Internal and external coupled reverse / cross flow hydrogenation reactor and application thereof

Abstract

The invention discloses an internal and external coupled reverse / cross flow hydrogenation reactor and application thereof in hydrogenation reaction. The internal and external coupled reverse / cross flow hydrogenation reactor comprises a shell and an inner cylinder, an annular space is formed between the shell and the inner cylinder, and the inner cylinder is communicated with the annular space by forming one or more through holes in the cylinder wall of the inner cylinder; the top end of the inner cylinder is opened for receiving a liquid reaction raw material; the top end of the annular space is closed, and the bottom end is open; the inner cylinder is filled with one or more layers of integral modular catalyst units; and the annular space is filled with a non-monolithic catalyst. According to the invention, fluid guidance is carried out on the reaction materials in the hydrogenation reaction process, the whole hydrogenation reaction efficiency is improved, efficient mass and heat transfer is always maintained in the hydrogenation reaction process, and the method has the advantages of wide raw material adaptability, flexible and easy-to-control production operation, high conversion rate and selectivity and the like.

Description

Technical Field

[0001] The invention relates to the technical field of hydrogenation, and in particular to an internally and externally coupled reverse / cross-flow hydrogenation reactor and application thereof. Background Art

[0002] There are many types of hydrogenation reaction processes and reactors, such as fixed bed hydrogenation processes and reactors, suspended bed hydrogenation processes and reactors, and fluidized bed hydrogenation processes and reactors. Among them, fixed bed hydrogenation reactors are the most widely used and can be used in various types of hydrogenation processes. Fixed bed hydrogenation processes are divided into many types of reaction forms, such as gas-liquid co-current, gas-liquid countercurrent, downward liquid phase hydrogenation, and upward liquid phase hydrogenation. Among them, the gas-liquid countercurrent hydrogenation reaction process is based on the simplicity of the process flow and can significantly improve the efficiency of the hydrogenation reaction, becoming an important research hotspot for fixed bed hydrogenation reaction processes.

[0003] Patent application CN116948701A proposes a hydrogenation process for blended bio-oil, wherein hydrogen enters from a gas-liquid contact zone, partially passes through the gas-liquid contact zone, the gas-liquid countercurrent zone, the gas-liquid separation zone and the gas phase reaction zone in sequence, and partially exchanges heat with the liquid phase material flowing out of the gas-liquid countercurrent zone and is mixed into the liquid phase reaction zone; the raw material for blending bio-oil enters from the gas-liquid separation zone, partially converts into gas phase, and enters the gas phase reaction zone together with the gas phase material from the gas-liquid countercurrent zone for hydrogenation reaction, and the gas phase reaction product flows out from the top of the reactor; the liquid phase raw material in the gas-liquid separation zone enters the gas-liquid countercurrent zone, countercurrently contacts with hydrogen and enters the gas-liquid contact zone for reaction, and the liquid phase material enters the gas-liquid contact zone downward for liquid phase hydrogenation reaction, and the liquid phase reaction product flows out from the bottom of the reactor.

[0004] Patent CN102041063B proposes a method for deep desulfurization of diesel, in which the diesel feedstock and hydrogen first pass through a gas-liquid countercurrent hydrogenation reaction zone, and the effluent of the gas-liquid countercurrent hydrogenation reaction zone enters a gas-liquid parallel 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.

[0005] Patent CN102041069B proposes a gas-liquid countercurrent hydrogenation method for diesel desulfurization, denitrogenation and aromatic saturation. Under the conditions of diesel fraction hydrogenation, hydrogen and diesel feedstock pass through the catalyst bed in a countercurrent manner; the reactor is divided into at least two reaction zones, each reaction zone is composed of at least one hydrogenation catalyst bed; the reactor increases in diameter from the lower reaction zone to the upper reaction zone; a liquid accumulation zone is set at the diameter change at the junction of at least one reaction zone, and a liquid accumulation lead-out pipeline is set at the bottom or side of the liquid accumulation zone to introduce the liquid in the liquid accumulation zone into the lower reaction zone of the reactor as a cooling flow.

[0006] As for the existing gas-liquid countercurrent hydrogenation technology, almost all of them directly operate the conventional gas-liquid parallel flow fixed bed reactor as a gas-liquid countercurrent reactor, without making substantial improvements to the internal structure of the reactor and the catalyst loading method according to the flow state of the gas-liquid countercurrent reaction process. In fact, the reaction flow state, reactor structure and catalyst loading method of the countercurrent hydrogenation reactor and the parallel flow hydrogenation reactor are essentially different. Therefore, for the countercurrent hydrogenation reaction process and reactor, it is of great significance to adopt effective means, such as developing new countercurrent hydrogenation processes, reactor structures and catalyst loading methods, to give full play to the significant advantages of the countercurrent hydrogenation reaction process. Summary of the invention

[0007] In view of the above technical problems and the deficiencies in the art, the present invention provides an internally and externally coupled reverse / cross-flow hydrogenation reactor and its application. The present invention conducts fluid guidance on the reaction materials during the hydrogenation reaction by designing a special hydrogenation reactor structure and coupling it with the catalyst loading method, which can effectively avoid the problems of wall flow, short-circuit flow, gas phase centering, liquid flooding, etc. that affect gas-liquid mass transfer in the existing fixed-bed hydrogenation reactor. While improving the overall hydrogenation reaction efficiency, the hydrogenation reaction process always maintains efficient mass transfer and heat transfer, and has the advantages of wide raw material adaptability, flexible and easy-to-control production operation, high conversion rate and selectivity, etc.

