Variable-diameter hydrogenation reaction system and application thereof

Abstract

The invention discloses a variable-diameter hydrogenation reaction system and application thereof. The variable-diameter hydrogenation reaction system comprises a hydrogenation reactor I and a hydrogenation reactor II; the hydrogenation reactor I is a variable-diameter gas-liquid countercurrent hydrogenation reactor and comprises a gas-liquid removal section, an upper reaction section, a countercurrent enhanced mass transfer section, a lower reaction section and a liquid degassing section which are sequentially communicated from top to bottom; the diameters of the upper reaction section and the lower reaction section are greater than the diameter of the countercurrent enhanced mass transfer section; a liquid feeding hole is formed between the gas-liquid removal section and the upper reaction section; a gas feeding hole is formed between the lower reaction section and the liquid degassing section; a gas discharge hole is formed above the gas-liquid removal section; a liquid discharge hole is formed below the liquid degassing section; the hydrogenation reactor II comprises at least one up-flow tubular reactor; and a feed port connected with a gas discharge port and a liquid discharge port of the hydrogenation reactor I is formed in the bottom of the up-flow tubular reactor.

Description

Technical Field

[0001] The invention relates to the technical field of hydrogenation, and in particular to a variable diameter hydrogenation reaction system and application thereof. Background Art

[0002] Catalytic hydrogenation technology is generally a process in which certain components containing unsaturated groups in the raw materials undergo hydrogenation reactions to generate target products under the atmosphere of hydrogen and catalyst. It is widely used in the fields of oil refining, chemical industry, biochemical industry, etc. The fixed bed catalytic hydrogenation process mostly adopts the traditional trickle bed hydrogenation process and the gas-liquid-solid three-phase fixed bed reactor. During the reaction process, the gas and liquid generally flow downward through the fixed catalyst bed layer to complete the catalytic hydrogenation reaction. In the existing industrial trickle bed hydrogenation process, since the liquid passes through the catalyst bed layer in the form of a liquid film, it is easy to cause uneven liquid distribution, channeling and short circuiting, thereby reducing the utilization rate and reaction rate of the catalyst. Therefore, in order to ensure that the hydrogenation reaction of the reactants is more thorough, it is generally necessary to adopt more stringent reaction conditions, such as a higher hydrogen-to-liquid ratio, a longer reaction residence time, a higher temperature and hydrogen partial pressure, etc., which not only has high equipment investment and energy consumption, but also has problems such as low reaction efficiency, low catalyst utilization, uneven reaction, and many side reactions.

[0003] In order to solve the above problems, a variety of improved processes and improved reactors have emerged in the field of hydrogenation reactions. Patent CN109305882B proposes a method and device for preparing sorbitol by continuous hydrogenation of glucose, which is to continuously add glucose liquid and hydrogen to a fixed bed reactor and a slurry bed reactor to carry out hydrogenation reactions in sequence. Although this process formally realizes continuous hydrogenation reactions, it still has problems such as low mass transfer reaction rate, long total material residence time, harsh reaction conditions, high device investment and energy consumption.

[0004] Patent application CN116948701A proposes a hydrogenation process for blending bio-oil, wherein hydrogen enters from the 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 from the gas-liquid countercurrent zone and mixes 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 flow 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, and reacts with the hydrogen countercurrent to enter the gas-liquid contact zone, 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. On the one hand, the scope of application of this method is relatively limited, and it can only be applied to the reaction process and reaction raw materials in the patented technology, and conventional gas-liquid countercurrent reactors generally have the problems of insufficient contact and low mass transfer efficiency after engineering amplification.

[0005] Patent application CN112852477A proposes an upflow hydrogenation reactor, reactor system and catalytic hydrogenation process with multiple partitions. The upflow hydrogenation reactor includes a reactor shell, a support grid is provided at the bottom of the reactor shell, a pressurization zone is provided below the support grid, a plurality of parallel upflow reaction zones are connected to the top of the support grid, each upflow reaction zone is independent of each other and each upflow reaction zone has the same flow area, each upflow reaction zone is loaded with the same catalyst height and volume, an interception grid is provided at the top of each upflow reaction zone, and the outside of the interception grid is a gas-liquid separation zone. The reactor of this patent technology is provided with multiple independent reaction zones to prevent the problem of uneven radial distribution of materials, but the reactor is not only complex in structure, but also does not solve the problem of uneven distribution of materials and uneven distribution of reaction heat, which is not conducive to heat conduction, especially for reactions with relatively large heat release.

[0006] In summary, the existing hydrogenation processes and hydrogenation reactor forms, whether using a fixed bed reactor combined with other forms of reactors, or a fixed bed co-current / countercurrent or down-flow / up-flow reactor structure, are often designed to solve a problem in a certain reaction system and lack overall economy, resulting in most processes having problems such as high hydrogen-to-liquid ratio, harsh reaction conditions, low production efficiency, high energy consumption and investment. Summary of the invention

[0007] In view of the above technical problems and the shortcomings in the art, the present invention provides a variable diameter hydrogenation reaction system and its application. The present invention couples the variable diameter gas-liquid countercurrent hydrogenation reactor with the upflow tubular reactor to achieve segmented intensification of the entire hydrogenation reaction process, greatly improves the hydrogenation reaction efficiency and hydrogen utilization rate, reduces the hydrogen-liquid ratio, shortens the reaction time, reduces device consumption and investment, and is suitable for hydrogenation reaction processes in industries such as oil refining, chemical industry, biochemical industry, pharmaceutical industry and food industry.

