Counter-current hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid and application of counter-current hydrogenation reaction device

Abstract

The invention 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 the hydrogen-poor fluid and the 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 and is used for mixing a raw material solution I and hydrogen I to form a hydrogen-poor fluid; the hydrogen-rich fluid forming area comprises at least one hydrogen dissolving device II and is used for mixing the raw material liquid II and the hydrogen II to form a hydrogen-rich fluid; the countercurrent hydrogenation reaction zone comprises at least one countercurrent hydrogenation reactor. The raw material liquid and the hydrogen respectively form the hydrogen-poor fluid and the hydrogen-rich fluid, and the hydrogen-poor fluid and the hydrogen-rich fluid enter the countercurrent hydrogenation reactor for hydrogenation reaction, so that the hydrogenation reaction rate and the hydrogenation conversion depth are greatly enhanced, coking on the surface of the catalyst is effectively inhibited, the hydrogenation reaction is more uniform, and the service life of the catalyst is prolonged.

Description

Technical Field

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

[0002] Hydrogenation technology is a process technology that uses a catalyst to react raw materials with hydrogen to obtain the target product under a certain temperature and hydrogen partial pressure. Fixed bed hydrogenation processes and reactors are the most widely used and can be used in various types of hydrogenation processes. Fixed bed hydrogenation can be divided into two types: upflow (downflow) and downflow (upper flow) according to the overall feeding direction of the material. The downflow (upper flow), especially the gas-liquid co-flow downflow (upper flow) fixed bed hydrogenation process, is the most widely used.

[0003] Although the gas-liquid co-current fixed bed hydrogenation process has been widely used, the following problems still exist: (1) The liquid passes through the catalyst bed in the form of a liquid film, and the gas-liquid mass transfer rate is low. Generally, relatively harsh reaction conditions are required, such as high temperature, high pressure, and low air velocity, resulting in high energy consumption; (2) The hydrogenation process requires a large hydrogen-to-oil ratio, and generally a relatively large hydrogen-to-oil ratio is required to achieve the ideal reaction effect. Therefore, the size of the reactor and the reaction system is large and the investment is high; (3) The raw material has a long residence time under high temperature, high pressure, and low air velocity conditions, resulting in serious side reactions and catalyst coking; (4) After the hydrogen is consumed in the reaction process, the hydrogen molecules do not have time to transfer and diffuse to the main body of the raw material in large quantities, resulting in hydrogen deficiency and coking on the catalyst surface, causing uneven reaction and even unable to operate for a long period of time. The reason is that on the one hand, the fixed bed gas-liquid co-current process, reactor form, and catalyst loading method need to be improved to strengthen the hydrogenation reaction process; on the other hand, the raw material needs to always have hydrogen molecules during the reaction process to maintain a high mass transfer and hydrogen-rich state, so as to solve this problem. Here, the fixed bed hydrogenation process based on gas-liquid countercurrent can not only improve the efficiency of the hydrogenation reaction, but also alleviate the problem of catalyst coking, becoming a research hotspot for fixed bed hydrogenation reaction technology.

[0004] Patent CN101343563B proposes a light hydrocarbon hydrogenation method, which uses a countercurrent hydrogenation reactor and a conventional parallel flow hydrogenation reactor in series. The raw material enters the flash zone of the countercurrent hydrogenation reactor at a relatively low temperature, and the gaseous hydrocarbon flows upward to react with diolefins and mercaptans to form sulfide and diolefin hydrogenation in the upper part of the countercurrent reactor. The high-boiling sulfide produced by the upper reaction and the liquid hydrocarbon after the raw material flash flow downward together, and thiophene sulfur and olefin undergo alkylation reaction; hydrogen enters from the bottom of the countercurrent reactor and flows upward; the liquid phase discharged from the bottom of the countercurrent reactor is mixed with new hydrogen and heated before entering the parallel flow hydrogenation reactor for deep hydrodesulfurization, selective cracking or isomerization reactions.

[0005] Patent CN103805240B proposes a low-cost combined hydrogenation refining method for oil products, including: first, hydrogen is mixed into liquid phase materials, the mixed hydrogen-soluble liquid phase materials enter the liquid phase hydrogenation reactor for reaction, the materials after the liquid phase hydrogenation reaction enter the countercurrent reactor from the top 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 part of the liquid product after the reaction is circulated 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, in which the diesel feedstock and hydrogen first pass through a gas-liquid countercurrent hydrogenation reaction zone, and the effluent of the gas-liquid countercurrent hydrogenation reaction zone enters a gas-liquid parallel flow hydrogenation reaction zone. The gas-liquid parallel flow hydrogenation reaction zone adopts a gas-liquid parallel flow downward flow operation mode, wherein the gas-liquid countercurrent hydrogenation reaction zone uses a Mo-Co type hydrogenation refining catalyst, and the gas-liquid parallel flow hydrogenation reaction zone uses a Mo-Ni type hydrogenation refining catalyst or a W-Mo-Ni type hydrogenation refining catalyst.