[0008] [1] An internally and externally coupled counter-current / cross-flow hydrogenation reactor, comprising an outer shell and an inner cylinder, an annular space between the outer shell and the inner cylinder, one or more through holes are provided in the inner cylinder wall to interconnect the inner cylinder and the annular space; the inner cylinder is closed at the bottom and open at the top for receiving liquid reaction raw materials; the annular space is closed at the top and open at the bottom for receiving hydrogen feed; the inner cylinder is filled with one or more layers of integral modular catalyst units; and the annular space is filled with non-integral catalysts.

[0009] In the internally and externally coupled counter-flow / cross-flow hydrogenation reactor of the present invention, the flow mode of hydrogen is to gradually diffuse from the annular space to the inner cylinder in a bottom-up process, and the flow mode of liquid reaction raw materials is to diffuse from the inner cylinder to the annular space in a top-down process, that is, hydrogen and liquid reaction raw materials respectively flow axially and radially during the hydrogenation reaction, so that the two are in counter-flow and cross-flow contact at the same time, greatly enhancing mass transfer and heat transfer.

[0010] In some embodiments, the internally and externally coupled reverse / cross-flow hydrogenation reactor includes a gas deliquidation zone, a hydrogenation reaction zone, and a liquid degassing zone, which are sequentially connected from top to bottom, and the inner cylinder and the annular space are located in the hydrogenation reaction zone. A liquid reaction raw material feed port can be set between the gas deliquidation zone and the hydrogenation reaction zone, and the liquid reaction raw material feed port can be connected to the open top of the inner cylinder, and is not connected to the top of the annular space. A hydrogen feed port can be set between the hydrogenation reaction zone and the liquid degassing zone, and the hydrogen feed port can be connected to the open bottom of the annular space, and is not connected to the bottom of the inner cylinder. A residual gas discharge port can be set above the gas deliquidation zone. A liquid reaction product discharge port can be set below the liquid degassing zone. That is, the liquid reaction raw material feed port can be set at the upper part of the shell, the hydrogen feed port can be set at the lower part, the residual gas discharge port can be set at the top, and the liquid reaction product discharge port can be set at the bottom.

[0011] In the internally and externally coupled reverse / cross-flow hydrogenation reactor, the gas-liquid separation zone may be provided with a component having a gas-liquid separation function to perform gas-liquid separation. Further, the component having a gas-liquid separation function may be one or more of a baffle structure, a cyclone / centrifugal structure, a filler, and a wire mesh structure.

[0012] In the internally and externally coupled reverse / cross-flow hydrogenation reactor, the liquid degassing zone can be provided with liquid level control and a certain liquid level height to maintain sufficient residence time of the liquid to achieve liquid degassing, and components with liquid degassing function may or may not be provided inside.

[0013] In the internally and externally coupled reverse / cross-flow hydrogenation reactor, the diameters of the gas deliquidation zone, the hydrogenation reaction zone and the liquid degassing zone may be the same or different, preferably the same.

[0014] The height-to-diameter ratio of the internally and externally coupled counter-flow / cross-flow hydrogenation reactor may be 0.5 to 10:1, preferably 1 to 5:1, such as 2:1, 2.5:1, 4:1, etc.

[0015] In the internally and externally coupled reverse / cross-flow hydrogenation reactor, the inner cylinder may be a cylindrical cylinder.

[0016] In some embodiments, the ratio of the inner barrel diameter to the diameter of the internally and externally coupled counter-flow / cross-flow hydrogenation reactor may be 1:1.05-30, preferably 1:1.5-5, such as 1:2, 1:4, etc.

[0017] In the internal and external coupled reverse / cross flow hydrogenation reactor, the through hole is provided on the wall surface of the inner cylinder to achieve material diffusion between the inner cylinder and the annular space. The through hole can be any one or more combinations of circular, elliptical, teardrop, Ω, ∞, triangular, rectangular, pentagonal and above polygons, preferably circular.

[0018] In the internally and externally coupled counter / cross-flow hydrogenation reactor, the ratio of the through hole area of ​​the inner barrel wall to the side area of ​​the inner barrel wall can be 1:1.05-20, preferably 1:1.5-5, for example 1:2.5, 1:3, 1:4, etc.

[0019] In the internally and externally coupled reverse / cross-flow hydrogenation reactor, the diameter of the through hole may be 0.1 to 100 mm, preferably 2 to 20 mm, such as 4 mm, 6 mm, 8 mm, etc.

[0020] In some embodiments, in the internally and externally coupled counter / cross-flow hydrogenation reactor, the through holes opened on the inner cylinder wall have uniform apertures or vary along the axial direction of the inner cylinder. Furthermore, the variation mode may be one or more combinations of increasing, decreasing, alternating large and small, irregular changes, or partial area closure.

[0021] In the internal-external coupled reverse / cross-flow hydrogenation reactor, a support grid I may be provided at the bottom of the integral modular catalyst unit, and a compression grid I may be provided at the top to fix the modular catalyst. The support grid I may be a flat closed structure, and the material cannot pass through the support grid I. The compression grid I may be an open structure, and the material can pass through the compression grid I.

[0022] The inner cylinder of the internally and externally coupled reverse / cross-flow hydrogenation reactor can be loaded with 2 to 100 layers, preferably 5 to 60 layers (eg, 15 layers, 22 layers, 30 layers, etc.) of integral modular catalyst units.

[0023] In the internally and externally coupled counter-flow / cross-flow hydrogenation reactor, the height of the single-layer integral modular catalyst unit can be 50 to 1500 mm, preferably 100 to 600 mm, such as 450 mm.

[0024] In the internally and externally coupled reverse / cross-flow hydrogenation reactor, the porosity of the integral modular catalyst unit bed filled in the inner cylinder can be 60% to 90%, preferably 70% to 80%.