[0008] The "upflow" mentioned in the present invention refers to the flow of the reactant flow in the reactor from bottom to top; the "height-to-diameter ratio" generally refers to the ratio of the axial height of the reactor (or catalyst bed) to the cross-sectional diameter.

[0009] [1] A variable diameter hydrogenation reaction system, comprising a hydrogenation reactor I and a hydrogenation reactor II;

[0010] The hydrogenation reactor I is a variable diameter gas-liquid countercurrent hydrogenation reactor, comprising a gas deliquid section, an upper reaction section, a countercurrent enhanced mass transfer section, a lower reaction section and a liquid degassing section which are sequentially connected and arranged from top to bottom; the diameters of the upper reaction section and the lower reaction section are both larger than the diameter of the countercurrent enhanced mass transfer section; a liquid feed port is arranged between the gas deliquid section and the upper reaction section; a gas feed port is arranged between the lower 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;

[0011] The hydrogenation reactor II comprises at least one upflow tubular reactor; a feed port connected to the gas discharge port and the liquid discharge port of the hydrogenation reactor I is arranged at the bottom of the upflow tubular reactor.

[0012] The liquid flows from top to bottom in the hydrogenation reactor 1, and the gas flows from bottom to top. The gas-liquid two phases undergo countercurrent contact mass transfer in the hydrogenation reactor 1.

[0013] In the variable diameter hydrogenation reaction system, the gas-liquid separation section is used to remove liquid from the residual hydrogen after the reaction is completed. The gas-liquid separation section can be provided with a component having a gas-liquid separation function to perform gas-liquid separation. The component having the gas-liquid separation function can be one or more of a baffle structure, a cyclone / centrifugal structure, a filler, and a wire mesh structure.

[0014] In the variable diameter hydrogenation reaction system, the liquid degassing section is used to remove gas from the reaction liquid after the reaction is completed. The liquid degassing section can be set with liquid level control and a certain liquid level height to keep the liquid for a sufficient residence time to achieve liquid degassing, and components with liquid degassing function may or may not be set inside.

[0015] In the variable diameter hydrogenation reaction system, the height-to-diameter ratio of the countercurrent enhanced mass transfer section can be 2 to 30:1, preferably 3 to 10:1, such as 3.5:1, 4:1, 5:1, 8:1, etc.

[0016] In the variable diameter hydrogenation reaction system, the height-to-diameter ratios of the gas deliquid section, the upper reaction section, the lower reaction section, and the liquid degassing section may be all the same, or not all the same, or all different, and may be independently 0.5 to 5:1, preferably 1 to 3:1, such as 2:1, 2.5:1, etc. In the variable diameter hydrogenation reaction system, the height-to-diameter ratios of the gas deliquid section, the upper reaction section, the lower reaction section, and the liquid degassing section are preferably all the same.

[0017] In the variable diameter hydrogenation reaction system, the ratio of the material residence time in the upper reaction section to the countercurrent enhanced mass transfer section can be 1 to 100:10, preferably 1 to 2:2, such as 1:1.5.

[0018] In the variable diameter hydrogenation reaction system, the ratio of the material residence time in the lower reaction section to the countercurrent enhanced mass transfer section can be 1 to 100:10, preferably 1 to 2:2, such as 1:1.5.

[0019] In some embodiments, in the variable diameter hydrogenation reaction system, the upper reaction section, the countercurrent enhanced mass transfer section and the lower reaction section are all loaded with catalysts.

[0020] In some embodiments, in the variable diameter hydrogenation reaction system, the porosity of the catalyst bed loaded in the upper reaction section and the lower reaction section is less than the porosity of the catalyst bed loaded in the countercurrent enhanced mass transfer section. The porosity of the catalyst bed loaded in the upper reaction section and the lower reaction section may be the same or different. The porosity of the catalyst bed loaded in the upper reaction section and the lower reaction section may be 10% to 50% independently, preferably 20% to 40%, such as 25%, 25.5%, 30%, 30.5%, 31.4%, 38.9%, 40%, etc. The porosity of the catalyst bed loaded in the countercurrent enhanced mass transfer section may be 30% to 90%, such as 52.5%, 60%, 62.5%, 70%, 80%, etc., preferably 50% to 80%. The porosity of the catalyst bed loaded in the upper reaction section and the lower reaction section is preferably the same.

[0021] In some embodiments, in the variable diameter hydrogenation reaction system, the catalyst particle size loaded in the upper reaction section and the lower reaction section is smaller than the catalyst particle size loaded in the countercurrent enhanced mass transfer section. The catalyst particle size loaded in the upper reaction section and the lower reaction section may be the same or different. The catalyst particle size loaded in the upper reaction section and the lower reaction section may be 0.3-3 mm, preferably 0.5-2 mm, such as 0.8-1.0 mm, 1.0-1.2 mm, 1.2-1.6 mm, 1.5-2 mm, etc. The catalyst particle size loaded in the countercurrent enhanced mass transfer section may be 2-10 mm, preferably 3-6 mm, such as 2-3 mm, 2.8-3.8 mm, 3.2-3.6 mm, 4.0-4.6 mm, 4.5-5.5 mm, 6.0-6.6 mm, 7.5-8.5 mm, etc. The catalyst particle size loaded in the upper reaction section and the lower reaction section is preferably the same.

