the inner cylinder II of the lower reaction zone is filled with catalyst B1 / B4; the void ratios of the catalyst beds of A1, A2, A3, and A4 are 72.8%, 73.1%, 77.2%, and 75.5%, respectively, and the void ratios of the catalyst beds of B1, B2, B3, and B4 are 65.4%, 66.3%, 83.2%, and 80.5%, respectively.

[0119] The device was used to investigate the reaction effects of hydrogenation of wax oil mixed raw materials and biomass sugar (glucose) hydrogenation under different conditions. First, the reaction raw materials were prepared into hydrogen-containing fluids I / II / III respectively, and after being adjusted to the required temperature of the hydrogenation reaction device, they entered from the upper, middle and lower parts of the hydrogenation reaction device. Countercurrent and cross-current hydrogenation reactions occurred in the catalyst beds of the upper and lower reaction zones of the hydrogenation reaction device. The residual gas after the hydrogenation reaction left from the top, and the liquid product of the hydrogenation reaction left from the bottom.

[0120] The operating conditions of the hydrogenation reaction unit are shown in Table 5, and the reaction results are shown in Table 6.

[0121] Example 2

[0122] A reverse / cross-flow hydrogenation reaction device and a hydrogenation method with step-wise hydrogen supply introduced in the specific embodiment of the present invention are used. The formation of hydrogen-containing fluid I / II / III is obtained by a dissolved air pump. The height-to-diameter ratio of the hydrogenation reaction device is 2.5:1, the height-to-diameter ratio of the inner cylinder I is 2:1, the ratio of the diameter of the inner cylinder I to the diameter of the hydrogenation reaction device is 1:2, the height-to-diameter ratio of the inner cylinder II is 2:1, and the ratio of the diameter of the inner cylinder II to the diameter of the hydrogenation reaction device is 1:4; the through holes opened on the wall surfaces of the inner cylinders I and II are circular holes, and the hole size is evenly distributed along the surface of the inner cylinder I or II; the ratio of the opening area of ​​the inner cylinder I wall to the side area of ​​the inner cylinder I wall is 1:4, and the size of the opening of the inner cylinder I wall is 4mm; the ratio of the opening area of ​​the inner cylinder II wall to the side area of ​​the inner cylinder II wall is 1:2, and the size of the opening of the inner cylinder II wall is 10mm. The aperture of the isolation wire mesh between the inner cylinder I / II and the annular space I / II is 12 meshes.

[0123] The upper reaction zone and the lower reaction zone in the hydrogenation reaction device are filled with catalysts required for their respective reactions: the inner cylinder I of the upper reaction zone is filled with 20 layers of catalyst A1 / A3, the annular space I of the upper reaction zone is filled with catalyst B1 / B3, the annular space II of the lower reaction zone is filled with 10 catalysts A2 / A4, and the inner cylinder II of the lower reaction zone is filled with catalyst B2 / B4; the void ratios of the catalyst beds of A1, A2, A3, and A4 are 72.8%, 73.1%, 77.2%, and 75.5%, respectively, and the void ratios of the catalyst beds of B1, B2, B3, and B4 are 65.4%, 66.3%, 83.2%, and 80.5%, respectively.

[0124] The device was used to investigate the reaction effects of hydrogenation of wax oil mixed raw materials and biomass sugar (glucose) hydrogenation under different conditions. First, the reaction raw materials were prepared into hydrogen-containing fluids I / II / III respectively, and after being adjusted to the required temperature of the hydrogenation reaction device, they entered from the upper, middle and lower parts of the hydrogenation reaction device. Countercurrent and cross-current hydrogenation reactions occurred in the catalyst beds of the upper and lower reaction zones of the hydrogenation reaction device. The residual gas after the hydrogenation reaction left from the top, and the liquid product of the hydrogenation reaction left from the bottom.

[0125] The operating conditions of the hydrogenation reaction unit are shown in Table 5, and the reaction results are shown in Table 6.

