Counterflow hydrogenation reactor based on lean hydrogen fluid and hydrogen-rich fluid and applications thereof

Abstract

The application discloses a countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid and application of the countercurrent hydrogenation reaction device in hydrogenation reaction. The countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid comprises a hydrogen-poor fluid forming area, a hydrogen-rich fluid forming area and a countercurrent hydrogenation reaction area; the hydrogen-poor fluid forming area comprises at least one hydrogen dissolving device I for mixing raw material liquid I and hydrogen I to form hydrogen-poor fluid; the hydrogen-rich fluid forming area comprises at least one hydrogen dissolving device II for mixing raw material liquid II and hydrogen II to form hydrogen-rich fluid; and the countercurrent hydrogenation reaction area comprises at least one countercurrent hydrogenation reactor. According to the application, raw material liquid and hydrogen are formed into hydrogen-poor fluid and hydrogen-rich fluid respectively, and then enter the countercurrent hydrogenation reactor to generate hydrogenation reaction, so that the hydrogenation reaction rate and hydrogenation conversion depth are greatly strengthened, the catalyst surface coking is effectively inhibited, the hydrogenation reaction is more uniform, and the catalyst service life is prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogenation, in particular to a countercurrent hydrogenation reaction device based on a hydrogen-poor fluid and a hydrogen-rich fluid and application thereof. BACKGROUND

[0002] Hydrogenation technology is a process technology that makes raw materials react with hydrogen under certain temperature and hydrogen partial pressure to obtain target products through the catalytic action of catalysts. Fixed bed hydrogenation process and reactors are the most widely used and can be used for various types of hydrogenation processes. Fixed bed hydrogenation can be divided into upflow (downward feeding) and downflow (upward feeding) according to the overall feeding direction of the material, and downflow (upward feeding) is the most widely used, especially the downflow (upward feeding) fixed bed hydrogenation process with gas-liquid co-current.

[0003] Although the gas-liquid co-current fixed bed hydrogenation process has been widely used, there are still the following problems: (1) the liquid passes through the catalyst bed in the form of a liquid film, the gas-liquid mass transfer rate is low, and harsh reaction conditions such as high temperature, high pressure, and low space velocity are generally required, resulting in high energy consumption; (2) a large hydrogen-oil ratio is required for the hydrogenation process, and a large hydrogen-oil ratio is generally required to achieve ideal reaction results, so the size of the reactor and the reaction system is large, and the investment is high; (3) under the conditions of high temperature, high pressure, and low space velocity, the residence time of the raw material is long, resulting in serious side reactions and catalyst coking; (4) after hydrogen consumption in the reaction process, hydrogen molecules cannot diffuse to the main body of the raw material in a large amount, resulting in lack of hydrogen on the surface of the catalyst and coking, causing uneven reaction and even unable to run for a long period. The reason is that on the one hand, the fixed bed gas-liquid co-current process, the form of the reactor, and the catalyst loading method need to be improved to strengthen the hydrogenation reaction process; on the other hand, in the reaction process, hydrogen molecules need to be present in the raw material at all times to maintain a high mass transfer and hydrogen-rich state to solve the problem. Here, the fixed bed hydrogenation process based on the gas-liquid countercurrent form not only can improve the hydrogenation reaction efficiency, but also can alleviate the catalyst coking problem, and has become a research hotspot of fixed bed hydrogenation reaction process.

[0004] Patent CN101343563B proposes a light hydrocarbon hydrogenation method, which adopts a series connection of a one-stage countercurrent hydrogenation reactor and a conventional co-current hydrogenation reactor. The raw material enters the flash zone of the countercurrent hydrogenation reactor at a lower temperature, the gas-phase hydrocarbon flows 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 hydrocarbon after flashing of the raw material flow downward together, and the thiophene sulfur and olefin 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.

[0005] Patent CN103805240B proposes a low-cost combined hydrofining method for oil products, which includes: first, mixing hydrogen into liquid phase materials, mixing the hydrogen-dissolved liquid phase materials into a liquid phase hydrogenation reactor for reaction, and then the liquid phase hydrogenation reaction materials enter a 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, and the reacted liquid product is partially recycled to the front of the liquid phase hydrogenation reactor, and the rest is used as the hydrogenation product.

[0006] Patent CN102041063B proposes a method for deep desulfurization of diesel oil, which is that the diesel oil raw material and hydrogen gas first pass through a gas-liquid countercurrent hydrogenation reaction zone, the effluent of the gas-liquid countercurrent hydrogenation reaction zone enters a gas-liquid co-current hydrogenation reaction zone, the gas-liquid co-current hydrogenation reaction zone adopts a gas-liquid co-current downward flow operation mode, wherein the gas-liquid countercurrent hydrogenation reaction zone uses a Mo-Co type hydrofining catalyst, and the gas-liquid co-current hydrogenation reaction zone uses a Mo-Ni type hydrofining catalyst or a W-Mo-Ni type hydrofining catalyst.

[0007] In the above-mentioned countercurrent hydrogenation invention method, the first hydrogenation reactor in the hydrogenation process is simply changed from a conventional gas-liquid co-current reactor to a gas-liquid countercurrent reactor, and there is no substantial improvement in the process flow, internal structure of the reactor and catalyst loading mode according to the characteristics of the gas-liquid countercurrent reaction process. Here, the process requirements, internal structure of the reactor, catalyst loading mode, etc. of the countercurrent hydrogenation reaction process and the co-current hydrogenation reaction process are essentially different. Simply changing the parts cannot solve the problems existing in the current gas-liquid co-current fixed bed hydrogenation reaction process, so as to play the process intensification role of the gas-liquid countercurrent reactor. SUMMARY

[0008] In view of the above technical problems and the deficiencies in the field, the present application provides a countercurrent hydrogenation reaction device based on lean hydrogen fluid and rich hydrogen fluid and its application. The present application forms lean hydrogen fluid and rich hydrogen fluid by respectively feeding raw material liquid and hydrogen gas into the countercurrent hydrogenation reactor for hydrogenation reaction, greatly intensifies the hydrogenation reaction rate and hydrogenation conversion depth, effectively inhibits the coking on the surface of the catalyst, makes the hydrogenation reaction more uniform, and prolongs the service life of the catalyst.