[0007] In the above-mentioned countercurrent hydrogenation invention methods, the first hydrogenation reactor in the hydrogenation process is simply changed from a conventional gas-liquid parallel flow reactor to a gas-liquid countercurrent reactor, without targetedly improving the process flow, the internal structure of the reactor, the catalyst loading method and other substantial contents according to the characteristics of the gas-liquid countercurrent reaction process. Here, based on the essential differences between the process requirements, the internal structure of the reactor, the catalyst loading method, etc. of the countercurrent hydrogenation reaction process and the parallel flow hydrogenation reaction process, it is difficult to solve the problems existing in the existing gas-liquid parallel flow fixed bed hydrogenation reaction process with simple modifications, thereby giving play to the process intensification effect of the gas-liquid countercurrent reactor. Summary of the invention

[0008] In view of the above technical problems and the shortcomings in the art, the present invention provides a countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid and its application. The present invention forms hydrogen-poor fluid and hydrogen-rich fluid respectively from raw material liquid and hydrogen gas, and enters the countercurrent hydrogenation reactor for hydrogenation reaction, thereby greatly enhancing the hydrogenation reaction rate and hydrogenation conversion depth, effectively inhibiting coking on the catalyst surface, making the hydrogenation reaction more uniform, and extending the catalyst life.

[0009] [1] A countercurrent hydrogenation reaction device based on a hydrogen-poor fluid and a hydrogen-rich fluid, comprising a hydrogen-poor fluid formation zone, a hydrogen-rich fluid formation zone and a countercurrent hydrogenation reaction zone;

[0010] The hydrogen-poor fluid forming area includes at least one hydrogen dissolving device I, which is used to mix the raw material liquid I and the hydrogen I to form a hydrogen-poor fluid; the hydrogen-poor fluid is a fluid containing a small amount of nano / micro hydrogen bubbles and mainly in a liquid phase flow state, and can carry the nano / micro hydrogen bubbles dissolved and / or dispersed therein and flow downward under the action of gravity;

[0011] The hydrogen-rich fluid forming area includes at least one hydrogen dissolving device II, which is used to mix the raw material liquid II and hydrogen II to form a hydrogen-rich fluid; the hydrogen-rich fluid is a fluid containing a large number of nano / micro hydrogen 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 together;

[0012] The countercurrent hydrogenation reaction zone includes at least one countercurrent hydrogenation reactor, and the countercurrent hydrogenation reactor includes a gas deliquid section, a countercurrent hydrogenation reaction section and a liquid degassing section which are sequentially connected from top to bottom; a hydrogen-poor fluid feed port connected to the outlet of the hydrogen-poor fluid formation zone is arranged between the gas deliquid section and the countercurrent hydrogenation reaction section; a hydrogen-rich fluid feed port connected to the outlet of the hydrogen-rich fluid formation zone is arranged between the countercurrent hydrogenation reaction section and the liquid degassing section; a gas discharge port is arranged above the gas deliquid section; and a liquid discharge port is arranged below the liquid degassing section.

[0013] The purpose of the hydrogen-poor fluid is to ensure that hydrogen is gradually consumed during the enhanced reaction without a hydrogen-deficient state, and to enable the fluid to remain in a liquid-phase flow state, which is beneficial to the countercurrent enhanced mass transfer of materials.

[0014] The hydrogen-rich fluid is to ensure that the overall fluid has the characteristic tendency of upward diffusion like the gas phase fluid, and to make the fluid have a certain density difference with the descending "hydrogen-poor fluid". Furthermore, 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 100~550kg / m 3 , thereby maintaining good countercurrent enhanced mass transfer characteristics. In the present invention, 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.

[0015] In some embodiments, the hydrogen dissolving device I includes a membrane assembly I and a shell I, the membrane assembly I includes one or more membrane tube bundles I containing nano / micron pores, the raw liquid I pipeline is connected to the inlet end of the membrane tube bundle I, the hydrogen I pipeline is connected to the space of the shell I, the hydrogen I diffuses into the membrane tube bundle I through the membrane tube wall, and forms a hydrogen-depleted fluid with the raw liquid I, and the outlet end of the membrane tube bundle I is a hydrogen-depleted fluid outlet.