[0025] In the internally and externally coupled reverse / cross-flow hydrogenation reactor, the modular catalyst monomers in the integral modular catalyst unit may have any shape of cylinder, rectangle, square, diamond, polygon, etc., preferably rectangle.

[0026] In the internally and externally coupled reverse / cross-flow hydrogenation reactor, the modular catalyst monomers in the integral modular catalyst unit can all be provided with a honeycomb pore structure arranged in an array. The honeycomb pore structure can be interconnected, which can not only increase the gas-liquid mass transfer contact area, but also facilitate material diffusion flow and mass transfer and heat transfer.

[0027] In the internally and externally coupled counter-flow / cross-flow hydrogenation reactor, the through-hole size on the surface of the integral modular catalyst unit may be 1 mm×1 mm to 10 mm×10 mm, preferably 3 mm×3 mm to 8 mm×8 mm.

[0028] The modular catalyst monomer in the integral modular catalyst unit of the internally and externally coupled reverse / cross-flow hydrogenation reactor is generally composed of an integral honeycomb substrate, a coating material and an active component; during the preparation process, the integral honeycomb monomer is used as the substrate, and a method of stepwise impregnation of the high specific surface area coating and the active component is adopted, and the thickness of the active component impregnation can be controlled by adjusting the coating amount; the modular catalyst unit can use commercially available products as needed, or improve the commercially available products as needed, or can be prepared according to conventional knowledge in the field.

[0029] In the internal-external coupled reverse / cross-flow hydrogenation reactor, a support grid II may be provided at the lower end of the non-monolithic catalyst, and a compression grid II may be provided at the upper end to limit the non-monolithic catalyst therein. The support grid II may be an open structure, and the material may pass through the support grid II. The compression grid II may be a flat closed structure, and the material cannot pass through the compression grid II.

[0030] In the internally and externally coupled reverse / cross-flow hydrogenation reactor, the void ratio of the non-integrated catalyst bed filled in the annular space can be 60% to 95%, preferably 65% ​​to 85%.

[0031] The said internally and externally coupled reverse / cross-flow hydrogenation reactor, the non-monolithic catalyst filled in the annular space, the catalyst shape can be one or more combinations of sphere, toothed sphere, sheet, strip, clover, four-leaf clover, hollow ring, multi-hole column, etc., and the radial dimension of the catalyst cross section can be 0.5-10 mm, preferably 1-6 mm. .

[0032] In the internal and external coupled reverse / cross-flow hydrogenation reactor, the non-integral catalyst filled in the annular space is generally a supported catalyst, wherein the catalyst carrier can be SiO 2 、Al 2 O 3 、SiO 2 -Al 2 O 3 、TiO 2 , activated carbon, MgO, molecular sieve, etc. The non-monolithic catalyst filled in the annular space can be a commercial product as needed, or can be prepared according to conventional knowledge in the art.

[0033] The internally and externally coupled reverse / cross-flow hydrogenation reactor, the integral modular catalyst unit loaded in the inner tube, and the non-integral catalyst loaded in the annular space can be independently catalysts with hydrogenation function, and the hydrogenation active components can be selected according to the type of hydrogenation reaction, such as any one or more of hydrogenation saturation catalyst, hydrodesulfurization catalyst, hydrodenitrogenation catalyst, hydrodemetallization, hydrodeoxygenation, hydrocracking, aromatics hydrogenation saturation catalyst, etc.; the catalyst active components include but are not limited to one or more combinations of precious metals, Co, Mo, Ni, W, Mg, Zn, rare earth elements, etc.

[0034] In the internally and externally coupled reverse / cross-flow hydrogenation reactor, a liquid distributor may be provided at the top of the inner cylinder to evenly distribute the liquid reaction raw materials. Further, the liquid distributor may be any one or more combinations of tubular, jet, trough, and disc types.

[0035] In the internally and externally coupled reverse / cross-flow hydrogenation reactor, a gas distributor may be provided at the bottom of the annular space to evenly distribute the hydrogen. The gas distributor may be any one or more combinations of plate type, tube type, bubble type, and nozzle type.

[0036] [2] Application of the internally and externally coupled counter-flow / cross-flow hydrogenation reactor according to [1] in hydrogenation reactions.

[0037] The internally and externally coupled reverse / cross-flow hydrogenation reactor of the present invention can be used as the main hydrogenation reaction, pre-hydrogenation reaction or post-hydrogenation reaction in the hydrogenation process, and can also be connected in series or in parallel with processes such as gas-liquid co-current fixed bed hydrogenation, upflow or downflow liquid phase hydrogenation, ebullating bed hydrogenation, and suspended bed hydrogenation.

[0038] [3] A hydrogenation method, using the internally and externally coupled counter-current / cross-current hydrogenation reactor described in [1].

[0039] In some embodiments, in the hydrogenation method, the liquid reaction raw material enters from the upper part of the internally and externally coupled reverse / cross-flow hydrogenation reactor, flows downward into the inner cylinder to undergo a hydrogenation reaction, and gradually diffuses to the annular space during the reaction; hydrogen enters from the lower part of the internally and externally coupled reverse / cross-flow hydrogenation reactor, flows upward into the annular space, and gradually diffuses to the inner cylinder; the liquid reaction raw material and hydrogen undergo a reverse / cross-flow hydrogenation reaction during this process. Furthermore, the remaining hydrogen after the reaction is completed can leave from the top of the internally and externally coupled reverse / cross-flow hydrogenation reactor, and the liquid reaction product after the reaction is completed can leave from the bottom of the internally and externally coupled reverse / cross-flow hydrogenation reactor.

[0040] In some embodiments, the hydrogenation method is mainly carried out in the inner cylinder in the early stage of the reaction, and in the annular space in the late stage of the reaction; the early stage of the reaction refers to the stage when the conversion rate of the key components of the hydrogenation reaction is lower than 70%, and the late stage of the reaction refers to the stage when the conversion rate of the key components of the hydrogenation reaction is higher than 70%.