[0022] In the hydrogenation reactor I and the upflow tubular reactor, a catalyst with a hydrogenation function commonly used in the corresponding reaction can be selected according to different reactions, such as a copper series, a nickel series, a noble metal palladium series, etc. The reaction generally selects the best type of catalyst according to the type of hydrogenation reaction; the hydrogenation catalyst is preferably a supported catalyst, wherein the catalyst carrier can be one or more of SiO2, Al2O3, SiO2-Al2O3, TiO2, activated carbon, MgO, molecular sieves, etc.; the shape of the hydrogenation catalyst can be one or more of a sphere, a strip, a clover shape, a toothed ball shape, etc.; the hydrogenation catalyst can use a commercially available product as needed, or it can be prepared according to conventional knowledge in the art.

[0023] In the variable diameter hydrogenation reaction system, heat can be taken or removed between the hydrogenation reactor I and the upflow tubular reactor according to the reaction requirements to achieve the best reaction effect.

[0024] In the variable diameter hydrogenation reaction system, the specific number of the upflow tubular reactors can be set according to actual needs, for example, 1 to 6.

[0025] In the variable diameter hydrogenation reaction system, a discharge port can be arranged at the top of the upflow tubular reactor. The material flow in the upflow tubular reactor can be from bottom to top.

[0026] In some embodiments, in the variable diameter hydrogenation reaction system, the hydrogenation reactor II may include a plurality of parallel upflow tubular reactors.

[0027] In the variable diameter hydrogenation reaction system, the height-to-diameter ratio of the upflow tubular reactor may be 2 to 15:1, preferably 3 to 8:1, such as 4:1, 5:1, 6:1, etc.

[0028] In the variable diameter hydrogenation reaction system, the upflow tubular reactor can be loaded with a catalyst.

[0029] The voidage of the catalyst bed loaded in the upflow tubular reactor may be 10% to 80%, for example 38.5%, 42.5%, 52.5%, 58.2%, 60%, 70%, 70.3%, etc., preferably 30% to 60%.

[0030] The size of the catalyst particles loaded in the upflow tubular reactor may be 1.5 to 5 mm, preferably 2 to 4.5 mm, such as 2 to 2.2 mm, 2.4 to 2.6 mm, 3.5 to 4.5 mm, etc.

[0031] The variable diameter hydrogenation reaction system, the reaction feed of the upflow tubular reactor can be a liquid phase containing nano / micron dispersed hydrogen, the liquid phase is formed by dissolving and / or dispersing part or all of the hydrogen discharged from the gas outlet of the hydrogenation reactor I in part or all of the reaction liquid discharged from the liquid outlet of the hydrogenation reactor I with or without additional hydrogen supplementation, and what occurs in the upflow tubular reactor is an upflow liquid phase hydrogenation reaction, and the liquid phase hydrogenation refers to hydrogen being pre-dissolved and / or dispersed in the liquid reactant and then liquid-solid two-phase hydrogenation. The remaining hydrogen of the hydrogenation reactor I can be used in whole or in part as a hydrogen source for the upflow tubular reactor. For a reaction process with a large amount of hydrogen consumption, a supplementary hydrogen pipeline can also be set in the upflow tubular reactor to supplement the hydrogen required by the upflow tubular reactor.

[0032] The "dissolving and / or dispersing" can be achieved by using a mixing device. The mixing device generally adopts one or more combinations of devices with liquid-liquid and / or gas-liquid mixing functions, such as a dissolved air pump, a mechanical stirring device, a colloid mill, a microporous plate nano / micro hydrogen dispersion component, a micro bubble generator, a ceramic membrane nano / micro hydrogen dispersion component, and a microchannel mixer.

[0033] [2] Application of the variable diameter hydrogenation reaction system according to [1] in hydrogenation reaction.

[0034] The variable diameter hydrogenation reaction system of the present invention is 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., and can undergo hydrogenation conversion of sulfur / nitrogen / oxygen / metal, hydrogenation saturation of olefins and dienes, partial hydrogenation saturation of aromatics, hydrocracking and other reactions during the hydrogenation process; 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 chemical industry, 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 other reactions.

[0035] [3] A hydrogenation method, using the variable diameter hydrogenation reaction system described in [1].

[0036] In some embodiments, the hydrogenation method is as follows: the raw liquid enters the hydrogenation reactor I from the liquid feed port, and the hydrogen enters the hydrogenation reactor I from the gas feed port. The raw liquid and the hydrogen undergo a countercurrent hydrogenation reaction in the hydrogenation reactor I. The remaining hydrogen after the reaction is completed leaves from the gas discharge port and partially or completely enters the upflow tubular reactor. The reaction liquid after the reaction is completed leaves from the liquid discharge port and partially or completely enters the upflow tubular reactor; part or all of the remaining hydrogen discharged from the gas discharge port of the hydrogenation reactor I is dissolved and / or dispersed in part or all of the reaction liquid discharged from the liquid discharge port of the hydrogenation reactor I with or without additional hydrogen supplementation to form a liquid phase containing nano / micron dispersed hydrogen, and an upflow liquid phase hydrogenation reaction occurs in the upflow tubular reactor.

[0037] The gas-liquid ratio of the upflow tubular reactor can be adjusted according to the reaction requirements, hydrogen consumption and the need to control the conversion rate. In principle, the total hydrogen consumption is minimized under the premise of ensuring the best reaction effect. The preferred reaction process among all adjustment schemes is to use the remaining hydrogen in the hydrogenation reactor I as the hydrogen source of the upflow tubular reactor for hydrogenation reaction.

[0038] In the hydrogenation method, the feed ratio of hydrogen to raw liquid in the hydrogenation reactor I can be 1 to 500 Nm 3 / h:1m 3 / h, preferably 5 to 100 Nm 3 / h:1m 3 / h.