[0016] In some embodiments, the hydrogen dissolving device II includes a membrane assembly II and a shell II, the membrane assembly II includes one or more membrane tube bundles II containing nano / micron pores, the raw liquid II pipeline is connected to the inlet end of the membrane tube bundle II, the hydrogen II pipeline is connected to the space of the shell II, the hydrogen II diffuses into the membrane tube bundle II through the membrane tube wall, and forms a hydrogen-rich fluid with the raw 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 more combinations 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 mass fraction of hydrogen in the hydrogen-poor fluid is ≤1.0 wt %, and the mass fraction of hydrogen in the hydrogen-rich fluid is >1.0 wt %.

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

[0020] In some embodiments, the sizes of nano / micro hydrogen bubbles contained in the hydrogen-poor fluid and the hydrogen-rich fluid may be independently 10 nm to 1000 μm.

[0021] The countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid, the countercurrent hydrogenation reaction section can include one or more layers of monolithic catalyst unit modules. The shape of the monolithic catalyst unit module can be any one of cylindrical, rectangular, square, rhombus, polygonal, etc., preferably rectangular.

[0022] The height of the single-layer monolithic catalyst unit module may be 50 to 1500 mm, preferably 200 to 900 mm, such as 450 mm.

[0023] The monolithic catalyst unit module may be provided with an array-arranged honeycomb pore structure, and the opening rate may be 5% to 90%, preferably 45% to 85%, such as 46.4%, 47.2%, 52.1%, 60.7%, 75.4%, 83.6%, etc. The honeycomb pore structure is interconnected, which can increase the gas-liquid mass transfer contact area and is also beneficial to the material diffusion flow and mass transfer and heat transfer. The opening rate of the present invention refers to the ratio of the opening area in the catalyst unit module to the surface area of ​​the entire module.

[0024] In some embodiments, the porosity in the monolithic catalyst unit module increases along the flow direction of the hydrogen-poor fluid because the intensity of the hydrogenation reaction and the reaction temperature gradually increase along the flow direction of the hydrogen-poor fluid under the reaction conditions, and the catalyst coking tendency gradually increases. The increase in the porosity inside the monolithic catalyst unit module can effectively improve the diffusion mass transfer and heat transfer of the material, which is conducive to a more uniform reaction and prevents catalyst coking. Further, the porosity of the monolithic catalyst unit module gradually increases along the flow direction of the hydrogen-poor fluid, and the increase rate of the porosity of the adjacent two layers of catalyst unit modules is 0.1% to 10%, preferably 1% to 5%. The increase in the porosity can be achieved by increasing the number of openings, the length of the single or multiple sides of the holes, or one or more combinations thereof.

[0025] The internal pore size of the integral catalyst unit module can be 1mm×1mm~20mm×20mm, preferably 3mm×3mm~15mm×15mm, such as 6mm×6mm, 8mm×8mm, 10mm×10mm, etc.

[0026] The integral catalyst unit module is generally composed of an integral honeycomb substrate, coating materials and active components; the integral honeycomb is used as the substrate during the preparation process, and a step-by-step impregnation method is adopted to load the high specific surface area coating and active components, and the thickness of the active component impregnation can be controlled by adjusting the coating amount; the integral modular catalyst can generally use commercially available products as needed, or it can be prepared according to conventional knowledge in the field.

[0027] The active metal in the integral catalyst unit module can be selected as a catalyst with a hydrogenation function, that is, the best catalyst active component can be selected according to the type of hydrogenation reaction, such as one or more active components with the functions of hydrogenation saturation catalyst, hydrodesulfurization catalyst, hydrodenitrogenation catalyst, hydrodemetallization, hydrodeoxygenation, hydrocracking, aromatics hydrogenation saturation, etc.

[0028] In the countercurrent hydrogenation reactor, the diameters of the gas deliquid section, the countercurrent hydrogenation reaction section and the liquid degassing section may be the same or different, preferably the same.

[0029] The gas-liquid separation section may be provided with a component with gas-liquid separation function to perform gas-liquid separation; the component with gas-liquid separation function may be one or more of a baffle structure, a cyclone / centrifugal structure, a filler and a wire mesh structure.

[0030] The liquid degassing section can be set with liquid level control and a certain liquid level height to keep the liquid for sufficient residence time to achieve liquid degassing, and components with liquid degassing function may or may not be set inside.

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

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

[0033] In some embodiments, a compression grid may be disposed on the upper portion of the integral catalyst unit module. Further, the compression grid and the inner wall of the countercurrent hydrogenation reactor may be a movable connection structure.

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

[0035] [2] Application of the countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid according to [1] in hydrogenation reaction.