[0041] In the hydrogenation method, the space velocity of the integral modular catalyst unit filled in the inner cylinder can be 1 to 30 h -1 , preferably 2 to 15 hours -1 , for example 3.5h -1 , 4.2h -1 , 4.5h -1 , 4.88h -1 , 5.0h -1 , 5.5h -1 , 6.0h -1 wait.

[0042] In the hydrogenation method, the space velocity of the non-monolithic catalyst filled in the annular space can be 0.1 to 10 h -1 , preferably 0.1 to 5 hours -1 , for example 0.65h -1 , 0.8h -1 、0.9h -1 , 0.94h -1 , 1.0h -1 , 1.2h -1 wait.

[0043] The hydrogen (Nm 3 / h) and liquid reaction raw materials (m 3 / h) can be adjusted according to various hydrogenation reaction requirements, hydrogen consumption, conversion rate and selectivity. In principle, the total hydrogen-to-liquid ratio is the lowest and the energy consumption is the lowest under the premise of ensuring the best reaction effect. In some embodiments, the feed ratio of hydrogen to liquid reaction raw material in the hydrogenation method can be 1 to 1500 Nm 3 / h:1m 3 / h, preferably 10 to 500 Nm 3 / h:1m 3 / h.

[0044] The process conditions of the hydrogenation reaction are generally determined by those skilled in the art according to the properties of the raw materials, the quality requirements of the final product, etc. In some embodiments, the process conditions of the internally and externally coupled reverse / cross-flow hydrogenation reactor may include: a reaction temperature of room temperature to 500° C., and a reaction pressure of 0.1 to 20 MPaG.

[0045] The internal and external coupled reverse / cross-flow hydrogenation reactor and hydrogenation method of the present invention are applicable to various raw materials that can undergo hydrogenation reaction with hydrogen in the fields of petrochemical, medicine, food, etc., and can be crude oil and secondary processed oil such as crude oil, gasoline, kerosene, diesel, residual oil, heavy oil, wax oil, lubricating oil, deasphalted oil, biodiesel, animal oil or vegetable oil, coal tar, anthracene oil, etc.; it can also be various raw materials containing carbon-carbon double bonds, carbon-carbon triple bonds and organic functional groups that can undergo hydrogenation reaction in the fields of chemical, medicine, food, etc., such as olefin hydrogenation, alkyne hydrogenation, aldehyde compound hydrogenation, ketone compound hydrogenation, ester compound hydrogenation, nitro compound hydrogenation, carbonyl compound hydrogenation, nitrile compound hydrogenation and the like.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] (1) The present invention creatively designs a special structure of the hydrogenation reactor and couples it with the catalyst loading method to achieve fluid guidance of the reaction materials while greatly enhancing the mass transfer and heat transfer in the hydrogenation reaction process, thereby effectively improving the hydrogenation reaction efficiency and making the hydrogenation reaction process more uniform, efficient and easy to control.

[0048] (2) The hydrogenation reactor is provided with a structure such as an inner cylinder and an annular space, mainly because in the conventional countercurrent hydrogenation reaction process, the contact between the liquid reaction raw material and the hydrogen is completely reversed, which is not only prone to problems such as bias flow, short-circuit flow, liquid flooding, and large pressure drop, but also leads to low gas-liquid contact efficiency, which in serious cases will affect the normal operation of the reactor. After adopting the structure of the inner cylinder and annular space, the hydrogen and liquid reaction raw materials can be guided by fluid, so that the gas-liquid contact becomes countercurrent / cross-current and takes place simultaneously, effectively strengthening the hydrogenation reaction while solving problems such as bias flow, short-circuit flow, and liquid flooding.

[0049] (3) In view of the characteristics of the flow of the liquid phase and the gas phase in the reactor, that is, the liquid phase is prone to wall flow and the gas phase is prone to centering, which leads to insufficient gas-liquid contact during the reaction and reduces the reaction mass transfer and heat transfer efficiency. By setting up the liquid phase to diffuse from the inner cylinder to the annular space in the hydrogenation reactor and the gas phase to diffuse from the annular space to the inner cylinder, the problems of wall flow and gas phase centering in the entire hydrogenation reaction process can be solved, thereby maintaining the high efficiency of the hydrogenation reaction process.

[0050] (4) The inner cylinder of the hydrogenation reactor is filled with modular catalyst units, and the annular space is filled with conventional catalysts. This catalyst filling method is closely related to the structure of the reactor and the flow mode of the reaction materials. It is mainly considered that for fresh liquid reaction raw materials, the reaction materials in the inner cylinder are the materials in the early stage of the reaction, which have the characteristics of high reaction substrate concentration, fast reaction rate, and large heat release, which cause problems such as uneven hydrogenation reaction, difficult to control selectivity, and easy coking and deactivation of the catalyst. The use of modular catalyst units not only has a small pressure drop, but also its surface through holes can effectively improve the flow of materials, prevent material accumulation, and reduce the residence time of materials on the catalyst surface, thereby uniformizing the reaction heat and preventing the catalyst from coking and deactivation; the annular space of the hydrogenation reactor is filled with conventional catalysts, mainly considering that for fresh liquid reaction raw materials, the reaction materials in the annular space are the materials in the late stage of the reaction, which have the characteristics of low reaction substrate concentration and slow reaction rate, making improving the conversion rate of the hydrogenation reaction a key direction. Since hydrogen is added from the annular space, it can be guaranteed that there are enough hydrogen molecules on the surface of the conventional catalyst during the reaction process, thereby effectively ensuring efficient hydrogenation during the reaction process, thereby improving the conversion rate of the hydrogenation reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 It is a schematic structural diagram of an internally and externally coupled reverse / cross-flow hydrogenation reactor of the present invention. DETAILED DESCRIPTION

