Column reactor and its application in preparation of chemicals by catalytic hydrogenation of carbon dioxide

Abstract

The application relates to the field of reactors, and discloses a tube reactor and application of the tube reactor in preparation of chemicals through catalytic hydrogenation of carbon dioxide. The tube reactor comprises a reactor box and a plurality of reaction tubes arranged in the reactor box, the reaction tube comprises an inner tube and an outer tube sleeved outside the inner tube, the inner tube is filled with a catalyst, and the inner tube and the outer tube are filled with inert fillers. The tube reactor can effectively avoid problems such as reduction of catalyst activity caused by water generated in the process of preparing chemicals through catalytic hydrogenation of carbon dioxide, improve the reaction efficiency of the preparation of chemicals through catalytic hydrogenation of carbon dioxide, and improve the yield of the chemicals.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of reactors, in particular to a shell-and-tube reactor and its application in the preparation of chemicals by catalytic hydrogenation of carbon dioxide. BACKGROUND

[0002] The technology of preparing chemicals by catalytic hydrogenation of carbon dioxide has attracted much attention as an important CO2 resource utilization technology, because it can form high-value-added fuels or chemicals such as methanol, ethanol, formic acid or gasoline through catalytic reaction using CO2 as raw material. On the one hand, the technology of preparing chemicals by hydrogenation of carbon dioxide can well realize the reduction of carbon dioxide emission, and on the other hand, the chemicals prepared by the technology can reduce the current dependence on fossil fuels and increase the recycling value of carbon dioxide.

[0003] At present, the technology of preparing chemicals by catalytic hydrogenation of carbon dioxide usually uses a shell-and-tube reactor as a reaction unit. However, a large amount of water vapor is inevitably produced during the reaction process of catalytic hydrogenation of carbon dioxide, and the water vapor produced during the reaction is difficult to remove from the entire reaction system, thereby causing the catalyst used for catalytic hydrogenation of carbon dioxide to be easily deactivated, reducing the catalytic activity of the catalyst, and adversely affecting the yield and reaction efficiency of the chemicals prepared by catalytic hydrogenation of carbon dioxide. SUMMARY

[0004] The present application aims to overcome the problems of catalyst deactivation caused by water produced during the process of preparing chemicals by hydrogenation of carbon dioxide in the prior art, and provides a shell-and-tube reactor and its application in the preparation of chemicals by catalytic hydrogenation of carbon dioxide. The shell-and-tube reactor can effectively avoid the problems of reduced catalyst activity caused by water vapor produced during the process of preparing chemicals by catalytic hydrogenation of carbon dioxide, improve the reaction efficiency of the preparation of chemicals by catalytic hydrogenation of carbon dioxide, and improve the yield of chemicals.

[0005] To achieve the above-mentioned purpose, the present application provides a shell-and-tube reactor, which comprises a reactor box and a plurality of reaction tubes arranged in the reactor box. The reaction tube comprises an inner tube and an outer tube sleeved outside the inner tube. The inner tube is filled with a catalyst, and the inner tube and the outer tube are filled with inert fillers.

[0006] Preferably, the inner tube and the outer tube are in communication.

[0007] Preferably, the inner tube is a rigid wire mesh.

[0008] Preferably, the rigid wire mesh is selected from one of a rigid iron wire mesh, a rigid titanium wire mesh or a rigid steel wire mesh.

[0009] Preferably, the outer tube is a pervaporation membrane.

[0010] Preferably, the pervaporation membrane is selected from one of PVA membrane, PI membrane and PVA / PAN composite membrane.

[0011] Preferably, the reactor box comprises an upper head, a reactor cylinder and a lower head which are sequentially communicated.

[0012] The upper head is provided with a raw material inlet for inputting raw materials required for reaction into the tube-type reactor.

[0013] The lower head is provided with a product outlet for outputting products obtained in the reaction tube and unreacted raw materials.

[0014] The upper part of the reactor cylinder is provided with a cooling medium inlet for inputting cooling medium for heat exchange with materials in the reaction tube.

[0015] The lower part of the reactor cylinder is provided with a cooling medium outlet for outputting the heat-exchanged cooling medium.

[0016] Preferably, the ratio of the inner diameter of the inner tube to the inner diameter of the outer tube is 1:1.1-2.

[0017] Preferably, the ratio of the inner diameter of the inner tube to the inner diameter of the outer tube is 1:1.2-1.5.

[0018] The second aspect of the present application provides a use of the above-mentioned tube-type reactor in the preparation of chemicals by catalytic hydrogenation of carbon dioxide.

[0019] Preferably, the chemicals are selected from methanol or ethanol.