[0036] The countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid of the present invention is suitable for various raw materials that can undergo hydrogenation reaction with hydrogen in the fields of petrochemical, medicine, food, etc., and can be crude oil and secondary processed oil such as crude oil, gasoline, kerosene, diesel, residual oil, heavy oil, wax oil, lubricating oil, deasphalted oil, biodiesel, animal oil or vegetable oil, coal tar, anthracene oil, etc.; it can also be various raw materials containing carbon-carbon double bonds, carbon-carbon triple bonds and organic functional groups that can undergo hydrogenation reaction in the fields of chemical, medicine, food, etc., such as olefin hydrogenation, alkyne hydrogenation, aldehyde compound hydrogenation, ketone compound hydrogenation, ester compound hydrogenation, nitro compound hydrogenation, carbonyl compound hydrogenation, nitrile compound hydrogenation and the like.

[0037] [3] A hydrogenation method, using the countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid described in [1].

[0038] In some embodiments, in the hydrogenation method, the raw material liquid I and a small amount of hydrogen I are formed into a hydrogen-poor fluid through a hydrogen dissolving device I, and enter the countercurrent hydrogenation reactor through a hydrogen-poor fluid feed port, and hydrogen II and a small amount of raw material liquid II are formed into a hydrogen-rich fluid through a hydrogen dissolving device II, and enter the countercurrent hydrogenation reactor through a hydrogen-rich fluid feed port, and the two undergo a countercurrent hydrogenation reaction in the countercurrent hydrogenation reaction section, and the remaining hydrogen after the reaction is completed is separated from the gas and liquid in the gas degassing section and leaves from the gas outlet, and the reaction liquid after the reaction is completed is separated from the liquid degassing section and leaves from the liquid outlet.

[0039] In the hydrogenation method, the hydrogen-poor fluid and the hydrogen-rich fluid can be independently introduced into the countercurrent hydrogenation reactor in any one or more combinations selected from the following:

[0040] Method 1: Setting a stream to be introduced from the lower or upper part of the countercurrent hydrogenation reaction section;

[0041] Method 2: multiple streams are arranged to be introduced multiple times along the axial direction of the countercurrent hydrogenation reactor into any position of the countercurrent hydrogenation reaction section.

[0042] In some embodiments, the feed ratio of hydrogen gas I to raw liquid I in the hydrogen-poor fluid may be 0.5 to 50 Nm 3 / h:1m 3 / h.

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

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

[0045] In some embodiments, the process conditions of the countercurrent hydrogenation reactor may include: a reaction temperature of room temperature to 500°C, a reaction pressure of 0.1 to 20 MPaG, and a liquid hourly volume space velocity of 0.1 to 20 h -1 .

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

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] (1) The hydrogenation reaction raw material liquid is made into a hydrogen-poor fluid, which is a fluid containing a small amount of nano / micro hydrogen bubbles and mainly in a liquid phase flow state. This form can effectively improve the diffusion and mass transfer of hydrogen molecules, thereby greatly improving the hydrogenation reaction rate. On the other hand, it can improve the hydrogen deficiency state of the catalyst surface during the reaction process, solve the problem of catalyst coking and deactivation, and keep the entire hydrogenation reaction process continuously and efficiently;

[0049] (2) Hydrogen is made into a hydrogen-rich fluid. A hydrogen-rich fluid is a fluid that contains a large amount of nano / micron hydrogen bubbles and is mainly in a gas phase flow state. This form can greatly reduce the diffusion and mass transfer resistance, provide sufficient hydrogen source for the hydrogenation reaction process, and thus maintain a good effect under more moderate conditions. On the other hand, the average density of the hydrogen-rich fluid is higher than that of hydrogen but much lower than that of the raw liquid, in order to reduce the rate of its upward diffusion movement, reduce the probability of bubble aggregation, and prevent problems such as gas short circuits from reducing the reaction efficiency, thereby maintaining a continuous and efficient hydrogenation reaction;

[0050] (3) The countercurrent hydrogenation catalyst is composed of stacked modular units, and the porosity of the integral catalyst unit module gradually increases along the axial direction of the reactor and the flow direction of the hydrogen-depleted fluid. This is mainly because in the countercurrent hydrogenation reactor, along the flow direction of the hydrogen-depleted fluid, the intensity of the hydrogenation reaction and the reaction temperature gradually increase, and the catalyst coking tendency gradually increases. The gradual increase in the porosity of the internal channels of the integral catalyst unit module can effectively improve the diffusion, mass transfer and heat transfer of the materials, prevent the catalyst from coking, and make the reaction more uniform. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 It is a schematic structural diagram of a countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid according to the present invention. DETAILED DESCRIPTION

[0052] The present invention will be further described below in conjunction with the accompanying drawings and specific examples. It should be understood that these examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention. The operating methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturer.