[0009] [1] A countercurrent hydrogenation reaction device based on lean hydrogen fluid and rich hydrogen fluid, comprising a lean hydrogen fluid forming zone, a rich hydrogen fluid forming zone and a countercurrent hydrogenation reaction zone.

[0010] The lean hydrogen fluid forming zone comprises at least one hydrogen dissolving device I for mixing raw material liquid I and hydrogen I to form lean hydrogen fluid; the lean hydrogen fluid is a fluid mainly in liquid phase flow state containing a small amount of nano / micron hydrogen gas bubbles, which can carry the dissolved and / or dispersed nano / micron hydrogen gas bubbles to flow downward under the action of gravity;

[0011] The hydrogen-rich fluid forming zone comprises at least one hydrogen dissolving device II for mixing raw material liquid II and hydrogen II to form a hydrogen-rich fluid; the hydrogen-rich fluid is a fluid containing a large amount of nano / micro hydrogen gas bubbles and mainly in a gas phase flow state, and has a characteristic tendency of upward diffusion like a gas phase fluid, and can carry the raw material liquid components therein to flow upward;

[0012] The countercurrent hydrogenation reaction zone comprises at least one countercurrent hydrogenation reactor, and the countercurrent hydrogenation reactor comprises a gas-liquid separation section, a countercurrent hydrogenation reaction section and a liquid-gas separation section which are sequentially and communicatively arranged from top to bottom; a hydrogen-poor fluid feeding port connected with the outlet of the hydrogen-poor fluid forming zone is arranged between the gas-liquid separation section and the countercurrent hydrogenation reaction section; a hydrogen-rich fluid feeding port connected with the outlet of the hydrogen-rich fluid forming zone is arranged between the countercurrent hydrogenation reaction section and the liquid-gas separation section; a gas outlet is arranged above the gas-liquid separation section; and a liquid outlet is arranged below the liquid-gas separation section.

[0013] The hydrogen-poor fluid is used to ensure that hydrogen is gradually consumed in the reaction process without a lack of hydrogen, and the fluid can still maintain a liquid phase flow state, which is beneficial to the countercurrent intensified mass transfer of the material.

[0014] The hydrogen-rich fluid is used to ensure that the fluid has a characteristic tendency of upward diffusion like a gas phase fluid, and the fluid has a certain density difference with the descending hydrogen-poor fluid. Further, the difference between the average density of the hydrogen-poor fluid and the average density of the hydrogen-rich fluid can be 50-900 kg / m 3 , preferably 100-550 kg / m 3 , so as to maintain good countercurrent intensified mass transfer characteristics. In the present application, 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 gas phase volume at standard conditions and the liquid volume at standard conditions.

[0015] In some embodiments, the hydrogen dissolving device I comprises a membrane assembly I and a shell I, the membrane assembly I comprises one or more membrane tube bundles I containing nano / micro holes, the raw material liquid I pipeline is in communication with the inlet end of the membrane tube bundle I, the hydrogen I pipeline is in space communication with the shell I, the hydrogen I diffuses into the membrane tube bundle I through the membrane tube wall to form a hydrogen-poor fluid with the raw material liquid I, and the outlet end of the membrane tube bundle I is the hydrogen-poor fluid outlet.

[0016] In some embodiments, the hydrogen dissolving device II comprises a membrane assembly II and a shell II, the membrane assembly II comprises one or more membrane tube bundles II containing nano / micro holes, the raw material liquid II pipeline is in communication with the inlet end of the membrane tube bundle II, the hydrogen II pipeline is in space communication with the shell II, the hydrogen II diffuses into the membrane tube bundle II through the membrane tube wall to form a hydrogen-rich fluid with the raw material liquid II, and the outlet end of the membrane tube bundle II is the hydrogen-rich fluid outlet.

[0017] The membrane tube bundle I and the membrane tube bundle II can be independently any one or a combination of ceramic membranes, metal membranes, metal ceramic composite membranes, alloy membranes, molecular sieve composite membranes, zeolite membranes, glass membranes, etc.

[0018] In some embodiments, the hydrogen mass fraction in the hydrogen-lean fluid is ≤1.0wt%, and the hydrogen mass fraction in the hydrogen-rich fluid is >1.0wt%.

[0019] In some embodiments, the average density of the hydrogen-rich fluid is less than the average density of the hydrogen-lean fluid. Further, the average density of the hydrogen-lean fluid can be 100-1000 kg / m 3 , and the average density of the hydrogen-rich fluid can be 5-400 kg / m 3 .

[0020] In some embodiments, the nanometer / micrometer hydrogen bubble size contained in the hydrogen-lean fluid and the hydrogen-rich fluid can be independently 10 nm-1000 μm.

[0021] The countercurrent hydrogenation reaction device based on the hydrogen-lean fluid and the hydrogen-rich fluid can comprise one or more monolithic catalyst unit modules. The shape of the monolithic catalyst unit module can be any one of a cylindrical shape, a rectangular shape, a square shape, a rhombic shape, a polygonal shape, etc., and is preferably a rectangular shape.

[0022] The height of the monolithic catalyst unit module can be 50-1500 mm, and is preferably 200-900 mm, such as 450 mm, etc.

[0023] The monolithic catalyst unit module can be provided with an array of honeycomb hole structures, and the opening ratio can be 5%-90%, and is preferably 45%-85%, such as 46.4%, 47.2%, 52.1%, 60.7%, 75.4%, 83.6%, etc. The honeycomb hole structures are mutually penetrable, which can increase the gas-liquid mass transfer contact area, and is also conducive to material diffusion flow and mass transfer and heat transfer. The opening ratio of the present application refers to the proportion of the opening area in the catalyst unit module to the entire module surface area.