[0126] Example 3

[0127] A reverse / cross-flow hydrogenation reaction device and a hydrogenation method with step-wise hydrogen supply introduced in a specific embodiment of the present invention are used. The formation of hydrogen-containing fluid I / II / III is obtained by a dissolved air pump. The height-to-diameter ratio of the hydrogenation reaction device is 2.5:1, the height-to-diameter ratio of the inner cylinder I is 3:1, and the ratio of the diameter of the inner cylinder I to the diameter of the hydrogenation reaction device is 1:2; the height-to-diameter ratio of the inner cylinder II is 2:1, and the ratio of the diameter of the inner cylinder II to the diameter of the hydrogenation reaction device is 1:3; the through holes opened on the wall surfaces of the inner cylinders I and II are circular holes, and the hole size is evenly distributed along the surface of the inner cylinder I or II; the ratio of the opening area of ​​the inner cylinder I wall to the side area of ​​the inner cylinder I wall is 1:6, and the size of the opening of the inner cylinder I wall is 4mm; the ratio of the opening area of ​​the inner cylinder II wall to the side area of ​​the inner cylinder II wall is 1:3, and the size of the opening of the inner cylinder II wall is 12mm. The aperture of the isolation wire mesh between the inner cylinder I / II and the annular space I / II is 12 meshes.

[0128] The upper reaction zone and the lower reaction zone in the hydrogenation reaction device are filled with catalysts required for the respective reactions: the inner cylinder I of the upper reaction zone is filled with 10 layers of catalyst A1 / A4, the annular space I of the upper reaction zone is filled with catalyst B1 / B4, the annular space II of the lower reaction zone is filled with 20 layers of catalyst A2 / A3, and the inner cylinder II of the lower reaction zone is filled with catalyst B2 / B3. The voidage of the catalyst beds of A1, A2, A3, and A4 is 72.8%, 73.1%, 77.2%, and 75.5%, respectively, and the voidage of the catalyst beds of B1, B2, B3, and B4 is 65.4%, 66.3%, 83.2%, and 80.5%, respectively.

[0129] The device was used to investigate the reaction effects of hydrogenation of wax oil mixed raw materials and biomass sugar (glucose) hydrogenation under different conditions. First, the reaction raw materials were prepared into hydrogen-containing fluids I / II / III respectively, and after being adjusted to the required temperature of the hydrogenation reaction device, they entered from the upper, middle and lower parts of the hydrogenation reaction device. Countercurrent and cross-current hydrogenation reactions occurred in the catalyst beds of the upper and lower reaction zones of the hydrogenation reaction device. The residual gas after the hydrogenation reaction left from the top, and the liquid product of the hydrogenation reaction left from the bottom.

[0130] The operating conditions of the hydrogenation reaction unit are shown in Table 5, and the reaction results are shown in Table 6.

[0131] Table 5 Operating conditions of hydrogenation reactor (device)

[0132]

[0133] Table 6 Hydrogenation reaction results

[0134]

[0135] Δt11\Δt12\Δt13: average radial temperature difference between the upper, middle and lower parts of the upper reaction zone in the hydrogenation reaction unit; Δt21\Δt22\Δt23: average radial temperature difference between the upper, middle and lower parts of the lower reaction zone in the hydrogenation reaction unit.

[0136] It can be seen from the effects of the embodiments of the present invention and the comparative examples that the hydrogenation reaction device and the hydrogenation method of the present invention are used to divide the hydrogenation reaction device into an upper reaction zone and a lower reaction zone, and each is coupled with a special structure and a catalyst loading method, so that the material in the early stage of the reaction undergoes a hydrogenation reaction in the upper reaction zone, and the material in the late stage of the reaction undergoes a hydrogenation reaction in the lower reaction zone. It can be seen that not only the hydrogenation reaction rate is greatly improved, but also the temperature distribution of the upper reaction zone and the lower reaction zone of the hydrogenation reactor is very uniform, and the radial temperature difference is ≤3°C, that is, the device and method of the present invention effectively enhance the convective mass transfer and heat transfer diffusion of the material in the reaction process, which can greatly improve the conversion rate and selectivity of the hydrogenation reaction.