[0053] See also Figure 1 A countercurrent hydrogenation reaction device based on a hydrogen-poor fluid and a hydrogen-rich fluid comprises a hydrogen-poor fluid forming zone, a hydrogen-rich fluid forming zone and a countercurrent hydrogenation reaction zone.

[0054] The hydrogen-poor fluid formation zone includes a hydrogen dissolving device 13, which is used to mix the raw material liquid 11 and the hydrogen 12 to form the hydrogen-poor fluid 4. The hydrogen-poor fluid 4 is a fluid containing a small amount of nano / micron hydrogen bubbles and mainly in a liquid phase flow state, which can carry the nano / micron hydrogen bubbles dissolved and / or dispersed therein and flow downward under the action of gravity. The hydrogen dissolving device 13 includes a membrane assembly 1 and a shell 1, the membrane assembly 1 includes one or more membrane tube bundles 1 containing nano / micron pores, the raw material liquid 1 pipeline is connected to the inlet end of the membrane tube bundle 1, the hydrogen 1 pipeline is connected to the space of the shell 1, the hydrogen 12 diffuses into the membrane tube bundle 1 through the membrane tube wall, and forms the hydrogen-poor fluid 4 with the raw material liquid 11, and the outlet end of the membrane tube bundle 1 is the hydrogen-poor fluid outlet.

[0055] The hydrogen-rich fluid forming area includes a hydrogen dissolving device II 7, which is used to mix the raw liquid II 5 and the hydrogen II 6 to form a hydrogen-rich fluid 8. The hydrogen-rich fluid 8 is a fluid containing a large number of nano / micro hydrogen bubbles and mainly in a gas phase flow state. The whole has a characteristic tendency of diffusing upward like a gas phase fluid, and can carry the raw liquid components therein to flow upward together. The hydrogen dissolving device II7 includes a membrane assembly II and a shell II, the membrane assembly II includes one or more membrane tube bundles II containing nano / micro pores, the raw liquid II pipeline is connected to the inlet end of the membrane tube bundle II, the hydrogen II pipeline is connected to the shell II space, the hydrogen II 6 diffuses into the membrane tube bundle II through the membrane tube wall, and forms a hydrogen-rich fluid 8 with the raw 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 any one or more combinations of ceramic membranes, metal membranes, metal-ceramic composite membranes, alloy membranes, molecular sieve composite membranes, zeolite membranes, and glass membranes, respectively and independently.

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

[0058] The countercurrent hydrogenation reaction zone includes a countercurrent hydrogenation reactor 11, which includes a gas deliquidation section 14, a countercurrent hydrogenation reaction section 16 and a liquid degassing section 15 which are sequentially connected from top to bottom. A hydrogen-poor fluid feed port connected to the outlet of the hydrogen dissolving device I 3 is provided between the gas deliquidation section 14 and the countercurrent hydrogenation reaction section 16 to receive the hydrogen-poor fluid 4. A hydrogen-rich fluid feed port connected to the outlet of the hydrogen dissolving device II 7 is provided between the countercurrent hydrogenation reaction section 16 and the liquid degassing section 15 to receive the hydrogen-rich fluid 8. A gas discharge port is provided above the gas deliquidation section 14. A liquid discharge port is provided below the liquid degassing section 15.

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

[0060] First, the raw material liquid I1 and hydrogen I2 are dissolved in hydrogen by hydrogen dissolving equipment I3 to form a hydrogen-poor fluid 4, which enters the countercurrent hydrogenation reactor 11 from the top; the raw material liquid II5 and hydrogen II6 are dissolved in hydrogen by hydrogen dissolving equipment II7 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 by the upper distributor 12 and the lower distributor 13 respectively, and then enter the integral catalyst unit module 17 in the countercurrent hydrogenation reaction section 16 for countercurrent hydrogenation reaction, and the residual gas 9 after the reaction is completed is separated from the gas by the gas-liquid separation section 14 and then leaves, and the liquid reaction product 10 is separated from the gas by the liquid degassing section 15 and then leaves.

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

[0062] Table 1 Properties of straight-run diesel feedstock

[0063] project Crude oil <![CDATA[Density, g / cm 3 > 0.834 <![CDATA[Viscosity, mm 2 / s]]> 765.8 Sulfur, wt% 0.61 Nitrogen, μg / g 101 Distillation range, ℃ IBP / 5% 201 / 235 10％ / 30％ 256 / 267 50％ / 70％ 288 / 300 90％ / 95％ 320 / 331 EBP 353

[0064] Table 2 Physical and chemical indicators of straight-run diesel hydrogenation catalyst

[0065]

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

[0067] project index Characteristics Colorless transparent liquid Concentration, mol / L 1.5

[0068] Table 4 Biomass sugar (glucose) solution hydrogenation catalyst properties

[0069]

[0070] Comparative Example 1

[0071] The conventional gas-liquid co-current fixed bed hydrogenation process was adopted, and the height-to-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 this device; the hydrogenation reactor was loaded with non-integrated modular catalysts corresponding to each reaction.