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

[0053] See also Figure 1, an internally and externally coupled reverse / cross-flow hydrogenation reactor 5, comprising an outer shell and an inner cylinder, the inner cylinder is a cylindrical cylinder, an annular space is formed between the outer shell and the inner cylinder, and the inner cylinder wall 19 is provided with one or more through holes to interconnect the inner cylinder and the annular space; the bottom end of the inner cylinder is a closed support plate 15, and the top end is open for receiving liquid reaction raw materials; the top end of the annular space is a closed compression plate 18, and the bottom end is open for receiving hydrogen feed; the inner cylinder is filled with one or more layers of integral modular catalyst units 13, and the through hole size of the surface of the integral modular catalyst unit 13 is 1mm×1mm~10mm×10mm, preferably 3mm×3mm~8mm×8mm; the annular space is filled with non-integral catalyst 14 (conventional catalyst). A support grid I is provided at the bottom of the integral modular catalyst unit 13, and a compression grid I17 is provided at the top to fix the modular catalyst; the support grid I is a flat closed structure, and the material cannot pass through the support grid I; the compression grid I17 is an open structure, and the material can pass through the compression grid I17. A support grid II 16 is provided at the lower end of the non-integral catalyst 14, and a compression grid II is provided at the upper end, which is used to limit the non-integral catalyst therein; the support grid II 16 is an open structure, and the material can pass through the support grid II 16; the compression grid II is a flat closed structure, and the material cannot pass through the compression grid II. A liquid distributor 11 is provided at the top of the inner cylinder, which is used to evenly distribute the liquid reaction raw materials. A gas distributor 12 is provided at the bottom end of the annular space, which is used to evenly distribute the hydrogen.

[0054] Specifically, the internally and externally coupled reverse / cross-flow hydrogenation reactor 5 includes a gas deliquidation zone 6, a hydrogenation reaction zone 7 and a liquid degassing zone 10 which are sequentially connected from top to bottom. The inner cylinder and the annular space are located in the hydrogenation reaction zone 7, corresponding to the inner cylinder hydrogenation reaction zone 8 and the annular space hydrogenation reaction zone 9, respectively. A liquid reaction raw material feed port is arranged between the gas deliquidation zone 6 and the hydrogenation reaction zone 7. The liquid reaction raw material feed port is connected to the open top of the inner cylinder and is not connected to the top of the annular space. A hydrogen feed port is arranged between the hydrogenation reaction zone 6 and the liquid degassing zone 10, and the hydrogen feed port is connected to the open bottom of the annular space and is not connected to the bottom of the inner cylinder. A residual gas discharge port is arranged above the gas deliquidation zone 6. A liquid reaction product discharge port is arranged below the liquid degassing zone 10. The diameters of the gas deliquidation zone 6, the hydrogenation reaction zone 7 and the liquid degassing zone 10 are the same.

[0055] A hydrogenation method, using the above Figure 1 The internally and externally coupled reverse / cross-flow hydrogenation reactor 5 shown comprises:

[0056] The liquid reaction raw material 1 and the hydrogen 2 enter the internally and externally coupled counter-current / cross-current hydrogenation reactor 5 from the liquid reaction raw material feed port and the hydrogen feed port respectively; after the liquid reaction raw material 1 enters the internally and externally coupled counter-current / cross-current hydrogenation reactor 5, it is evenly distributed by the liquid distributor 11, flows through the bed of the integral modular catalyst unit 13 filled in the inner cylinder hydrogenation reaction zone 8, and passes through the inner cylinder wall 19 to enter the non-integral catalyst 14 filled in the annular space hydrogenation reaction zone 9, and then leaves the hydrogenation reaction zone 7 to enter the liquid degassing zone 10, and passes through the liquid degassing zone 1 0 is degassed and leaves the internally and externally coupled counter / cross-flow hydrogenation reactor 5 as a liquid reaction product 4; after the hydrogen 2 enters the internally and externally coupled counter / cross-flow hydrogenation reactor 5, it is evenly distributed by the gas distributor 12, flows through the bed layer of the non-integrated catalyst 14 filled in the annular space hydrogenation reaction zone 9, and passes through the inner cylinder wall 19 to enter the bed layer of the integral modular catalyst unit 13 filled in the inner cylinder hydrogenation reaction zone 8, and then leaves the hydrogenation reaction zone 7 and enters the gas deliquidation zone 6 for gas-liquid separation, and then leaves the hydrogenation reactor 5 as the reaction residual gas 3.

[0057] The above-mentioned internally and externally coupled reverse / cross-flow hydrogenation reactor 5 and hydrogenation method are respectively applied to catalytic diesel hydrogenation, wax oil hydrogenation, and biomass sugar (glucose) solution hydrogenation processes. The properties of catalytic diesel feedstock are shown in Table 1, and the properties of catalytic diesel hydrogenation catalysts are shown in Table 2; the properties of wax oil feedstock are shown in Table 3, and the properties of wax oil hydrogenation catalysts are shown in Table 4; the properties of biomass sugar (glucose) hydrogenation feedstock are shown in Table 5, and the properties of biomass sugar (glucose) solution hydrogenation catalysts are shown in Table 6. All the above-mentioned raw materials are commercially available, and all hydrogenation catalysts are homemade.