[0039] In the hydrogenation method, the feed ratio of hydrogen to reaction liquid in the upflow tubular reactor can be 1 to 100 Nm 3 / h:1m 3 / h, preferably 2 to 20 Nm 3 / h:1m 3 / h.

[0040] The hydrogenation method may use hydrogen with a purity greater than 90 vol%, preferably pure hydrogen greater than 99.9 vol%.

[0041] In the hydrogenation method, the reaction liquid after the reaction in the hydrogenation reactor I is completed can be partially recycled back to the hydrogenation reactor I as the first circulating material. Furthermore, the first circulating material can account for 0-90wt% of the total fresh raw material liquid, preferably 5wt%-50wt%.

[0042] In the hydrogenation method, the product of the upflow tubular reactor can be partially recycled back to the hydrogenation reactor I and / or the upflow tubular reactor as the second circulating material. Further, the second circulating material can account for 5wt% to 50wt% of the total fresh raw material liquid, preferably 1wt% to 20wt%.

[0043] The process conditions of the hydrogenation reactor I and the upflow tubular reactor are generally determined by those skilled in the art based on the properties of the raw materials, the quality requirements of the final product, etc.

[0044] In some embodiments, the process conditions of the hydrogenation reactor I 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 10 h -1 .

[0045] In some embodiments, the process conditions of the upflow tubular reactor in the hydrogenation method 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 1 to 20 h -1 .

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

[0047] In the present invention, the hydrogenation reactor I adopts a variable diameter countercurrent reactor structure, and the reaction gas-liquid mass transfer zone is divided into an upper reaction section, a countercurrent enhanced mass transfer section and a lower reaction section, wherein the upper reaction section / lower reaction section and the countercurrent enhanced mass transfer section are configured with variable diameters. This is mainly because as hydrogen and raw material substrates are continuously consumed during the reaction process, the gas-liquid ratio from the upper reaction section to the countercurrent enhanced mass transfer section and the lower reaction section increases successively, and the fresh raw material concentration decreases successively. That is, although the gas-liquid ratio in the upper reaction section is relatively low, the feed liquid is fresh raw material, the mass transfer driving force is large, and the reaction rate is fast; although the lower reaction section The concentration of fresh raw materials is low, but the gas-liquid ratio is high, the liquid film mass transfer resistance is greatly reduced, and the reaction rate is also faster; while the gas-liquid ratio and raw material substrate concentration of the countercurrent enhanced mass transfer section are in an intermediate state, and the reaction rate is lower than that of the upper reaction section and the lower reaction section to a certain extent, which is the key to affecting the overall countercurrent reaction rate. Therefore, the present invention sets a variable diameter for the countercurrent enhanced mass transfer section, that is, by increasing the apparent flow velocity while maintaining the original gas-liquid ratio, so that the material reaches a highly turbulent state, thereby reducing the liquid film mass transfer resistance, increasing the mass transfer rate, and achieving the goal of enhancing the countercurrent mass transfer process.

[0048] In addition, each section is filled with catalysts of different porosities and particle sizes, i.e., the upper reaction section / lower reaction section is filled with catalysts of low porosity and small particle size, which can further improve the catalytic reaction mass transfer surface area, in order to realize the synergistic enhancement of reaction rate and catalyst in this region; the catalyst of high porosity and large particle size is filled in the countercurrent enhanced mass transfer section, which is based on the material in this region passing through at high speed and in a high turbulent state, and the short contact time with the catalyst can achieve the desired reaction effect, and the high porosity and large particle size are set to be more conducive to the maintenance of material diffusion and turbulent state, so as to realize the synergistic enhancement of reaction rate and catalyst in this region. In this way, the mass transfer reaction rate of the entire reaction process in the hydrogenation reactor I has reached an overall higher state through segmented enhancement.

[0049] The hydrogenation reactor II adopts an upflow tubular reactor structure. On the one hand, considering that the concentration of the residual reaction substrate in the liquid material that has not completed the reaction of the hydrogenation reactor I is low, it is difficult to achieve the ideal reaction depth if the reactor structure of any type such as fixed bed cocurrent or countercurrent is continued in series. Therefore, the process is set to adopt an upflow tubular reactor structure, which is to force the hydrogen and liquid materials to mix into a uniform "liquid phase material" and cause a plug flow liquid phase hydrogenation reaction in the upflow tubular reactor. This can greatly reduce or even eliminate the gas-liquid film interphase mass transfer resistance while reducing back mixing, so that the reaction can achieve an ideal reaction rate and reaction depth, which is particularly suitable for achieving a higher reaction depth when the reaction substrate concentration is low; on the other hand, based on the fact that there is still some residual hydrogen in the hydrogenation reactor I, it is more suitable as a hydrogen source for the upflow tubular reactor. During the reaction process, the hydrogen supply can be appropriately adjusted according to the reaction effect of each stage, hydrogen consumption and overall reaction depth, so as to maximize the synergistic enhancement of the hydrogenation reactor I and the upflow tubular reactor. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 It is a structural schematic diagram of a variable diameter hydrogenation reaction system of the present invention. DETAILED DESCRIPTION

[0051] 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.

[0052] See also Figure 1 , a variable diameter hydrogenation reaction system, comprising a first hydrogenation reaction zone and a second hydrogenation reaction zone.