[0072] First, the mixture of raw materials and hydrogen is temperature-adjusted to the inlet temperature of the hydrogenation reactor, then enters the top of the hydrogenation reactor and undergoes a hydrogenation reaction from top to bottom through the catalyst bed, and leaves after the hydrogenation 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 liquid hourly volume space velocity, which will not be described in detail below.

[0074] Comparative Example 2

[0075] The conventional gas-liquid countercurrent fixed bed hydrogenation process was adopted, and the height-to-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 this device. The hydrogenation reactor was loaded with non-integrated modular catalysts corresponding to each reaction.

[0076] First, the raw liquid is temperature-adjusted to the inlet temperature of the hydrogenation reactor and then enters from the top of the hydrogenation reactor. The hydrogen gas is temperature-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 hydrogenation reactor to obtain liquid products and residual gas and leave after the hydrogenation reaction is 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 and reactor configuration are the same as those of Comparative Example 2, except that the hydrogenation reactor is loaded with 35 layers of integral modular catalysts corresponding to respective reactions, wherein the catalyst unit pore size is 6 mm×6 mm.

[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 hydrogen-poor fluid and hydrogen-rich fluid introduced in the specific embodiment of the present invention are adopted. The height-to-diameter ratio of the countercurrent hydrogenation reactor is 2.0; the countercurrent hydrogenation reaction section is loaded with 20 layers of integral modular catalysts; wherein the opening rate of the first layer catalyst unit module is 52.1%, the opening rate of the 20th layer catalyst unit module is 75.4%, and the opening rates of the first to 20th layers of catalyst unit modules increase uniformly, and the hole size is 6mm×6mm. Along the flow direction of the hydrogen-poor fluid is the direction in which the number of layers of the catalyst unit modules increases, such as the first layer catalyst unit is the position for adding the hydrogen-poor fluid, and along the flow direction of the hydrogen-poor fluid are the second layer, the third layer, and so on.

[0083] The device was used to investigate the reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation under different conditions.

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

[0085] The operating 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 the hydrogen-poor fluid and the hydrogen-rich fluid introduced in the specific embodiment of the present invention are used, and the process flow is the same as that of Example 1. The differences are the hydrogen-liquid ratio of the hydrogen-poor fluid and the hydrogen-rich fluid, the height-to-diameter ratio of the countercurrent hydrogenation reactor, and the catalyst unit module, which are as follows:

[0088] The height-to-diameter ratio of the countercurrent hydrogenation reactor is 3.0; the countercurrent hydrogenation reaction section is loaded with 30 layers of integral modular catalysts; the opening rate of the first layer of catalyst unit modules is 46.4%, the opening rate of the 30th layer of catalyst unit modules is 60.7%, and the opening rates of the catalyst unit modules from the first layer to the 30th layer increase uniformly; the hole size is 10mm×10mm. The number of layers of the catalyst unit modules increases along the flow direction of the hydrogen-poor fluid, such as the first layer of catalyst units is the position where the hydrogen-poor fluid is added, and along the flow direction of the hydrogen-poor fluid are the second layer, the third layer, and so on.

[0089] The device was used to investigate the reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation under different conditions.

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

[0091] The operating 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 hydrogen-poor fluid and the hydrogen-rich fluid introduced in the specific embodiment of the present invention are used, and the process flow is the same as that of Example 1. The differences are the hydrogen-liquid ratio of the hydrogen-poor fluid and the hydrogen-rich fluid, the height-to-diameter ratio of the countercurrent hydrogenation reactor, and the catalyst unit module, which are as follows:

[0094] The height-to-diameter ratio of the countercurrent hydrogenation reactor is 4.0; the countercurrent hydrogenation reaction section is loaded with 40 layers of integral modular catalysts; the opening rate of the first layer of catalyst unit modules is 47.2%, the opening rate of the 40th layer of catalyst unit modules is 83.6%, and the opening rates of the catalyst unit modules from the first layer to the 40th layer increase uniformly; and the channel size of the catalyst unit modules from the first to the 20th layer is 3mm×3mm, and the channel size of the catalyst unit modules from the 21st to the 40th layer is 8mm×8mm. The number of layers of the catalyst unit modules increases along the flow direction of the hydrogen-poor fluid, such as the first layer of catalyst units is the position where the hydrogen-poor fluid is added, and along the flow direction of the hydrogen-poor fluid are the second layer, the third layer, and so on.