[0058] Table 1 Catalytic diesel feedstock properties

[0059] project Catalytic diesel <![CDATA[Density, g / cm 3 > 0.8620 Distillation range (ASTM D86), ℃ IBP / 10% 203 / 245 20％ / 50％ 278 / 304 90% / FBP 336 / 368 Sulfur, μg / g 5270 Nitrogen content, μg / g 1350

[0060] Table 2 Properties of Catalytic Diesel Hydrogenation Catalyst

[0061]

[0062] Table 3 Wax oil raw material properties

[0063]

[0064] Table 4 Properties of Wax Oil Hydrogenation Catalyst

[0065]

[0066] Table 5 Biomass sugar (glucose) solution raw materials

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

[0068] Table 6 Biomass sugar (glucose) solution hydrogenation catalyst properties

[0069]

[0070] Comparative Example 1

[0071] A conventional fixed-bed gas-liquid cocurrent hydrogenation process and a hydrogenation reactor were used, and the height-to-diameter ratio of the hydrogenation reactor was 2.5. The hydrogenation reaction effects of catalytic diesel hydrogenation (Table 1), wax oil hydrogenation (Table 3), and biomass sugar (glucose) (Table 5) were investigated under different conditions using the device; the hydrogenation reactors were filled with conventional catalysts corresponding to the respective reaction processes (Table 2, Table 4, Table 6), and the catalyst bed voidages were 82.4% (catalytic diesel hydrogenation catalyst), 67.1% (wax oil hydrogenation catalyst), and 75.6% (biomass sugar hydrogenation catalyst).

[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 7, and the reaction results are shown in Table 8.

[0074] Comparative Example 2

[0075] A conventional fixed-bed gas-liquid countercurrent hydrogenation process and a hydrogenation reactor were used, and the height-to-diameter ratio of the hydrogenation reactor was 2.5. The hydrogenation reaction effects of catalytic diesel hydrogenation (Table 1), wax oil hydrogenation (Table 3), and biomass sugar (glucose) (Table 5) were investigated under different conditions using the device; the hydrogenation reactors were filled with conventional catalysts corresponding to the respective reaction processes (Table 2, Table 4, Table 6), and the catalyst bed porosity was the same as that of Comparative Example 1.

[0076] First, the raw materials and hydrogen are respectively adjusted to the inlet temperature of the hydrogenation reactor, and then enter the catalyst bed from the top and bottom of the hydrogenation reactor to undergo a hydrogenation reaction. After the hydrogenation reaction is completed, the remaining gas leaves from the top and the liquid reaction product leaves from the bottom.

[0077] The operating conditions of the hydrogenation reactor are shown in Table 7, and the reaction results are shown in Table 8.

[0078] Comparative Example 3

[0079] The process flow is the same as that of Comparative Example 2, except that 40 layers of integral modular catalyst are loaded inside the reactor. The device was used to investigate the hydrogenation reaction effects of catalytic diesel hydrogenation (Table 1), wax oil hydrogenation (Table 3), and biomass sugar (glucose) (Table 5) under different conditions; the porosity of the modular catalyst bed was 77.2% (catalytic diesel hydrogenation catalyst), 74.3% (wax oil hydrogenation catalyst), and 78.6% (biomass sugar hydrogenation catalyst).

[0080] The operating conditions of the hydrogenation reactor are shown in Table 7, and the reaction results are shown in Table 8.

[0081] Example 1

[0082] The internal and external coupled reverse / cross-flow hydrogenation reactor and hydrogenation method introduced in the specific embodiment of the present invention are used. The height-to-diameter ratio of the hydrogenation reactor is 2.5, wherein the catalyst I filled in the inner cylinder is a modular catalyst unit, and the catalyst II filled in the annular region is a conventional catalyst, see Table 2, Table 4, and Table 6. The hydrogenation reaction effects of catalytic diesel hydrogenation (Table 1), wax oil hydrogenation (Table 3), and biomass sugar (glucose) (Table 5) were investigated under different conditions using this process. Among them, the porosity of the modular catalyst bed is 77.2% (catalytic diesel hydrogenation catalyst), 74.3% (wax oil hydrogenation catalyst), and 78.6% (biomass sugar hydrogenation catalyst); the porosity of the conventional catalyst bed is 82.4% (catalytic diesel hydrogenation catalyst), 67.1% (wax oil hydrogenation catalyst), and 75.6% (biomass sugar hydrogenation catalyst).

[0083] The inner cylinder of the hydrogenation reactor is a cylindrical cylinder, and the ratio of the inner cylinder diameter to the reactor diameter is 1:2; circular holes are evenly opened on the inner cylinder wall, and the ratio of the inner cylinder wall opening area to the inner cylinder wall side area is 1:3, and the inner cylinder wall opening size is 8mm. In the inner cylinder of the hydrogenation reactor, the lower support grid of the hydrogenation catalyst I is a flat closed structure, and the upper compression grid is an open structure; in the annular area of ​​the hydrogenation reactor, the lower support grid of the hydrogenation catalyst II is an open structure, and the upper compression grid is a flat closed structure. The height of the modular catalyst unit loaded in the inner cylinder of the hydrogenation reactor is 450mm, and a total of 15 layers of modular catalyst units are loaded.

[0084] The hydrogenation reaction process is as follows: the liquid reaction raw material and hydrogen enter the hydrogenation reactor through the upper liquid reaction raw material feed port and the lower hydrogen feed port respectively, the liquid reaction raw material diffuses into the annular space through the inner cylinder, and the hydrogen diffuses into the inner cylinder through the annular space, and the two undergo a counter / cross-current hydrogenation reaction in this process. The remaining hydrogen after the reaction is completed leaves from the top, and the liquid reaction product after the reaction is completed leaves from the bottom.

[0085] The operating conditions of the hydrogenation reactor are shown in Table 7, and the reaction results are shown in Table 8.