[0020] Through the above technical solution, the reaction tube in the tubular reactor of the present invention has a double-layered tube structure, and the inner tube and the outer tube of the reactor are connected. The inner tube of the reaction tube is filled with a catalyst for the catalytic hydrogenation of carbon dioxide to catalyze the reaction. At the same time, the inner tube of the reaction tube is a rigid wire mesh with a large pore structure, and the outer tube is a pervaporation membrane that allows water vapor to pass through. In the application process, the water vapor generated in the reaction of carbon dioxide hydrogenation to prepare chemicals can enter the shell side of the tubular reactor from the reaction tube under the drive of the temperature difference between the inside and outside of the reaction tube. After condensing into liquid water, it mixes with the cooling medium used for heat exchange in the shell side and is discharged from the tubular reactor. This effectively avoids the problems of reduced specific surface area and reduced activity of the catalyst in the inner tube of the reaction tube after it comes into contact with water, thereby improving the reaction efficiency of carbon dioxide catalytic hydrogenation. In addition, the reaction tube of the present invention has better heat dissipation performance. Therefore, the heat transfer performance of the reaction tube of the present invention is better than that of the prior art. The tubular reactor of the present invention can better control the reaction temperature and avoid problems such as catalyst sintering and deactivation. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the structure of the tubular reactor described in this invention;

[0022] Figure 2 This is a cross-sectional view of the reaction tube described in this invention.

[0023] Explanation of reference numerals in the attached figures

[0024] 1 Reactor housing; 2 Reactor tube; 3 Upper head; 4 Lower head; 5 Reactor cylinder; 6 Raw material inlet; 7 Product outlet; 8 Cooling medium inlet; 9 Cooling medium outlet; 21 Inner tube of the reaction tube; 22 Outer tube of the reaction tube. Detailed Implementation

[0025] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0026] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0027] In addition, the terms indicating the orientation or relative position relationship such as "upper", "lower", "top", "bottom", "inner", "outer" and the like are described based on the orientation or relative position relationship shown in the drawings, which is only for the convenience of the simplified description of the present application and does not indicate that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present application.

[0028] In addition, unless otherwise explicitly specified and limited, the term "connection" should be understood broadly, for example, it can be a fixed connection, or a detachable connection, or an integral connection; it can be a mechanical connection, or an electrical connection; it can be a direct connection, or an indirect connection through an intermediate medium, or a connection between two elements. For those skilled in the art, the specific meaning of the above-mentioned terms in the present application can be understood according to the specific circumstances.

[0029] In the present application, "tube side" refers to the area inside the reaction tube 2 of the shell-and-tube reactor, and "shell side" refers to the area between the reaction tube 2 outside the shell-and-tube reactor and the reactor cylinder 5.

[0030] The present application provides a shell-and-tube reactor, a structural schematic diagram of which is shown in Figure 1 The shell-and-tube reactor comprises a reactor box 1 and a plurality of reaction tubes 2 arranged in the reactor box 1, the reaction tube 2 comprises an inner tube 21 and an outer tube 22 sleeved outside the inner tube, the inner tube 21 is filled with a catalyst, the inner tube 21 and the outer tube 22 are filled with inert fillers, and a sectional view of the reaction tube 2 is shown in Figure 2 .

[0031] In the shell-and-tube reactor, the inner tube 21 and the outer tube 22 are in communication.

[0032] In the shell-and-tube reactor, the reactor box 1 comprises an upper head 3, a reactor cylinder 5 and a lower head 4 in sequence;

[0033] The upper head 3 is provided with a raw material inlet 6, which is used for inputting raw materials required for the reaction into the shell-and-tube reactor;

[0034] The lower head 4 is provided with a product outlet 7, which is used for outputting the products obtained in the reaction tube 2 and the unreacted raw materials;

[0035] A cooling medium inlet 8 is arranged at the upper part of the reactor cylinder 5, which is used for inputting a cooling medium for heat exchange with the materials in the reaction tube 2;

[0036] A cooling medium outlet 9 is arranged at the lower part of the reactor cylinder 5, and is used to output the cooling medium after heat exchange.

[0037] In the shell-and-tube reactor, the cooling medium can be water.

[0038] In the shell-and-tube reactor, the upper head 3 is arranged at the top of the reactor box 1, the lower head 4 is arranged at the bottom of the reactor box 1, and the reaction tubes 2 are fixed by the upper head 3 and the lower head 4 and arranged in parallel and spaced apart in the reactor cylinder 5.

[0039] In the shell-and-tube reactor, the top of the reaction tube 2 is higher than the bottom of the upper head 3, and the bottom of the reaction tube 2 is lower than the top of the lower head 4. When the reactor is running, the raw material enters the upper head 3 and enters the reaction tube 2 for reaction. After the reaction is completed, the material in the reaction tube 2 is first transported to the lower head 4 and then discharged from the shell-and-tube reactor. Therefore, in the shell-and-tube reactor, the cooling medium used for heat exchange with the material in the reaction tube 2 in the shell side can be effectively prevented from entering the reaction tube 2, thereby avoiding problems such as catalyst deactivation.

[0040] In the shell-and-tube reactor, the number of the reaction tubes 2 is 20-30, preferably 25-28.