[0137] 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 with cascade hydrogen supply, characterized in that: It includes a gas deliquid zone, an upper reaction zone, a lower reaction zone and a liquid degassing zone which are sequentially connected from top to bottom; The upper reaction zone includes an inner tube I and an annular space I located outside the inner tube I. The top end of the inner tube I is connected to the hydrogen-containing fluid I, the bottom end is closed, and a through hole I is provided on the tube wall for connecting the inner tube I and the annular space I. The bottom end of the annular space I is connected to the hydrogen-containing fluid II, and the top end is closed; The lower reaction zone includes an inner cylinder II and an annular space II located outside the inner cylinder II. The top of the annular space II is connected to the hydrogen-containing fluid II and the bottom is closed. The bottom of the inner cylinder II is connected to the hydrogen-containing fluid III, the top is closed, and a through hole II is provided on the cylinder wall for connecting the inner cylinder II and the annular space II. The average density of hydrogen-containing fluid I ≥ the average density of hydrogen-containing fluid II ≥ the average density of hydrogen-containing fluid III; The average density is defined as the sum of the masses of the gas phase and the liquid in the fluid divided by the sum of the standard volume of the gas phase and the standard volume of the liquid; The inner cylinder I and the annular space II are filled with a monolithic catalyst; the annular space I and the inner cylinder II are filled with a non-monolithic catalyst.

2. The reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply according to claim 1, characterized in that: A feed port for hydrogen-containing fluid I is provided between the gas deliquidation zone and the upper reaction zone, and the feed port for hydrogen-containing fluid I is connected to the top of the inner cylinder I but is not connected to the annular space I; A feed port for hydrogen-containing fluid II is arranged between the upper reaction zone and the lower reaction zone, and the feed port for hydrogen-containing fluid II is connected with the annular space I and the annular space II, but is not connected with the inner cylinder I and the inner cylinder II; A feed port for hydrogen-containing fluid III is arranged between the lower reaction zone and the liquid degassing zone, and the feed port for hydrogen-containing fluid III is connected to the inner cylinder II but not to the annular space II; A residual gas outlet is provided at the top of the gas degassing zone; a liquid reaction product outlet is provided at the bottom of the liquid degassing zone; The diameters of the gas deliquid zone, the upper reaction zone, the lower reaction zone and the liquid degassing zone are the same or different; The height-to-diameter ratio of the reverse / cross-flow hydrogenation reaction device with step-wise hydrogen supply is 0.5 to 10:1, preferably 1 to 5:1; Both inner cylinder I and inner cylinder II are cylindrical cylinders; The height-to-diameter ratio of the inner cylinder I is 0.1 to 5:1, preferably 0.2 to 2:1; The ratio of the diameter of the inner cylinder I to the diameter of the counter-current / cross-current hydrogenation reaction device with step-wise hydrogen supply is 1:1.05-4, preferably 1:1.2-3; The height-to-diameter ratio of the inner cylinder II is 1 to 20:1, preferably 2 to 8:1; The ratio of the diameter of the inner cylinder II to the diameter of the counter-current / cross-current hydrogenation reaction device with step-wise hydrogen supply is 1:2 to 20, preferably 1:3 to 8; The diameter of inner cylinder I is not less than the diameter of inner cylinder II.