[0086] Example 2

[0087] The internal and external coupled reverse / cross-flow hydrogenation reactor and hydrogenation method introduced in the specific embodiment of the present invention are adopted. The process flow is the same as that of Example 1, except that: the height-to-diameter ratio of the hydrogenation reactor is 2.0; the inner barrel of the hydrogenation reactor is a cylindrical barrel, and the ratio of the inner barrel diameter to the reactor diameter is 1:4; circular holes are evenly opened on the inner barrel wall, and the ratio of the inner barrel wall opening area to the inner barrel wall side area is 1:2.5, and the inner barrel wall opening size is 6mm. In the inner barrel of the hydrogenation reactor, the lower support grid of the hydrogenation catalyst inner barrel is a flat closed structure, and the upper compression grid is an open structure; the lower support grid of the annular area of ​​the hydrogenation reactor is an open structure, and the upper compression grid is a flat closed structure. The height of the modular catalyst unit loaded in the inner barrel of the hydrogenation reactor is 450mm, and a total of 22 layers of modular catalyst units are loaded. Among them, the porosity of the modular catalyst bed is 79.2% (catalytic diesel hydrogenation catalyst), 78.3% (wax oil hydrogenation catalyst), and 79.6% (biomass sugar hydrogenation catalyst); the porosity of the conventional catalyst bed is 83.4% (catalytic diesel hydrogenation catalyst), 84.7% (wax oil hydrogenation catalyst), and 83.6% (biomass sugar hydrogenation catalyst).

[0088] The hydrogenation reaction effects of catalytic diesel hydrogenation (Table 1), wax oil hydrogenation (Table 3), and biomass sugar (glucose) (Table 5) were investigated under different conditions using this process.

[0089] The operating conditions of the hydrogenation reactor are shown in Table 7, and the reaction results are shown in Table 8.

[0090] Example 3

[0091] The internal and external coupled reverse / cross-flow hydrogenation reactor and hydrogenation method introduced in the specific embodiment of the present invention are adopted. The process flow is the same as that of Example 1, except that: the height-to-diameter ratio of the hydrogenation reactor is 4.0; the inner barrel of the hydrogenation reactor is a cylindrical barrel, and the ratio of the inner barrel diameter to the reactor diameter is 1:2; circular holes are evenly opened on the inner barrel wall, and the ratio of the inner barrel wall opening area to the inner barrel wall side area is 1:4, and the inner barrel wall opening size is 4mm. In the inner barrel of the hydrogenation reactor, the lower support grid of the hydrogenation catalyst inner barrel is a flat closed structure, and the upper compression grid is an open structure; the lower support grid of the annular area of ​​the hydrogenation reactor is an open structure, and the upper compression grid is a flat closed structure. The height of the modular catalyst unit loaded in the inner barrel of the hydrogenation reactor is 450mm, and a total of 30 layers of modular catalyst units are loaded. Among them, the porosity of the modular catalyst bed is 71.2% (catalytic diesel hydrogenation catalyst), 72.5% (wax oil hydrogenation catalyst), and 70.7% (biomass sugar hydrogenation catalyst); the porosity of the conventional catalyst bed is 68.4% (catalytic diesel hydrogenation catalyst), 69.7% (wax oil hydrogenation catalyst), and 66.2% (biomass sugar hydrogenation catalyst).

[0092] The hydrogenation reaction effects of catalytic diesel hydrogenation (Table 1), wax oil hydrogenation (Table 3), and biomass sugar (glucose) (Table 5) were investigated under different conditions using this process.

[0093] The operating conditions of the hydrogenation reactor are shown in Table 7, and the reaction results are shown in Table 8.

[0094] Table 7 Operating conditions of hydrogenation reactor

[0095]

[0096] Table 8 Reaction results

[0097]

[0098] Note: Δt11\Δt12\Δt13 are the average radial temperature differences of the top\middle\bottom of the hydrogenation reactor.

[0099] It can be seen from the hydrogenation reaction effects of the embodiments of the present invention and the comparative examples that the hydrogenation reactor and the hydrogenation process of the present invention are adopted, and the fluid guidance of the reaction materials is realized by designing a hydrogenation reactor with a special structure and coupling it with a catalyst loading method, so as to prevent material accumulation and uniform reaction heat. The problems of wall flow, short-circuit flow, gas phase centering, liquid flooding and the like existing in the existing fixed-bed hydrogenation reactor that affect gas-liquid mass transfer can be effectively avoided. While improving the overall hydrogenation reaction efficiency, the hydrogenation reaction process can always maintain efficient mass and heat transfer, and is suitable for a variety of hydrogenation raw material systems.

[0100] 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. An internally and externally coupled reverse / cross-flow hydrogenation reactor, characterized in that: It includes an outer shell and an inner cylinder, with an annular space between the outer shell and the inner cylinder. The inner cylinder wall is connected to the annular space by opening one or more through holes; the bottom end of the inner cylinder is closed, and the top end is open for receiving liquid reaction raw materials; the top end of the annular space is closed, and the bottom end is open for receiving hydrogen feed; the inner cylinder is filled with one or more layers of integral modular catalyst units; and the annular space is filled with non-integral catalysts.

2. The internally and externally coupled reverse / cross-flow hydrogenation reactor according to claim 1, characterized in that: The internally and externally coupled reverse / cross-flow hydrogenation reactor comprises a gas deliquidation zone, a hydrogenation reaction zone and a liquid degassing zone which are sequentially connected from top to bottom, and the inner cylinder and the annular space are located in the hydrogenation reaction zone; a liquid reaction raw material feed port is arranged between the gas deliquidation zone and the hydrogenation reaction zone, and the liquid reaction raw material feed port is connected to the open top of the inner cylinder and is not connected to the top of the annular space; a hydrogen feed port is arranged between the hydrogenation reaction zone and the liquid degassing zone, and the hydrogen feed port is connected to the open bottom of the annular space and is not connected to the bottom of the inner cylinder; a residual gas discharge port is arranged above the gas deliquidation zone; and a liquid reaction product discharge port is arranged below the liquid degassing zone; The diameters of the gas deliquidation zone, the hydrogenation reaction zone, and the liquid degassing zone are the same or different; The height-to-diameter ratio of the internally and externally coupled counter-flow / cross-flow hydrogenation reactor is 0.5 to 10:1, preferably 1 to 5:

1.