[0053] The first hydrogenation reaction zone includes a hydrogenation reactor 1, which is a variable diameter gas-liquid countercurrent hydrogenation reactor 5, including a gas deliquid section 8, an upper reaction section 9, a countercurrent enhanced mass transfer section 10, a lower reaction section 11 and a liquid degassing section 12 which are sequentially connected from top to bottom; the diameters of the upper reaction section 9 and the lower reaction section 11 are both larger than the diameter of the countercurrent enhanced mass transfer section 10; a liquid feed port is arranged between the gas deliquid section 8 and the upper reaction section 9; a gas feed port is arranged between the lower reaction section 11 and the liquid degassing section 12; a gas discharge port is arranged above the gas deliquid section 8; and a liquid discharge port is arranged below the liquid degassing section 12. The upper reaction section 9, the countercurrent enhanced mass transfer section 10 and the lower reaction section 11 are all filled with catalysts. The porosity of the catalyst bed filled in the upper reaction section 9 and the lower reaction section 11 is less than the porosity of the catalyst bed filled in the countercurrent enhanced mass transfer section 10. The catalyst particles loaded in the upper reaction section 9 and the lower reaction section 11 have a smaller size than the catalyst particles loaded in the countercurrent enhanced mass transfer section 10 .

[0054] The second hydrogenation reaction zone includes a hydrogenation reactor II, which is one or more parallel upflow tubular reactors 18; a feed port connected to the gas outlet and liquid outlet of the hydrogenation reactor I is arranged at the bottom of the upflow tubular reactor 18. The upflow tubular reactor 18 is filled with a catalyst.

[0055] A hydrogenation method, using the above Figure 1 The variable diameter hydrogenation reaction system shown comprises:

[0056] In the first hydrogenation reaction zone, the liquid feed 1 and the hydrogen 2 are respectively introduced into the liquid feed port and the gas feed port of the hydrogenation reactor 1. After the liquid feed 1 is evenly distributed by the liquid feed distributor 6, it enters the first catalyst bed 13 in the upper reaction section 9 to undergo a countercurrent hydrogenation reaction with the gas rising from the lower part. The remaining hydrogen after the reaction is deliquidated by the gas deliquidation section 8 and leaves the reactor, and enters the second hydrogenation reaction zone as the remaining gas 3 of the first hydrogenation reaction zone; after the hydrogen 2 is evenly distributed by the hydrogen distributor 7, it enters the third catalyst bed 15 in the lower reaction section 11 to undergo a countercurrent hydrogenation reaction with the liquid descending from the upper part, and the reaction product leaves the reactor after being degassed by the liquid degassing section 12, and enters the second hydrogenation reaction zone as the reaction liquid product 4 of the first hydrogenation reaction zone; in the countercurrent enhanced mass transfer section 10, the liquid from the upper reaction section 9 and the gas from the lower reaction section 11 undergo enhanced mass transfer in the second catalyst bed 14, the gas product enters the upper reaction section 9, and the liquid product enters the lower reaction section 11;

[0057] In the second hydrogenation reaction zone, the residual gas 3 and the reaction liquid product 4 from the first hydrogenation reaction zone enter the mixer 16 for forced mixing, and the residual gas 3 is evenly dispersed in the reaction liquid product in the form of nanometers / micrometers to form a uniform liquid phase material as the feed 17 of the hydrogenation reactor II, which enters from the bottom of the hydrogenation reactor II, i.e., the upflow tubular reactor 18, and an upflow liquid phase hydrogenation reaction occurs through the fourth catalyst bed 19, and the reaction product 20 leaves from the top of the reactor.

[0058] The above-mentioned variable diameter hydrogenation reaction system and hydrogenation method can be applied to phenol hydrogenation, dimethyl maleate hydrogenation, and biomass sugar (glucose) solution hydrogenation processes. The properties of phenol raw materials are shown in Tables 1 and 2, and the properties of phenol hydrogenation catalysts are shown in Table 3; the properties of dimethyl maleate raw materials are shown in Table 4, and the properties of dimethyl maleate hydrogenation catalysts are shown in Table 5; the properties of biomass sugar (glucose) hydrogenation raw materials are shown in Table 6, and the properties of biomass sugar (glucose) solution hydrogenation catalysts are shown in Table 7. All of the above raw materials are commercially available, and all hydrogenation catalysts are homemade.

[0059] Table 1 Properties of phenol raw materials

[0060] project index Remark Content / wt% ≥99.9 grade Premium

[0061] Table 2 Properties of phenol hydrogenation solvent (water)

[0062] name index pH range (25℃) 5.0～7.5 Conductivity (25℃), mS / m≤ 0.50 Specific resistance (MΩ.cm, 25℃) ≥ 0.2 Oxidizable substances [in (O)], mg / L 0.40 Evaporation residue (105±2℃), mg / L≤ 2.0

[0063] Table 3 Phenol hydrogenation catalyst properties

[0064] Active Metals index Catalyst type Pd Catalyst carrier <![CDATA[Al2O3]]> Active metal content, wt% 0.1～2.0

[0065] Table 4 Dimethyl Maleate Raw Materials

[0066] project index Characteristics Colorless transparent oily liquid Content, wt / % 99.5 <![CDATA[Density, g / m 3 > 1.124

[0067] Table 5 Properties of dimethyl maleate hydrogenation catalyst

[0068] project index Catalyst type Copper base Active Metals copper Active metal content, wt% 10～50 Catalyst carrier ZnO

[0069] Table 6 Biomass sugar (glucose) solution raw materials

[0070] project index Characteristics Colorless transparent liquid Concentration, mol / L 1.5

[0071] Table 7 Biomass sugar (glucose) solution hydrogenation catalyst properties

[0072] project Specifications shape spherical Active Metals nickel Catalyst carrier <![CDATA[Al2O3]]> Nickel content, wt% 5～40