3. The reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply according to claim 1, characterized in that: The shapes of through hole I and through hole II are independently any one or more combinations of circle, ellipse, teardrop, Ω, ∞, triangle, rectangle, pentagon and above polygons; The apertures of through hole I and through hole II may vary or not vary independently along the axial direction of inner cylinder I and inner cylinder II, respectively, and the variation modes include one or more combinations of increasing, decreasing, alternating large and small, irregular variation, and partial area closure; The ratio of the area of ​​the through hole I opened in the wall of the inner cylinder I to the side area of ​​the wall of the inner cylinder I is 1:1.5-20, preferably 1:2-10; The diameter of the through hole I formed on the wall of the inner cylinder I is 0.1 to 100 mm, preferably 2 to 8 mm; The ratio of the area of ​​the through hole II opened on the wall of the inner cylinder II to the side area of ​​the wall of the inner cylinder II is 1:1.01-50, preferably 1:1.2-5; The diameter of the through hole II provided on the wall of the inner cylinder II is 1 to 100 mm, preferably 5 to 20 mm; The diameter of the through hole II formed in the wall of the inner cylinder II is not less than the diameter of the through hole I formed in the wall of the inner cylinder I; Isolation screens are independently arranged on the wall between inner tube I and annular space I and the wall between inner tube II and annular space II to prevent the non-integral catalyst from running away; the apertures of the isolation screens are independently 10 to 100 meshes.

4. The reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply according to claim 1, characterized in that: The lower and upper parts of the integral catalyst bed filled in the inner cylinder I and the annular space II and the non-integrated catalyst bed filled in the annular space I and the inner cylinder II are respectively provided with a supporting grid and a pressing grid, wherein the supporting grid of the integral catalyst bed is a flat plate closed structure and the pressing grid is an open structure, and the supporting grid of the non-integrated catalyst bed is an open structure and the pressing grid is a flat plate closed structure; The monolithic catalyst is provided with an array of interconnected honeycomb pore structures; The through-hole sizes of the surface of the monolithic catalyst filled in the inner cylinder I and the annular space II are independently 1 mm×1 mm to 10 mm×10 mm, preferably independently 3 mm×3 mm to 8 mm×8 mm; The height of the monolithic catalyst layer filled in the inner cylinder I and the annular space II is independently 50 to 1500 mm, preferably independently 100 to 600 mm; The porosity of the monolithic catalyst bed filled in the inner cylinder I and the annular space II is independently 60% to 90%, preferably 70% to 80%; The inner cylinder I and the annular space II are independently loaded with 2 to 100 layers, preferably 5 to 60 layers, of monolithic catalyst; the ratio of the number of monolithic catalyst layers loaded in the inner cylinder I and the annular space II is (1:10) to (10:1), preferably (1:5) to (5:1); The void ratios of the non-monolithic catalyst bed filled in the annular space I and the inner cylinder II are independently 60% to 95%, preferably independently 65% ​​to 85%; The shapes of the non-monolithic catalysts loaded in the annular space I and the inner cylinder II are independently spherical, toothed spherical, sheet-shaped, strip-shaped, three-leaf clover-shaped, four-leaf clover-shaped, hollow ring, multi-hole columnar, or a combination thereof; The radial dimension of the cross section of the non-integral catalyst filled in the annular space I and the inner cylinder II is 0.5 to 10 mm, preferably 1 to 6 mm.

5. The reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply according to claim 1, characterized in that: Material distributors are arranged at the top of the inner cylinder I and the annular space II, and at the bottom of the inner cylinder II and the annular space I, wherein the material distributor at the top of the inner cylinder I is connected to the hydrogen-containing fluid I, the material distributor at the bottom of the annular space I and the top of the annular space II is connected to the hydrogen-containing fluid II, and the material distributor at the bottom of the inner cylinder II is connected to the hydrogen-containing fluid III; The material distributors at the top of the inner cylinder I and the annular space II, and at the bottom of the inner cylinder II and the annular space I are independently any one or more combinations of tubular, plate, bubble, nozzle, jet, trough, disc, metal membrane tube, ceramic membrane tube, and microchannel.