[0024] In some embodiments, the opening ratio of the monolithic catalyst unit module increases along the hydrogen-lean fluid flow direction. Since the hydrogenation reaction is intense and the reaction temperature gradually increases along the hydrogen-lean fluid flow direction under the reaction conditions, the tendency of catalyst coking gradually increases, and the increase of the opening ratio of the monolithic catalyst unit module can effectively improve the diffusion, mass transfer and heat transfer of the material, which is conducive to more uniform reaction and prevents catalyst coking. Further, the opening ratio of the monolithic catalyst unit module gradually increases along the hydrogen-lean fluid flow direction, and the increase rate of the opening ratio of the adjacent two layers of catalyst unit modules is 0.1%-10%, and is preferably 1%-5%. The increase of the opening ratio can be achieved by increasing the number of openings, the single side or multi-side length of the holes, etc.

[0025] The internal channel size of the monolithic catalyst unit module can be 1 mm x 1 mm to 20 mm x 20 mm, preferably 3 mm x 3 mm to 15 mm x 15 mm, for example 6 mm x 6 mm, 8 mm x 8 mm, 10 mm x 10 mm, etc.

[0026] The monolithic catalyst unit module is generally composed of a monolithic honeycomb substrate, a coating material and an active component; in the preparation process, a monolithic honeycomb is used as the substrate, a method of loading a high specific surface coating and an active component in steps is adopted, and the active component impregnation thickness can be controlled by adjusting the coating amount; the monolithic modular catalyst can generally be a commercially available product or prepared according to conventional knowledge in the art as needed.

[0027] The active metal in the monolithic catalyst unit module can be a catalyst with hydrogenation function, i.e., one or more of the active components with functions such as hydrogenation saturation catalyst, hydrodesulfurization catalyst, hydrodenitrogenation catalyst, hydrodemetallization, hydrodeoxygenation, hydrocracking, aromatic hydrocarbon hydrogenation saturation, etc. can be selected according to the type of hydrogenation reaction.

[0028] In the countercurrent hydrogenation reactor, the diameters of the gas-liquid separation section, the countercurrent hydrogenation reaction section and the liquid-gas separation section can be the same or different, preferably the same.

[0029] The gas-liquid separation section can be provided with a component with gas-liquid separation function for gas-liquid separation; the component with gas-liquid separation function can be one or more of baffle plate structure, cyclone / centrifugal structure, packing and wire mesh structure, etc.

[0030] The liquid-gas separation section can be provided with liquid level control and a certain liquid level height to keep the liquid with sufficient residence time to realize liquid-gas separation, and can or can not be provided with a component with liquid-gas separation function inside.

[0031] In some embodiments, the height-diameter ratio of the countercurrent hydrogenation reactor can be 0.5 to 10:1, preferably 1 to 6:1, for example 2:1, 3:1, 4:1, etc.

[0032] In some embodiments, a support grid can be provided at the lower part of the monolithic catalyst unit module. Further, the support grid and the inner wall of the countercurrent hydrogenation reactor can be a welded structure.

[0033] In some embodiments, a compression grid can be provided at the upper part of the monolithic catalyst unit module. Further, the compression grid and the inner wall of the countercurrent hydrogenation reactor can be a movable connection structure.

[0034] In some embodiments, the countercurrent hydrogenation reaction section can contain 2 to 100 layers, preferably 10 to 60 layers (for example 20 layers, 30 layers, 40 layers, etc.) of monolithic catalyst unit modules.

[0035] [2] The use of the countercurrent hydrogenation reaction device based on lean hydrogen fluid and rich hydrogen fluid according to [1] in hydrogenation reaction.

[0036] The countercurrent hydrogenation reaction device based on lean hydrogen fluid and rich hydrogen fluid is suitable for various raw materials in the fields of petroleum chemical industry, medicine, food, etc. that can have 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. The device can also be used for various raw materials in the fields of chemical industry, medicine, food, etc. that can have 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.

[0037] [3] A hydrogenation method using the countercurrent hydrogenation reaction device based on lean hydrogen fluid and rich hydrogen fluid according to [1].

[0038] In some embodiments, the hydrogenation method, the lean hydrogen fluid is formed by dissolving hydrogen I and a small amount of raw material liquid I in a hydrogen dissolving device I and introduced into the countercurrent hydrogenation reactor through the lean hydrogen fluid inlet, the rich hydrogen fluid is formed by dissolving hydrogen II and a small amount of raw material liquid II in a hydrogen dissolving device II and introduced into the countercurrent hydrogenation reactor through the rich hydrogen fluid inlet, and the two have countercurrent hydrogenation reaction in the countercurrent hydrogenation reaction section. The remaining hydrogen after the reaction is completed is separated from the liquid through the gas-liquid separation section and then discharged from the gas outlet. The reaction liquid after the reaction is completed is separated from the gas through the liquid-gas separation section and then discharged from the liquid outlet.

[0039] The hydrogenation method, the lean hydrogen fluid and the rich hydrogen fluid can be introduced into the countercurrent hydrogenation reactor in any one or a combination of the following modes:

[0040] Mode one: introducing from the lower part or the upper part of the countercurrent hydrogenation reaction section;

[0041] Mode two: introducing multiple times along the axial direction of the countercurrent hydrogenation reactor to any position in the countercurrent hydrogenation reaction section.

[0042] In some embodiments, the hydrogenation method, the feed ratio of hydrogen I to raw material liquid I in the lean hydrogen fluid can be 0.5-50 Nm 3 / h: 1 m 3 / h.

[0043] In some embodiments, the hydrogenation method, the feed ratio of hydrogen II to reaction liquid II in the rich hydrogen fluid can be 10-1000 Nm 3 / h: 1 m 3 / h, preferably 10-400 Nm 3 / h: 1 m 3 / h, for example 15 Nm 3 / h: 1 m 3 / h, 20 Nm 3 / h: 1 m 3 / h, 25 Nm 3 / h: 1 m 3 / h, 200 Nm 3 / h: 1 m 3 / h, 220 Nm 3 / h: 1 m 3 / h, 280 Nm 3 / h: 1 m 3 / h, etc.