[0095] The device was used to investigate the reaction effects of straight-run diesel hydrogenation and biomass sugar (glucose) hydrogenation under different conditions.

[0096] First, the raw material liquid and a small amount of hydrogen are prepared into a hydrogen-poor fluid through a ceramic membrane mixing device, and the bubble size of the hydrogen is 10nm~1000μm. The material is temperature-adjusted to the reaction temperature and enters from the upper part of the countercurrent hydrogenation reactor. The hydrogen and a small amount of raw material liquid are prepared into a hydrogen-rich fluid through a ceramic membrane mixing device, and the bubble size of the hydrogen is 10nm~1000μm. The material is temperature-adjusted to the reaction temperature and enters from the lower part of the countercurrent hydrogenation reactor. The two undergo a countercurrent hydrogenation reaction in the catalyst bed, and the remaining gas and liquid products leave 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 countercurrent hydrogenation reactor

[0099]

[0100] Table 6 Reaction results of countercurrent hydrogenation reactor

[0101]

[0102] Note: Δt11\Δt12\Δt13 are the average radial temperature differences of the top\middle\bottom of the countercurrent hydrogenation reactor.

[0103] It can be seen from the hydrogenation reaction effects of the embodiments of the present invention and the comparative examples that the method of the present invention introduces the hydrogen-poor fluid and the hydrogen-rich fluid into the countercurrent hydrogenation reactor respectively, and enters the catalyst bed equipped with the catalyst unit module for countercurrent hydrogenation reaction, which greatly enhances the countercurrent hydrogenation reaction rate, reaction conversion depth, and reaction uniformity. Compared with the prior art, on the one hand, more moderate conditions can be adopted, such as lower temperature and pressure, higher space velocity, and lower hydrogen-liquid ratio, to achieve better hydrogenation conversion effect. On the other hand, based on the fact that the carbon deposition and coking of the catalyst can be greatly improved, the problem of reaction heat concentration and local hot spots is solved. While achieving the same hydrogenation reaction effect, the catalyst operation cycle is significantly extended, which greatly reduces the operating cost.

[0104] 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 countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid, characterized in that: It includes a hydrogen-poor fluid forming zone, a hydrogen-rich fluid forming zone and a countercurrent hydrogenation reaction zone; The hydrogen-poor fluid forming area includes at least one hydrogen dissolving device I, which is used to mix the raw material liquid I and the hydrogen I to form a hydrogen-poor fluid; the hydrogen-poor fluid is a fluid containing a small amount of nano / micro hydrogen bubbles and mainly in a liquid phase flow state, and can carry the nano / micro hydrogen bubbles dissolved and / or dispersed therein and flow downward under the action of gravity; The hydrogen-rich fluid forming area includes at least one hydrogen dissolving device II, which is used to mix the raw material liquid II and hydrogen II to form a hydrogen-rich fluid; the hydrogen-rich fluid is a fluid containing a large number of nano / micro hydrogen 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 together; The countercurrent hydrogenation reaction zone includes at least one countercurrent hydrogenation reactor, and the countercurrent hydrogenation reactor includes a gas deliquid section, a countercurrent hydrogenation reaction section and a liquid degassing section which are sequentially connected from top to bottom; a hydrogen-poor fluid feed port connected to the outlet of the hydrogen-poor fluid formation zone is arranged between the gas deliquid section and the countercurrent hydrogenation reaction section; a hydrogen-rich fluid feed port connected to the outlet of the hydrogen-rich fluid formation zone is arranged between the countercurrent hydrogenation reaction section and the liquid degassing section; a gas discharge port is arranged above the gas deliquid section; and a liquid discharge port is arranged below the liquid degassing section.

2. The countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid according to claim 1, characterized in that: 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 / micron pores. The raw liquid I pipeline is connected to the inlet end of the membrane tube bundle I. The hydrogen I pipeline is connected to the space of 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 liquid I. The outlet end of the membrane tube bundle I is the outlet of the hydrogen-poor fluid. 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 / micron pores. The raw liquid II pipeline is connected to the inlet end of the membrane tube bundle II. The hydrogen II pipeline is connected to the space of 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 liquid II. The outlet end of the membrane tube bundle II is the outlet of the hydrogen-rich fluid. The membrane-tube bundle I and the membrane-tube bundle II are independently any one or more combinations of ceramic membranes, metal membranes, metal-ceramic composite membranes, alloy membranes, molecular sieve composite membranes, zeolite membranes, and glass membranes.