[0073] Comparative Example 1

[0074] A gas-liquid countercurrent fixed bed hydrogenation reactor and an upflow tubular gas-liquid parallel flow reactor are connected in series, wherein a gas-liquid countercurrent hydrogenation reactor I is arranged in the first hydrogenation reaction zone, and the height-to-diameter ratio of the hydrogenation reactor I is 2.5; an upflow tubular gas-liquid parallel flow hydrogenation reactor II is arranged in the second hydrogenation reaction zone, and the height-to-diameter ratio of the hydrogenation reactor II is 2.5; the catalysts of the same specifications and sizes are filled in the hydrogenation reactors I and II, the catalyst porosity is 62.5%, and the catalyst particle size is

[0075] The device was used to investigate the reaction effects of phenol hydrogenation, dimethyl maleate hydrogenation, and biomass sugar (glucose) hydrogenation under different conditions. First, the raw material and hydrogen were introduced to the respective inlet temperatures of the hydrogenation reactor I in the first hydrogenation reaction zone after temperature adjustment, and then entered the catalyst bed from the top and bottom of the hydrogenation reactor I to undergo hydrogenation reaction. The top gas outlet and the bottom liquid outlet were forced to mix and temperature-adjusted before entering the bottom of the hydrogenation reactor II to continue the upflow hydrogenation reaction, and then left after the hydrogenation reaction was completed.

[0076] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 8, and the reaction results are shown in Table 9. The volume space velocity in Table 8 refers to the liquid time volume space velocity, which will not be repeated below.

[0077] Comparative Example 2

[0078] A gas-liquid countercurrent fixed-bed hydrogenation reactor and an upflow tubular gas-liquid parallel flow reactor are connected in series. A gas-liquid countercurrent hydrogenation reactor I is arranged in the first hydrogenation reaction zone. The hydrogenation reactor I is divided into three reaction zones: upper, middle and lower. The residence time ratio of the three reaction zones is 1:2:1. The height-to-diameter ratio of the upper and lower reaction zones is 2.0, and the height-to-diameter ratio of the middle reaction zone is 4.0. Two parallel gas-liquid parallel flow hydrogenation reactors II are arranged in the second hydrogenation reaction zone. The height-to-diameter ratios of the hydrogenation reactors II are both 3.0. Catalysts of the same specifications and sizes are loaded in the hydrogenation reactors I and II. The catalyst porosity is 62.5%, and the catalyst particle size is The hydrogenation reactor I and the hydrogenation reactor II are connected in series.

[0079] The device was used to investigate the reaction effects of phenol hydrogenation, dimethyl maleate hydrogenation, and biomass sugar (glucose) hydrogenation under different conditions. First, the raw material and hydrogen were temperature-adjusted to the inlet temperature of the hydrogenation reactor I in the first hydrogenation reaction zone, and then introduced into the gas-liquid countercurrent hydrogenation reactor I from the top and bottom, respectively. The two reacted in the hydrogenation reactor I to produce residual hydrogen and reaction liquid; the reaction liquid was temperature-adjusted and mixed with the residual hydrogen using a static mixer, and then entered from the bottom of the hydrogenation reactor II to continue the upflow hydrogenation reaction, and left after the hydrogenation reaction was completed.

[0080] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 8, and the reaction results are shown in Table 9.

[0081] Example 1

[0082] The system and method described in the specific embodiment of the present invention are adopted, and the first hydrogenation reaction zone is provided with a hydrogenation reactor I, and the first hydrogenation reactor I is a variable diameter gas-liquid countercurrent hydrogenation reactor structure, wherein the material residence time ratio of the upper reaction section to the countercurrent enhanced mass transfer section and the lower reaction section is 1:2:1, the height-to-diameter ratio of the upper reaction section and the lower reaction section is 2.0, the void ratio of the loaded catalyst is 31.4%, and the catalyst particle size is The height-to-diameter ratio of the countercurrent enhanced mass transfer section is 4.0, the void ratio of the loaded catalyst is 70%, and the catalyst particle size is The second hydrogenation reaction zone is provided with a hydrogenation reactor II, which is a structure of two parallel upflow tubular liquid phase hydrogenation reactors. The height-to-diameter ratio of the hydrogenation reactor II is 5.0, the void ratio of the loaded catalyst is 38.5%, and the catalyst particle size is

[0083] The system was used to investigate the reaction effects of phenol hydrogenation, dimethyl maleate hydrogenation, and biomass sugar (glucose) hydrogenation under different conditions. First, the raw material was temperature-adjusted to the inlet temperature of the hydrogenation reactor I in the first hydrogenation reaction zone, and then introduced into the gas-liquid countercurrent hydrogenation reactor I from the top. The hydrogen was temperature-adjusted and introduced from the bottom of the gas-liquid countercurrent hydrogenation reactor I. The two reacted in the hydrogenation reactor I with gas-liquid countercurrent hydrogenation, and then the remaining hydrogen and the reaction liquid were obtained respectively; the reaction liquid and the remaining hydrogen were temperature-adjusted to the reaction temperature, and after being uniformly mixed with a static mixer, they were introduced from the bottom of the hydrogenation reactor II, and an upflow hydrogenation reaction occurred from bottom to top through its catalyst bed, and the hydrogenation reaction was completed and then left.

[0084] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 8, and the reaction results are shown in Table 9.