[0044] The hydrogenation method can use hydrogen with a purity of greater than 90 vol%, preferably pure hydrogen of 99.9 vol% or more.

[0045] In some embodiments, the hydrogenation method, the process conditions of the countercurrent hydrogenation reactor can include: a reaction temperature of normal temperature to 500 DEG C, a reaction pressure of 0.1 to 20 MPaG, a liquid hourly space velocity of 0.1 to 20 h -1 .

[0046] In a conventional countercurrent hydrogenation process, a major problem existing in the prior art is that the gas-liquid-solid three-phase diffusion mass transfer and reaction efficiency is low, mainly due to the large resistance of hydrogen molecules to diffuse and mass transfer into the liquid phase and then to the surface of the catalyst during the reaction; on the other hand, as the hydrogenation reaction proceeds, especially for hydrogen-consuming hydrogenation reaction systems, the catalyst surface is always in a hydrogen-deficient state, which is extremely easy to coking and deactivation on the catalyst surface at a high reaction temperature; in addition, hydrogenation reactions are generally exothermic reactions, and as the reaction proceeds, the temperature gradually increases and the heat gradually accumulates, resulting in local hot spots in the catalyst bed, which not only makes the reaction extremely uneven, but also greatly increases the side reactions.

[0047] The present application has the following beneficial effects compared with the prior art:

[0048] (1) The hydrogenation reaction raw material liquid is made into a hydrogen-poor fluid form, the hydrogen-poor fluid is a fluid containing a small amount of nanometer / micron hydrogen gas bubbles and mainly in liquid phase flow state, using this form can effectively improve the diffusion and mass transfer of hydrogen molecules, thereby greatly increasing the hydrogenation reaction rate, and on the other hand, it can improve the hydrogen-deficient state of the catalyst surface during the reaction, solve the problem of catalyst coking and deactivation, and maintain the entire hydrogenation reaction process to proceed continuously and efficiently;

[0049] (2) hydrogen gas is made into a hydrogen-rich fluid, which is a fluid containing a large amount of nanometer / micrometer hydrogen gas bubbles and mainly in a gaseous phase flow state. In this form, on the one hand, the diffusion mass transfer resistance can be greatly reduced to provide sufficient hydrogen source for the hydrogenation reaction process, so that good results can be maintained under more moderate conditions. On the other hand, the average density of the hydrogen-rich fluid is higher than that of hydrogen gas but much lower than that of the raw material liquid. The purpose is to reduce the rate of upward diffusion movement of the hydrogen-rich fluid, reduce the probability of bubble coalescence, prevent problems such as gas short circuit and reduce the reaction efficiency, so as to maintain a sustained and efficient hydrogenation reaction.

[0050] (3) The countercurrent hydrogenation catalyst is adopted in the form of a whole modular unit stack, and the opening rate of the whole catalyst unit module gradually increases along the axial direction of the reactor and the flow direction of the hydrogen-poor fluid. This is mainly because in the countercurrent hydrogenation reactor, the hydrogenation reaction intensity and reaction temperature gradually increase along the flow direction of the hydrogen-poor fluid, and the coking tendency of the catalyst gradually increases. Gradual increase of the opening rate of the internal pore channel of the whole catalyst unit module can effectively improve the diffusion mass transfer and heat transfer of the material, prevent catalyst coking, and make the reaction more uniform. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 A countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid is shown in the structure diagram. DETAILED DESCRIPTION

[0052] The present application will be further described below in conjunction with the drawings and specific examples. It should be understood that these examples are only used to illustrate the present application and are not used to limit the scope of the present 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 countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid includes a hydrogen-poor fluid forming area, a hydrogen-rich fluid forming area, and a countercurrent hydrogenation reaction area.

[0054] The hydrogen-poor fluid forming area includes a hydrogen dissolving device I 3 for mixing the raw material liquid I 1 and hydrogen I 2 to form a hydrogen-poor fluid 4. The hydrogen-poor fluid 4 is a fluid containing a small amount of nanometer / micrometer hydrogen gas bubbles and mainly in a liquid phase flow state, which can carry the nanometer / micrometer hydrogen gas bubbles dissolved and / or dispersed therein to flow downward under the action of gravity. The hydrogen dissolving device I 3 includes a membrane assembly I and a shell I, the membrane assembly I includes one or more membrane tube bundles I containing nanometer / micrometer pores, the raw material liquid I pipeline is in communication with the inlet end of the membrane tube bundle I, the hydrogen I pipeline is in space communication with the shell I, the hydrogen I 2 diffuses through the membrane tube wall into the membrane tube bundle I to form the hydrogen-poor fluid 4 with the raw material liquid I 1, and the outlet end of the membrane tube bundle I is the hydrogen-poor fluid outlet.

[0055] The hydrogen-rich fluid forming section comprises a hydrogen dissolving device II 7 for mixing the raw material liquid II 5 and the hydrogen II 6 to form the hydrogen-rich fluid 8. The hydrogen-rich fluid 8 is a fluid containing a large amount of nano / micro hydrogen gas bubbles and mainly in a gas phase flow state, and has a characteristic tendency of upward diffusion as a gas phase fluid, and can carry the raw material liquid components therein to flow upward. The hydrogen dissolving device II 7 comprises a membrane assembly II and a shell II, the membrane assembly II comprises one or more membrane tube bundles II containing nano / micro-porous membrane tubes, the raw material liquid II pipeline is in communication with the inlet end of the membrane tube bundle II, the hydrogen II pipeline is in space communication with the shell II, the hydrogen II 6 diffuses through the membrane tube wall into the membrane tube bundle II to form the hydrogen-rich fluid 8 with the raw material liquid II 5, and the outlet end of the membrane tube bundle II is the hydrogen-rich fluid outlet.