6. The reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply according to claim 1, characterized in that: Hydrogen-containing fluid I, hydrogen-containing fluid II, and hydrogen-containing fluid III are mixtures of hydrogen-containing gas and liquid reaction raw materials; Hydrogen-containing fluid I, hydrogen-containing fluid II, and hydrogen-containing fluid III are gas-liquid mixed fluids containing nano / micro hydrogen bubbles, which provide the required hydrogen source according to different stages of the reaction; the size of the nano / micro hydrogen bubbles is 10nm to 1000μm; The average density of hydrogen-containing fluid I is 400-1000 kg / m 3 ; The average density of hydrogen-containing fluid II is 100-400 kg / m 3 ; The average density of hydrogen-containing fluid III is 5 to 100 kg / m 3 ; The mass fraction of hydrogen in the hydrogen-containing fluid I is 0.01wt% to 0.5wt%, preferably 0.1wt% to 0.3wt%; The mass fraction of hydrogen in the hydrogen-containing fluid II is 0.5wt% to 10wt%, preferably 1wt% to 5wt%; The mass fraction of hydrogen in the hydrogen-containing fluid III is 80wt% to 100wt%, preferably 85wt% to 95wt%; The hydrogen-containing fluid I, hydrogen-containing fluid II, and hydrogen-containing fluid III are formed independently by mixing gas-liquid mixing equipment I, gas-liquid mixing equipment II, and gas-liquid mixing equipment III respectively; gas-liquid mixing equipment I, gas-liquid mixing equipment II, and gas-liquid mixing equipment III respectively independently adopt one or more combinations of static mixers, dissolved air pumps, colloid mills, microporous plate nano / micron hydrogen dispersion components, and ceramic membrane nano / micron hydrogen dispersion components.

7. Use of the reverse / cross-flow hydrogenation reaction device with cascade hydrogen supply 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 with cascade hydrogen supply as described in any one of claims 1 to 6.

9. The hydrogenation method according to claim 8, characterized in that include: In the upper reaction zone, the hydrogen-containing fluid I enters the inner cylinder I, and gradually diffuses through the cylinder wall of the inner cylinder I to the annular space I, and undergoes a hydrogenation reaction with the material from the annular space I from bottom to top. The liquid reaction material after completing the hydrogenation reaction in the upper reaction zone enters the lower reaction zone to continue to react; In the lower reaction zone, the hydrogen-containing fluid II and the liquid reaction materials after the reaction in the upper reaction zone enter the annular space II together, and gradually diffuse through the wall of the inner tube II to the inner tube II, and undergo a hydrogenation reaction with the hydrogen-containing fluid III coming from the inner tube II from bottom to top. After the hydrogenation reaction is completed in the lower reaction zone, the remaining hydrogen leaves from the top of the lower reaction zone and enters the upper reaction zone.

10. The hydrogenation method according to claim 9, characterized in that: The early stage of the reaction is mainly carried out in the upper reaction zone, and the late stage of the reaction is mainly carried out in the lower reaction zone; the early stage of the reaction refers to the stage when the conversion rate of the key components of the hydrogenation reaction is lower than 70%, and the late stage of the reaction refers to the stage when the conversion rate of the key components of the hydrogenation reaction is higher than 70%; The space velocity of the integral modular catalyst unit filled in the inner cylinder I is 2 to 30 h -1 , preferably 5 to 20 hours -1 ; The space velocity of the non-monolithic catalyst filled in the annular space I is 0.1~10h -1 , preferably 0.5 to 4 hours -1 ; The space velocity of the non-monolithic catalyst loaded in the inner cylinder II is 0.1~10h -1 , preferably 1 to 5 hours -1 ; The space velocity of the integrated modular catalyst unit filled in the annular space II is 1 to 20 h -1 , preferably 3 to 15 hours -1 ; The space velocity of the integral modular catalyst unit filled in the inner cylinder I is not less than the space velocity of the integral modular catalyst unit filled in the annular space II; The space velocity of the non-monolithic catalyst loaded in the inner cylinder II is not less than the space velocity of the non-monolithic catalyst loaded in the annular space I; The hydrogenation method comprises a feed ratio of hydrogen to liquid reaction raw material of 1 to 1500 Nm 3 / h:1m 3 / h, preferably 5 to 500 Nm 3 / h:1m 3 / h; The process conditions of the internally and externally coupled reverse / cross-flow hydrogenation reactor include: a reaction temperature of room temperature to 500° C., and a reaction pressure of 0.1 to 20 MPaG.

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