3. The countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid according to claim 1, characterized in that: The mass fraction of hydrogen in the hydrogen-poor fluid is ≤1.0wt%, and the mass fraction of hydrogen in the hydrogen-rich fluid is >1.0wt%; The average density of hydrogen-rich fluid is less than that of hydrogen-poor fluid; the average density of hydrogen-poor fluid is 100-1000 kg / m 3 The average density of hydrogen-rich fluid is 5-400 kg / m 3 The difference between the average density of hydrogen-poor fluid and the average density of hydrogen-rich fluid is 50-900 kg / m 3 , preferably 100~550kg / m 3 ; 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; The sizes of the nano / micro hydrogen bubbles contained in the hydrogen-poor fluid and the hydrogen-rich fluid are independently 10 nm to 1000 μm.

4. The countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid according to claim 1, characterized in that: The countercurrent hydrogenation reaction section comprises one or more layers of monolithic catalyst unit modules; the height of the single-layer monolithic catalyst unit module is 50 to 1500 mm, preferably 200 to 900 mm; The monolithic catalyst unit module is provided with an array-arranged honeycomb pore structure, with an opening rate of 5% to 90%, preferably 45% to 85%, and the honeycomb pore structures are interconnected; The internal pore size of the monolithic catalyst unit module is 1mm×1mm~20mm×20mm, preferably 3mm×3mm~15mm×15mm; The porosity in the monolithic catalyst unit module increases along the flow direction of the hydrogen-poor fluid, and the increasing rate of the porosity of two adjacent layers of catalyst unit modules is 0.1% to 10%, preferably 1% to 5%. The increase in the porosity is achieved by increasing the number of openings, the length of a single or multiple sides of the holes, or a combination of multiple methods; In the countercurrent hydrogenation reactor, the diameters of the gas deliquid section, the countercurrent hydrogenation reaction section and the liquid degassing section are the same or different; The height-to-diameter ratio of the countercurrent hydrogenation reactor is 0.5 to 10:1, preferably 1 to 6:1; A support grid is arranged at the bottom of the integral catalyst unit module; the support grid and the inner wall of the countercurrent hydrogenation reactor are welded structures; A compression grid is arranged on the upper part of the integral catalyst unit module; the compression grid and the inner wall of the countercurrent hydrogenation reactor are in a movable connection structure.

5. The countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid according to claim 1 or 4, characterized in that: The countercurrent hydrogenation reaction section comprises 2 to 100 layers, preferably 10 to 60 layers, of integral catalyst unit modules.

6. Use of the countercurrent hydrogenation reaction device based on hydrogen-poor fluid and hydrogen-rich fluid according to any one of claims 1 to 5 in hydrogenation reaction.

7. A hydrogenation method, characterized in that: A countercurrent hydrogenation reaction device based on a hydrogen-poor fluid and a hydrogen-rich fluid as described in any one of claims 1 to 5 is used.

8. The hydrogenation method according to claim 7, characterized in that The raw material liquid I and a small amount of hydrogen I are formed into a hydrogen-poor fluid through the hydrogen dissolving device I, and enter the countercurrent hydrogenation reactor through the hydrogen-poor fluid feed port. The hydrogen II and a small amount of raw material liquid II are formed into a hydrogen-rich fluid through the hydrogen dissolving device II, and enter the countercurrent hydrogenation reactor through the hydrogen-rich fluid feed port. The two undergo a countercurrent hydrogenation reaction in the countercurrent hydrogenation reaction section. After the reaction is completed, the remaining hydrogen is separated from the gas and liquid in the gas degassing section and then leaves from the gas outlet. After the reaction is completed, the reaction liquid is separated from the liquid degassing section and then leaves from the liquid outlet.

9. The hydrogenation method according to claim 8, characterized in that The hydrogen-poor fluid and the hydrogen-rich fluid are independently introduced into the countercurrent hydrogenation reactor in any one or more combinations selected from the following: Method 1: Setting a stream to be introduced from the lower or upper part of the countercurrent hydrogenation reaction section; Method 2: multiple streams are arranged to be introduced multiple times along the axial direction of the countercurrent hydrogenation reactor into any position of the countercurrent hydrogenation reaction section.

10. The hydrogenation method according to claim 8 or 9, characterized in that: The feed ratio of hydrogen gas I to raw liquid I in the hydrogen-poor fluid is 0.5-50 Nm 3 / h:1m 3 / h; The feed ratio of hydrogen II to reaction liquid II in the hydrogen-rich fluid is 10 to 1000 Nm 3 / h:1m 3 / h, preferably 10 to 400 Nm 3 / h:1m 3 / h; The hydrogenation method uses hydrogen with a purity greater than 90 vol%, preferably more than 99.9 vol% pure hydrogen; The process conditions of the countercurrent hydrogenation reactor include: reaction temperature of room temperature to 500°C, reaction pressure of 0.1 to 20 MPaG, liquid hourly volume space velocity of 0.1 to 20 h -1 .

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