[0056] The membrane tube bundle I and the membrane tube bundle II can be independently any one or a combination of ceramic membranes, metal membranes, metal-ceramic composite membranes, alloy membranes, molecular sieve composite membranes, zeolite membranes, and glass membranes.

[0057] The hydrogen mass fraction in the hydrogen-poor fluid 4 is ≤1.0wt%, and the hydrogen mass fraction in the hydrogen-rich fluid 8 is >1.0wt%. The average density of the hydrogen-rich fluid is less than the average density of the hydrogen-poor fluid. The average density of the hydrogen-poor fluid can be 100-1000kg / m 3 . The average density of the hydrogen-rich fluid can be 5-400kg / m 3 . The difference between the average density of the hydrogen-poor fluid and the average density of the hydrogen-rich fluid can be 50-900kg / m 3 , preferably 100-550kg / m 3 . The size of the nano / micro hydrogen gas bubbles contained in the hydrogen-poor fluid and the hydrogen-rich fluid is independently 10nm-1000μm.

[0058] The countercurrent hydrogenation reaction section comprises a countercurrent hydrogenation reactor 11, which comprises a gas-liquid separation section 14, a countercurrent hydrogenation reaction section 16 and a liquid-gas separation section 15 arranged in sequence from top to bottom. A hydrogen-poor fluid inlet connected to the outlet of the hydrogen dissolving device I 3 is arranged between the gas-liquid separation section 14 and the countercurrent hydrogenation reaction section 16 to receive the hydrogen-poor fluid 4. A hydrogen-rich fluid inlet connected to the outlet of the hydrogen dissolving device II 7 is arranged between the countercurrent hydrogenation reaction section 16 and the liquid-gas separation section 15 to receive the hydrogen-rich fluid 8. A gas outlet is arranged above the gas-liquid separation section 14. A liquid outlet is arranged below the liquid-gas separation section 15.

[0059] A hydrogenation method using the countercurrent hydrogenation reaction device based on the hydrogen-poor fluid and the hydrogen-rich fluid as shown in Figure 1 , comprising:

[0060] Firstly, the raw material liquid I 1 and hydrogen I 2 are dissolved by the hydrogen dissolving equipment I 3 to form a hydrogen-poor fluid 4, which enters the countercurrent hydrogenation reactor 11 from the top; the raw material liquid II 5 and hydrogen II 6 are dissolved by the hydrogen dissolving equipment II 7 to form a hydrogen-rich fluid 8, which enters the countercurrent hydrogenation reactor 11 from the bottom; the hydrogen-poor fluid 4 and the hydrogen-rich fluid 8 are uniformly distributed through the upper distributor 12 and the lower distributor 13 respectively, and then enter the integrated catalyst unit module 17 in the countercurrent hydrogenation reaction section 16 to perform countercurrent hydrogenation reaction; the remaining gas 9 after the reaction is separated by the gas-liquid separation section 14 and then leaves; the liquid reaction product 10 is separated by the liquid-gas separation section 15 and then leaves.

[0061] The above-mentioned countercurrent hydrogenation reaction device and hydrogenation method based on hydrogen-poor fluid and hydrogen-rich fluid are applied to the hydrogenation processes of straight-run diesel and biomass sugar (glucose) solution. The properties of the straight-run diesel raw material are shown in Table 1, and the properties of the straight-run diesel hydrogenation catalyst are shown in Table 2; the properties of the biomass sugar (glucose) hydrogenation raw material are shown in Table 3, and the properties of the biomass sugar (glucose) solution hydrogenation catalyst are shown in Table 4. All the above-mentioned raw materials are commercially available, and all the hydrogenation catalysts are self-made.

[0062] Table 1 Properties of straight-run diesel raw material

[0063] Item Feed oil Density, g / cm 3 ]] 0.834 Viscosity, mm 2 / s]] 765.8 Sulfur, wt% 0.61 Nitrogen, pg / g 101 Distillation range, °C IBP / 5% 201 / 235 10％ / 30％ 256 / 267 50％ / 70％ 288 / 300 90％ / 95％ 320 / 331 EBP 353

[0064] Table 2 Physicochemical indexes of straight-run diesel hydrogenation catalyst

[0065]

[0066] Table 3 Biomass sugar (glucose) solution raw material

[0067] Item Indicator Property Colorless transparent liquid Concentration, mol / L 1.5

[0068] Table 4 Properties of biomass sugar (glucose) solution hydrogenation catalyst

[0069]

[0070] Comparative Example 1

[0071] A conventional gas-liquid concurrent fixed bed hydrogenation process is adopted, and the height-diameter ratio of the hydrogenation reactor is 2.5. The reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation are investigated under different conditions by using the device; the hydrogenation reactor is filled with non-integral modular catalysts corresponding to the respective reactions.

[0072] Firstly, the mixture of the raw material and hydrogen is adjusted to the inlet temperature of the hydrogenation reactor, and then enters the hydrogenation reactor from the top, and the hydrogenation reaction occurs through the catalyst bed from top to bottom, and the reaction is completed.

[0073] The operating conditions of the hydrogenation reactor are shown in Table 5, and the reaction results are shown in Table 6. The volume space velocity in Table 5 represents the volume space velocity in liquid time, which will not be repeated hereinafter.

[0074] Comparative Example 2

[0075] A conventional gas-liquid countercurrent fixed-bed hydrogenation process was used, and the height-diameter ratio of the hydrogenation reactor was 2.5. The reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation were investigated under different conditions using the device respectively. The hydrogenation reactor was filled with non-integral modular catalysts corresponding to the respective reactions.

[0076] First, the raw material liquid was adjusted to the inlet temperature of the hydrogenation reactor and then entered from the top of the hydrogenation reactor, and the hydrogen was adjusted to the inlet temperature of the hydrogenation reactor and then entered from the bottom of the hydrogenation reactor, and the hydrogenation reaction occurred in the hydrogenation reactor, and the liquid product and the remaining gas were obtained after the hydrogenation reaction was completed.