3. The internally and externally coupled reverse / cross-flow hydrogenation reactor according to claim 1, characterized in that: The inner cylinder is a cylindrical cylinder; The ratio of the diameter of the inner cylinder to the diameter of the internally and externally coupled counter-flow / cross-flow hydrogenation reactor is 1:1.05-30, preferably 1:1.5-5.

4. The internally and externally coupled reverse / cross-flow hydrogenation reactor according to claim 1, characterized in that: The through hole is any one or more combinations of a circle, an ellipse, a teardrop, an Ω, an ∞, a triangle, a rectangle, a polygon with five sides or more; The ratio of the through hole area of ​​the inner cylinder wall to the side area of ​​the inner cylinder wall is 1:1.05-20, preferably 1:1.5-5; The through hole has a diameter of 0.1 to 100 mm, preferably 2 to 20 mm; The diameter of the through holes formed on the inner cylinder wall is uniform or varies along the axial direction of the inner cylinder, and the variation is one or more combinations of increasing, decreasing, alternating large and small, irregularly changing or partially closed.

5. The internally and externally coupled reverse / cross-flow hydrogenation reactor according to claim 1, characterized in that: The lower part of the integrated modular catalyst unit is provided with a support grid I, and the upper part is provided with a compression grid I for fixing the modular catalyst; The support grid I is a flat closed structure, and the material cannot pass through the support grid I; The compression grid I is an open structure, and the material can pass through the compression grid I; The inner cylinder is filled with 2 to 100 layers, preferably 5 to 60 layers, of monolithic modular catalyst units; The height of the single-layer integrated modular catalyst unit is 50 to 1500 mm, preferably 100 to 600 mm; The porosity of the monolithic modular catalyst unit bed filled in the inner cylinder is 60% to 90%, preferably 70% to 80%; The modular catalyst monomers in the integrated modular catalyst unit are all provided with a honeycomb pore structure arranged in an array, and the honeycomb pore structures are interconnected; The through hole size on the surface of the integral modular catalyst unit is 1mm×1mm~10mm×10mm, preferably 3mm×3mm~8mm×8mm; A support grid II is provided at the lower end of the non-integral catalyst, and a compression grid II is provided at the upper end, which is used to limit the non-integral catalyst therein; the support grid II is an open structure, and the material can pass through the support grid II; the compression grid II is a flat closed structure, and the material cannot pass through the compression grid II; The void ratio of the non-monolithic catalyst bed filled in the annular space is 60% to 95%, preferably 65% ​​to 85%; The non-integral catalyst filled in the annular space has a catalyst shape that is a combination of one or more of spheres, toothed spheres, sheets, strips, clover leaves, four-leaf clover leaves, hollow rings, and multi-hole columns. The radial dimension of the catalyst cross section is 0.5 to 10 mm, preferably 1 to 6 mm.

6. The internally and externally coupled reverse / cross-flow hydrogenation reactor according to claim 1, characterized in that: A liquid distributor is arranged at the top of the inner cylinder to evenly distribute the liquid reaction raw materials; the liquid distributor can be any one or more combinations of tube type, jet type, trough type, and disc type; A gas distributor is arranged at the bottom of the annular space for evenly distributing the hydrogen; the gas distributor is any one or more combinations of plate type, tube type, bubble type and nozzle type.

7. Use of the internally and externally coupled reverse / cross-flow hydrogenation reactor according to any one of claims 1 to 6 in hydrogenation reactions.

8. A hydrogenation method, characterized in that: The internally and externally coupled reverse / cross-flow hydrogenation reactor according to any one of claims 1 to 6 is used.

9. The hydrogenation method according to claim 8, characterized in that Liquid reaction raw materials enter from the upper part of the internally and externally coupled counter / cross-flow hydrogenation reactor, flow downward into the inner cylinder to undergo a hydrogenation reaction, and gradually diffuse into the annular space during the reaction; hydrogen enters from the lower part of the internally and externally coupled counter / cross-flow hydrogenation reactor, flows upward into the annular space, and gradually diffuses into the inner cylinder; the liquid reaction raw materials and hydrogen undergo a counter / cross-flow hydrogenation reaction in this process.

10. The hydrogenation method according to claim 9, characterized in that: The early stage of the reaction is mainly carried out in the inner cylinder, and the late stage of the reaction is mainly carried out in the annular space; the early stage of the reaction refers to the stage when the conversion rate of the key components of the hydrogenation reaction is less than 70%, and the late stage of the reaction refers to the stage when the conversion rate of the key components of the hydrogenation reaction is more than 70%; The space velocity of the integral modular catalyst unit filled in the inner tube is 1 to 30h -1 , preferably 2 to 15 hours -1 ; The space velocity of the non-monolithic catalyst filled in the annular space is 0.1~10h -1 , preferably 0.1 to 5 hours -1 ; The hydrogenation method comprises a feed ratio of hydrogen to liquid reaction raw material of 1 to 1500 Nm 3 / h:1m 3 / h, preferably 10 to 500 Nm 3 / h:1m 3 / h; The process conditions of the internally and externally coupled reverse / cross-flow hydrogenation reactor include: a reaction temperature of room temperature to 500° C., and a reaction pressure of 0.1 to 20 MPaG.

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