[0085] Example 2

[0086] The system and method described in the specific embodiment of the present invention are used, and the process flow and reactor settings are the same as those in Example 1, except that: in the hydrogenation reactor I, the residence time ratio of the upper reaction section, the lower reaction section and the countercurrent enhanced mass transfer section is 1:1:1, the height-to-diameter ratio of the upper reaction section and the lower reaction section is 2.5, the void ratio of the loaded catalyst is 25.5%, and the catalyst particle size is The height-to-diameter ratio of the countercurrent enhanced mass transfer section is 3.5, the void ratio of the loaded catalyst is 52.5%, and the catalyst particle size is The hydrogenation reactor II is an upflow tubular liquid phase hydrogenation reactor structure. The height-to-diameter ratio of the hydrogenation reactor II is 4.0, the void ratio of the loaded catalyst is 42.5%, and the catalyst particle size is

[0087] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 8, and the reaction results are shown in Table 9.

[0088] Example 3

[0089] The system and method of the present invention are used, and the process flow and reactor configuration are the same as those of Example 1, except that the residence time ratio of the upper reaction section, the lower reaction section, and the countercurrent enhanced mass transfer section is 1:1.5:1, the height-to-diameter ratio of the upper reaction section and the lower reaction section is 2.5, the void ratio of the loaded catalyst is 30.5%, and the catalyst particle size is The height-to-diameter ratio of the countercurrent enhanced mass transfer section is 3.5, the void ratio of the loaded catalyst is 62.5%, and the catalyst particle size is The hydrogenation reactor II is an upflow tubular liquid phase hydrogenation reactor structure. The height-to-diameter ratio of the hydrogenation reactor II is 4.0, the void ratio of the loaded catalyst is 58.2%, and the catalyst particle size is

[0090] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 8, and the reaction results are shown in Table 9.

[0091] Example 4

[0092] The system and method described in the specific embodiment of the present invention are used, and the process flow and reactor configuration are the same as in Example 1, except that the residence time ratio of the upper reaction section, the lower reaction section and the countercurrent enhanced mass transfer section is 1:2:1, the height-to-diameter ratio of the upper reaction section and the lower reaction section is 3, the void ratio of the loaded catalyst is 38.9%, and the catalyst particle size is The height-to-diameter ratio of the countercurrent enhanced mass transfer section is 8, the void ratio of the loaded catalyst is 80%, and the catalyst particle size is The hydrogenation reactor II is an upflow tubular liquid phase hydrogenation reactor structure. The height-to-diameter ratio of the hydrogenation reactor II is 6.0, the void ratio of the loaded catalyst is 58.2%, and the catalyst particle size is

[0093] The operating conditions of hydrogenation reactor I and hydrogenation reactor II are shown in Table 8, and the reaction results are shown in Table 9.

[0094] Example 5

[0095] The system and method described in the specific embodiment of the present invention are adopted, and the process flow and reactor configuration are the same as those in Example 2. The difference lies in the reaction conditions of hydrogenation reactor I and the type of inlet material mixer of hydrogenation reactor II. Here, the inlet material mixer of hydrogenation reactor II adopts a dissolved air pump.

[0096] The operating conditions are shown in Table 8, and the reaction results are shown in Table 9.

[0097] Table 8 Operating conditions of hydrogenation reactor I and hydrogenation reactor II

[0098]

[0099] Table 9 Reaction effect

[0100]

[0101] It can be seen from the effects of the various embodiments and comparative examples of the present invention that the hydrogenation reaction system and hydrogenation method of the present invention are adopted, and the hydrogenation reactor I adopts a countercurrent variable diameter hydrogenation reactor, and each reaction stage in the countercurrent variable diameter hydrogenation reactor is coupled with a catalyst, which can effectively strengthen various types of hydrogenation reactions; the hydrogenation reactor II adopts an upflow tubular liquid phase hydrogenation reactor, which can realize liquid phase hydrogenation reaction in a plug flow mode, greatly reducing or even eliminating the gas-liquid film phase mass transfer resistance, while reducing back mixing, thereby achieving a higher reaction rate and reaction depth, and is particularly suitable for deep hydrogenation reaction in the case where the content of the intended hydrogenation component in the raw material is low. Therefore, the present invention couples the variable diameter reactor I of the first hydrogenation reaction zone with the upflow tubular reactor I of the second hydrogenation reaction zone, and the residual hydrogen of the first hydrogenation reaction zone is used as the hydrogen source of the second hydrogenation reaction zone, while realizing the segmented strengthening of the entire hydrogenation reaction process, greatly improving the hydrogen utilization rate, reducing the hydrogen-liquid ratio, shortening the reaction time, and reducing the device consumption and investment.

[0102] 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 variable diameter hydrogenation reaction system, characterized in that: It includes a hydrogenation reactor I and a hydrogenation reactor II; The hydrogenation reactor I is a variable diameter gas-liquid countercurrent hydrogenation reactor, comprising a gas deliquid section, an upper reaction section, a countercurrent enhanced mass transfer section, a lower reaction section and a liquid degassing section which are sequentially connected and arranged from top to bottom; the diameters of the upper reaction section and the lower reaction section are both larger than the diameter of the countercurrent enhanced mass transfer section; a liquid feed port is arranged between the gas deliquid section and the upper reaction section; a gas feed port is arranged between the lower 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; The hydrogenation reactor II comprises at least one upflow tubular reactor; a feed port connected to the gas discharge port and the liquid discharge port of the hydrogenation reactor I is arranged at the bottom of the upflow tubular reactor.

2. The variable diameter hydrogenation reaction system according to claim 1, characterized in that: The height-to-diameter ratio of the countercurrent enhanced mass transfer section is 2 to 30:1, preferably 3 to 10:1; The height-to-diameter ratios of the gas-to-liquid degassing section, the upper reaction section, the lower reaction section, and the liquid-to-gassing section are all the same or not all the same or all different, and are independently 0.5 to 5:1, preferably 1 to 3:1; The ratio of the material residence time in the upper reaction section to the countercurrent enhanced mass transfer section is 1 to 100:10, preferably 1 to 2:2; The ratio of the material residence time in the lower reaction section to the countercurrent enhanced mass transfer section is 1 to 100:10, preferably 1 to 2:

2.