[0077] The operating conditions of the hydrogenation reactor are shown in Table 5, and the reaction results are shown in Table 6.

[0078] Comparative Example 3

[0079] The hydrogenation process flow and reactor setting are the same as those in Comparative Example 2, and the difference lies in that the hydrogenation reactor is filled with 35 layers of integral modular catalysts corresponding to the respective reactions, and the hole size of the catalyst unit is 6mmx6mm.

[0080] The operating conditions of the hydrogenation reactor are shown in Table 5, and the reaction results are shown in Table 6.

[0081] Example 1

[0082] The countercurrent hydrogenation reaction device and hydrogenation method based on the lean hydrogen fluid and the rich hydrogen fluid introduced in the specific embodiment of the present application are used. The height-diameter ratio of the countercurrent hydrogenation reactor is 2.0; the countercurrent hydrogenation reaction section is filled with 20 layers of integral modular catalysts; the opening rate of the first layer of catalyst unit module is 52.1%, and the opening rate of the 20th layer of catalyst unit module is 75.4%, and the opening rates of the catalyst unit modules from the first layer to the 20th layer uniformly increase, and the hole size is 6mmx6mm. The number of layers of the catalyst unit modules increases in the direction of the flow of the lean hydrogen fluid, such as the first layer of catalyst unit being the position of the addition of the lean hydrogen fluid, and the second layer, the third layer, etc. in turn in the direction of the flow of the lean hydrogen fluid.

[0083] The reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation were investigated under different conditions using the device respectively.

[0084] Firstly, the raw material liquid and a small amount of hydrogen are prepared into a hydrogen-poor fluid by a ceramic membrane mixing device, the hydrogen bubble size is 10nm-1000μm, the material is adjusted to the reaction temperature and enters from the upper part of the countercurrent hydrogenation reactor, hydrogen and a small amount of raw material liquid are prepared into a hydrogen-rich fluid by a ceramic membrane mixing device, the hydrogen bubble size is 10nm-1000μm, the material is adjusted to the reaction temperature and enters from the lower part of the countercurrent hydrogenation reactor, the countercurrent hydrogenation reaction occurs in the catalyst bed, and the remaining gas and liquid products are discharged from the top and bottom, respectively.

[0085] The operation conditions of the countercurrent hydrogenation reactor are shown in Table 5, and the reaction results are shown in Table 6.

[0086] Example 2

[0087] The countercurrent hydrogenation reaction device and hydrogenation method based on hydrogen-poor fluid and hydrogen-rich fluid introduced in the specific embodiment of the application are used in the process flow of Example 1. The difference lies in the hydrogen liquid ratio of the hydrogen-poor fluid and the hydrogen-rich fluid, the height-diameter ratio of the countercurrent hydrogenation reactor and the catalyst unit module, which are as follows:

[0088] The height-diameter ratio of the countercurrent hydrogenation reactor is 3.0; the countercurrent hydrogenation reaction section is filled with 30 layers of integral modular catalyst; the opening rate of the first layer of catalyst unit module is 46.4%, the opening rate of the 30th layer of catalyst unit module is 60.7%, and the opening rate of the catalyst unit module from the first layer to the 30th layer increases uniformly; the hole size is 10mmx10mm. The number of layers of the catalyst unit module increases in the direction of the flow of the hydrogen-poor fluid, such as the first layer of catalyst unit being the hydrogen-poor fluid addition position, and the second layer, the third layer and the like in turn in the flow direction of the hydrogen-poor fluid.

[0089] The reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation are investigated under different conditions by using the device.

[0090] Firstly, the raw material liquid and a small amount of hydrogen are prepared into a hydrogen-poor fluid by a ceramic membrane mixing device, the hydrogen bubble size is 10nm-1000μm, the material is adjusted to the reaction temperature and enters from the upper part of the countercurrent hydrogenation reactor, hydrogen and a small amount of raw material liquid are prepared into a hydrogen-rich fluid by a ceramic membrane mixing device, the hydrogen bubble size is 10nm-1000μm, the material is adjusted to the reaction temperature and enters from the lower part of the countercurrent hydrogenation reactor, the countercurrent hydrogenation reaction occurs in the catalyst bed, and the remaining gas and liquid products are discharged from the top and bottom, respectively.

[0091] The operation conditions of the countercurrent hydrogenation reactor are shown in Table 5, and the reaction results are shown in Table 6.

[0092] Example 3

[0093] The countercurrent hydrogenation reaction device and hydrogenation method based on the lean hydrogen fluid and the rich hydrogen fluid introduced in the embodiment of the present application have the same process flow as that of Example 1. The difference lies in the hydrogen liquid ratio of the lean hydrogen fluid and the rich hydrogen fluid, the height-diameter ratio of the countercurrent hydrogenation reactor and the catalyst unit module, and the details are as follows:

[0094] The height-diameter ratio of the countercurrent hydrogenation reactor is 4.0; the countercurrent hydrogenation reaction section is filled with 40 layers of the integral modular catalyst; the opening ratio of the first layer of the catalyst unit module is 47.2%, the opening ratio of the 40th layer of the catalyst unit module is 83.6%, and the opening ratio of the catalyst unit module from the first layer to the 40th layer increases uniformly; and the channel size of the first-20th layer of the catalyst unit module is 3mm x 3mm, and the channel size of the 21st-40th layer of the catalyst unit module is 8mm x 8mm. The layer number of the catalyst unit module increases along the flow direction of the lean hydrogen fluid, for example, the first layer of the catalyst unit is the lean hydrogen fluid addition position, and the second layer, the third layer and the like are sequentially arranged along the flow direction of the lean hydrogen fluid.

[0095] The reaction effects of the straight-run diesel hydrogenation and the biomass sugar (glucose) hydrogenation are investigated under different conditions by using the device.

[0096] First, the raw material liquid is mixed with a small amount of hydrogen gas by a ceramic membrane mixing device to prepare a lean hydrogen fluid, the hydrogen gas bubble size is 10nm-1000μm, the material is adjusted to the reaction temperature and then enters from the upper part of the countercurrent hydrogenation reactor, the hydrogen gas and a small amount of raw material liquid are prepared into a rich hydrogen fluid by a ceramic membrane mixing device, the hydrogen gas bubble size is 10nm-1000μm, the material is adjusted to the reaction temperature and then enters from the lower part of the countercurrent hydrogenation reactor, and the countercurrent hydrogenation reaction occurs in the catalyst bed, and the remaining gas and liquid products are obtained from the top and bottom, respectively.

[0097] The operating conditions of the countercurrent hydrogenation reactor are shown in Table 5, and the reaction results are shown in Table 6.

[0098] Table 5 Operating conditions of the countercurrent hydrogenation reactor

[0099]

[0100] Table 6 Reaction results of the countercurrent hydrogenation reactor

[0101]

[0102] Note: Δt11, Δt12, Δt13 are the average radial temperature differences in the upper, middle and lower parts of the countercurrent hydrogenation reactor.

[0103] From the hydrogenation reaction effect of the examples and the comparative examples of the present application, it can be seen that the method of the present application introduces the hydrogen-poor fluid and the hydrogen-rich fluid into the countercurrent hydrogenation reactor respectively, and then into the catalyst bed provided with the catalyst unit module to perform countercurrent hydrogenation reaction, which greatly strengthens the countercurrent hydrogenation reaction rate, reaction conversion depth and reaction uniformity. Compared with the prior art, on the one hand, more moderate conditions such as lower temperature and pressure, higher space velocity and lower hydrogen liquid ratio can be adopted to achieve better hydrogenation conversion effect, and on the other hand, based on the fact that the carbon deposition and coking of the catalyst can be greatly improved, the problems of reaction heat concentration and local hot spots are solved, the catalyst operation cycle is significantly prolonged, and the operation cost is greatly reduced while achieving the same hydrogenation reaction effect.

[0104] Furthermore, it is to be understood that even though numerous characteristics and embodiments of the application have been set forth in the foregoing description, many modifications and / or changes of the embodiments of the application in addition to those described above are possible. Such modifications and changes are also intended to fall within the scope of the application as defined in the appended claims.

Claims

1. A countercurrent hydrogenation reactor based on hydrogen-poor and hydrogen-rich fluids, characterized in that, It includes a hydrogen-poor fluid formation zone, a hydrogen-rich fluid formation zone, and a countercurrent hydrogenation reaction zone; The hydrogen-deficient fluid formation zone includes at least one hydrogen dissolving device I for mixing the raw material liquid I and hydrogen gas I to form a hydrogen-deficient fluid; the hydrogen-deficient fluid is a fluid containing a small amount of nano / micron hydrogen gas bubbles and mainly in liquid phase flow, which can carry the dissolved and / or dispersed nano / micron hydrogen gas bubbles together and flow downward under the action of gravity. The hydrogen-rich fluid formation zone includes at least one hydrogen dissolving device II for mixing the raw material liquid II and hydrogen gas II to form a hydrogen-rich fluid; the hydrogen-rich fluid is a fluid containing a large number of nano / micron hydrogen bubbles and mainly in the gas phase flow state, with an overall upward diffusion characteristic like a gas phase fluid, and can carry the raw material liquid components therein upward. The countercurrent hydrogenation reaction zone includes at least one countercurrent hydrogenation reactor, which comprises a gas-to-liquid degassing section, a countercurrent hydrogenation reaction section, and a liquid-to-gas degassing section connected sequentially from top to bottom. A hydrogen-poor fluid inlet is provided between the gas-to-liquid degassing section and the countercurrent hydrogenation reaction section, connecting to the outlet of the hydrogen-poor fluid formation zone. A hydrogen-rich fluid inlet is provided between the countercurrent hydrogenation reaction section and the liquid-to-gas degassing section, connecting to the outlet of the hydrogen-rich fluid formation zone. A gas outlet is provided above the gas-to-liquid degassing section, and a liquid outlet is provided below the liquid-to-gas degassing section. The countercurrent hydrogenation reaction section contains one or more monolithic catalyst unit modules; the porosity in the monolithic catalyst unit module increases along the direction of hydrogen-poor fluid flow.

2. The countercurrent hydrogenation reactor based on hydrogen-poor and hydrogen-rich fluids according to claim 1, characterized in that, The hydrogen dissolving device I includes a membrane module I and a housing I. The membrane module I includes one or more membrane tube bundles I containing nano / micro pores. The feed liquid I pipeline is connected to the inlet end of the membrane tube bundle I, and the hydrogen I pipeline is connected to the space of the housing I. The hydrogen I diffuses into the membrane tube bundle I through the membrane tube wall and forms a hydrogen-deficient fluid with the feed liquid I. The outlet end of the membrane tube bundle I is the hydrogen-deficient fluid outlet. The hydrogen dissolving device II includes a membrane module II and a housing II. The membrane module II includes one or more membrane tube bundles II containing nano / micro pores. The feed liquid II pipeline is connected to the inlet end of the membrane tube bundle II, and the hydrogen II pipeline is connected to the space of the housing II. The hydrogen II diffuses into the membrane tube bundle II through the membrane tube wall and forms a hydrogen-rich fluid with the feed liquid II. The outlet end of the membrane tube bundle II is the hydrogen-rich fluid outlet. Membrane tube bundle I and membrane tube bundle II are each independently any one or more combinations of ceramic membrane, metal membrane, metal-ceramic composite membrane, alloy membrane, molecular sieve composite membrane, zeolite membrane, and glass membrane.