3. The variable diameter hydrogenation reaction system according to claim 1, characterized in that: The upper reaction section, the countercurrent enhanced mass transfer section and the lower reaction section are all filled with catalysts; The void ratio of the catalyst bed filled in the upper reaction section and the lower reaction section is smaller than the void ratio of the catalyst bed filled in the countercurrent enhanced mass transfer section; The porosity of the catalyst bed loaded in the upper reaction section and the lower reaction section is the same or different; the porosity of the catalyst bed loaded in the upper reaction section and the lower reaction section is independently 10% to 50%, preferably 20% to 40%; The void ratio of the catalyst bed filled in the countercurrent enhanced mass transfer section is 30% to 90%, preferably 50% to 80%; The catalyst particles in the upper reaction section and the lower reaction section are smaller than the catalyst particles in the countercurrent enhanced mass transfer section. The catalyst particles loaded in the upper reaction section and the lower reaction section have the same or different sizes; the catalyst particles loaded in the upper reaction section and the lower reaction section have sizes of 0.3 to 3 mm, preferably 0.5 to 2 mm, respectively; The size of the catalyst particles filled in the countercurrent enhanced mass transfer section is 2 to 10 mm, preferably 3 to 6 mm.

4. The variable diameter hydrogenation reaction system according to claim 1, characterized in that: The hydrogenation reactor II comprises a plurality of upflow tubular reactors connected in parallel.

5. The variable diameter hydrogenation reaction system according to claim 1, characterized in that: The upflow tubular reactor has a height-to-diameter ratio of 2 to 15:1, preferably 3 to 8:

1.

6. The variable diameter hydrogenation reaction system according to claim 1, characterized in that: The upflow tubular reactor is filled with a catalyst; the voidage of the catalyst bed filled in the upflow tubular reactor is 10% to 80%, preferably 30% to 60%; the particle size of the catalyst filled in the upflow tubular reactor is 1.5 to 5 mm, preferably 2 to 4.5 mm; The reaction feed of the upflow tubular reactor is a liquid phase containing nano / micron dispersed hydrogen, and the liquid phase is formed by dissolving and / or dispersing part or all of the hydrogen discharged from the gas outlet of the hydrogenation reactor I with or without additional hydrogen supplementation in part or all of the reaction liquid discharged from the liquid outlet of the hydrogenation reactor I. An upflow liquid phase hydrogenation reaction occurs in the upflow tubular reactor, and the liquid phase hydrogenation means that hydrogen is pre-dissolved and / or dispersed in the liquid reactant and then liquid-solid two-phase hydrogenation occurs.

7. Use of the variable diameter hydrogenation reaction system according to any one of claims 1 to 6 in hydrogenation reactions.

8. A hydrogenation method, characterized in that: A variable diameter hydrogenation reaction system as described in any one of claims 1 to 6 is used.

9. The hydrogenation method according to claim 8, characterized in that The raw material liquid enters the hydrogenation reactor I from the liquid feed port, and the hydrogen enters the hydrogenation reactor I from the gas feed port. The raw material liquid and the hydrogen undergo a countercurrent hydrogenation reaction in the hydrogenation reactor I. The remaining hydrogen after the reaction is completed leaves from the gas discharge port and partially or completely enters the upflow tubular reactor. The reaction liquid after the reaction is completed leaves from the liquid discharge port and partially or completely enters the upflow tubular reactor; part or all of the remaining hydrogen discharged from the gas discharge port of the hydrogenation reactor I is dissolved and / or dispersed in part or all of the reaction liquid discharged from the liquid discharge port of the hydrogenation reactor I with or without additional hydrogen supplementation to form a liquid phase containing nano / micron dispersed hydrogen, and an upflow liquid phase hydrogenation reaction occurs in the upflow tubular reactor.

10. The hydrogenation method according to claim 9, characterized in that: The feed ratio of hydrogen to raw liquid in hydrogenation reactor I is 1 to 500 Nm 3 / h:1m 3 / h, preferably 5 to 100 Nm 3 / h:1m 3 / h; The feed ratio of hydrogen to reaction liquid in the upflow tubular reactor is 1 to 100 Nm 3 / h:1m 3 / h, preferably 2 to 20 Nm 3 / h:1m 3 / h; The hydrogenation method uses hydrogen with a purity greater than 90 vol%, preferably using pure hydrogen greater than 99.9 vol%; The reaction liquid after the reaction in the hydrogenation reactor I is circulated back to the hydrogenation reactor I as the first circulating material, and the first circulating material accounts for 0 to 90 wt% of the total fresh raw material liquid, preferably 5 wt% to 50 wt%; The product portion of the upflow tubular reactor is circulated back to the hydrogenation reactor I and / or the upflow tubular reactor as the second circulating material, and the second circulating material accounts for 5wt% to 50wt% of the total fresh raw material liquid, preferably 1wt% to 20wt%; The process conditions of hydrogenation reactor I include: reaction temperature is room temperature to 500°C, reaction pressure is 0.1 to 20 MPaG, liquid hourly volume space velocity is 0.1 to 10 h -1 ; The process conditions of the upflow tubular reactor include: reaction temperature of room temperature to 500°C, reaction pressure of 0.1 to 20 MPaG, liquid hourly volume space velocity of 1 to 20 h -1 .

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