3. The countercurrent hydrogenation reactor based on hydrogen-poor and hydrogen-rich fluids according to claim 1, characterized in that, The hydrogen mass fraction in a hydrogen-poor fluid is ≤1.0wt%, and the hydrogen mass fraction in a hydrogen-rich fluid is >1.0wt%. The average density of hydrogen-rich fluids is less than that of hydrogen-poor fluids; the average density of hydrogen-poor fluids is 100–1000 kg / m³. 3 The average density of hydrogen-rich fluids is 5–400 kg / m³. 3 The difference between the average density of hydrogen-poor fluid and the average density of hydrogen-rich fluid is 50–900 kg / m³. 3 Average density is defined as the sum of the masses of the gas and liquid phases in a fluid divided by the sum of the standard volumes of the gas and liquid phases. The sizes of the nano / micron hydrogen bubbles contained in the hydrogen-poor fluid and the hydrogen-rich fluid are independently 10 nm to 1000 μm.

4. The countercurrent hydrogenation reactor based on hydrogen-poor and hydrogen-rich fluids according to claim 3, characterized in that, The difference between the average density of hydrogen-poor fluid and the average density of hydrogen-rich fluid is 100–550 kg / m³. 3 .

5. The countercurrent hydrogenation reactor based on hydrogen-poor and hydrogen-rich fluids according to claim 1, characterized in that, The height of a single-layer integral catalyst unit module is 50–1500 mm; The integral catalyst unit module is provided with an array of honeycomb pore structures with an opening rate of 5% to 90%, and the honeycomb pore structures are interconnected. The internal pore size of the integral catalyst unit module is 1mm×1mm~20mm×20mm; The rate of increase in porosity between two adjacent catalyst unit modules is 0.1% to 10%. The increase in porosity is achieved by increasing the number of openings, or by one or more combinations of increasing the single-sided or multi-sided side length of the openings. In a countercurrent hydrogenation reactor, the diameters of the gas-to-liquid section, the countercurrent hydrogenation reaction section, and the liquid-to-gas section may be the same or different. The height-to-diameter ratio of the countercurrent hydrogenation reactor is 0.5–10:1; The lower part of the integral catalyst unit module is equipped with a support grid; the support grid and the inner wall of the countercurrent hydrogenation reactor are welded together. The integral catalyst unit module is equipped with a compression grid on the top; the compression grid and the inner wall of the countercurrent hydrogenation reactor are connected by a movable structure.

6. The countercurrent hydrogenation reactor based on hydrogen-poor and hydrogen-rich fluids according to claim 5, characterized in that, The height of a single-layer integral catalyst unit module is 200–900 mm; The opening ratio of the integral catalyst unit module is 45% to 85%; The internal pore size of the integral catalyst unit module is 3mm×3mm~15mm×15mm; The rate of increase in porosity between adjacent catalyst unit modules is 1% to 5%; The height-to-diameter ratio of the countercurrent hydrogenation reactor is 1 to 6:

1.

7. The countercurrent hydrogenation reactor based on hydrogen-poor and hydrogen-rich fluids according to claim 1, 5, or 6, characterized in that, The countercurrent hydrogenation reaction section contains 2 to 100 layers of integral catalyst unit modules.

8. The countercurrent hydrogenation reactor based on hydrogen-poor and hydrogen-rich fluids according to claim 7, characterized in that, The countercurrent hydrogenation reaction section contains 10 to 60 layers of integral catalyst unit modules.

9. The application of the countercurrent hydrogenation reactor based on hydrogen-poor fluid and hydrogen-rich fluid according to any one of claims 1 to 8 in hydrogenation reactions.

10. A hydrogenation method, characterized in that, The countercurrent hydrogenation reactor based on hydrogen-poor fluid and hydrogen-rich fluid as described in any one of claims 1 to 8 is adopted.

11. The hydrogenation method according to claim 10, characterized in that, Raw material liquid I and a small amount of hydrogen gas I are processed by hydrogen dissolving equipment I to form a hydrogen-lean fluid, which enters the countercurrent hydrogenation reactor through the hydrogen-lean fluid inlet. Hydrogen gas II and a small amount of raw material liquid II are processed by hydrogen dissolving equipment II to form a hydrogen-rich fluid, which enters the countercurrent hydrogenation reactor through the hydrogen-rich fluid inlet. The two undergo a countercurrent hydrogenation reaction in the countercurrent hydrogenation reaction section. After the reaction is completed, the remaining hydrogen is separated into gas and liquid in the gas deliquencing section and leaves from the gas outlet. After the reaction is completed, the reaction liquid is separated into gas and liquid in the liquid degassing section and leaves from the liquid outlet.

12. The hydrogenation method according to claim 11, characterized in that, The hydrogen-lean fluid and the hydrogen-rich fluid are independently selected from any one or more combinations of the following methods and introduced into the countercurrent hydrogenation reactor: Method 1: Set up a flow source from the bottom or top of the countercurrent hydrogenation reaction section; Method 2: Multiple streams are introduced along the axial direction of the countercurrent hydrogenation reactor to any position in the countercurrent hydrogenation reaction section.

13. The hydrogenation method according to claim 11 or 12, characterized in that, The feed ratio of hydrogen gas I to feed liquid I in the hydrogen-deficient fluid is 0.5–50 Nm. 3 / h:1m 3 / h; The feed ratio of hydrogen gas II to reaction liquid II in the hydrogen-rich fluid is 10–1000 Nm. 3 / h:1m 3 / h; The hydrogenation method uses hydrogen gas with a purity greater than 90 vol%. The process conditions for the countercurrent hydrogenation reactor include: reaction temperature of ambient to 500℃, reaction pressure of 0.1 to 20 MPaG, and liquid hourly space velocity of 0.1 to 20 h⁻¹. -1 .

14. The hydrogenation method according to claim 13, characterized in that, The feed ratio of hydrogen gas II to reaction liquid II in the hydrogen-rich fluid is 10–400 Nm. 3 / h:1m 3 / h; The hydrogenation method uses pure hydrogen of 99.9 vol% or higher.

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