[0041] In the shell-and-tube reactor, the inner tube 21 is a rigid wire mesh, which is selected from one of rigid iron wire mesh, rigid titanium wire mesh or rigid steel wire mesh. In the present application, the inner tube 21 of the reaction tube 2 is selected to provide strength to the reaction tube 2, and the selection of the rigid wire mesh can also improve the heat exchange rate of the cooling medium and the material in the reaction tube 2, and facilitate the temperature control of the shell-and-tube reactor.

[0042] In the shell-and-tube reactor, the outer tube 22 is a pervaporation membrane, which is selected from one of PVA membrane, PI membrane and PVA / PAN composite membrane. The pervaporation membrane is a hydrophilic membrane, which can preferentially allow water vapor to pass through, so that the water vapor generated in the carbon dioxide catalytic hydrogenation reaction can be well removed from the reaction system. In addition, the pervaporation membrane also has excellent thermal stability and heat dissipation performance, which is also conducive to direct heat exchange between the cooling medium and the reaction system. The pervaporation membrane can be prepared according to the common method in the art or can be a common commercially available product.

[0043] In the shell-and-tube reactor, the temperature inside the reaction tube 2 is much higher than the temperature of the shell side, so the temperature difference between the tube side and the shell side drives the water vapor generated in the carbon dioxide catalytic hydrogenation reaction to spontaneously move from the tube side to the shell side, and the inner tube 21 and the outer tube 22 of the reactor in the present application are in communication with each other. Since the temperature of the shell side is low and the cooling medium of the shell side is water, when the water vapor generated in the reaction moves to the vicinity of the pervaporation membrane, the temperature of the water vapor is reduced to form a metastable substance, and then the metastable substance is condensed into liquid water in the shell side after passing through the pervaporation membrane. The liquid water is mixed with the water originally present in the shell side and is discharged through the cooling medium outlet 9 arranged at the lower part of the reactor cylinder 5.

[0044] In the shell-and-tube reactor, the inert filler filled between the inner tube 21 and the outer tube 22 of the reaction tube 2 can further increase the strength of the reaction tube 2, and there are many gaps between the inert fillers, which are helpful for the migration of the water vapor generated in the reaction to the shell side of the reactor and for the heat exchange between the reaction tube 2 and the cooling medium of the shell side during the reaction. In addition, the inert filler can also adsorb the raw material gas, avoiding the diffusion of a large amount of raw material gas from the inner tube 21 of the reaction tube 2 to the outside, thereby avoiding the waste of raw materials. The filler can be a metal oxide, such as SiO2, ZrO2, CuO or Al2O3.

[0045] In the shell-and-tube reactor, according to the application field of the reactor and the reaction occurring in the shell-and-tube reactor, a suitable catalyst can be selected for loading in the reaction tube 2, and the type of catalyst is not limited herein.

[0046] In the shell-and-tube reactor, in order to further improve the heat exchange efficiency of the reactor and to timely transfer the water generated in the inner tube 21 of the reactor to the shell side, the ratio of the inner diameter of the inner tube 21 to the inner diameter of the outer tube 22 in the reaction tube 2 is 1:1.1-2, and is further preferably 1:1.2-1.5. Specifically, the ratio of the inner diameter of the inner tube 21 to the inner diameter of the outer tube 22 is 1:1.2, 1:1.3, 1:1.4 or 1:5.

[0047] According to the first specific embodiment of the shell-and-tube reactor, the shell-and-tube reactor comprises a reactor box 1 and a plurality of reaction tubes 2 arranged in the reactor box 1. The reaction tube 2 comprises an inner tube 21 and an outer tube 22 sleeved outside the inner tube. The inner tube 21 is filled with a catalyst, and the inner tube 21 and the outer tube 22 are filled with an inert filler. The material of the inner tube 21 is a rigid wire mesh, and the rigid wire mesh is selected from one of a rigid iron wire mesh, a rigid titanium wire mesh or a rigid steel wire mesh.

[0048] According to another specific embodiment of the tubular reactor according to the present application, the tubular reactor comprises a reactor tank 1 and a plurality of reaction tubes 2 arranged in the reactor tank 1, the reaction tube 2 comprising an inner tube 21 filled with a catalyst and an outer tube 22 sleeved outside the inner tube, and the inner tube 21 and the outer tube 22 are filled with inert fillers; the inner tube 21 is a rigid wire mesh; the rigid wire mesh is selected from one of rigid iron wire mesh, rigid titanium wire mesh or rigid steel wire mesh; the outer tube 22 is a pervaporation membrane.

[0049] According to another specific embodiment of the tubular reactor according to the present application, the tubular reactor comprises a reactor tank 1 and a plurality of reaction tubes 2 arranged in the reactor tank 1, the reaction tube 2 comprising an inner tube 21 filled with a catalyst and an outer tube 22 sleeved outside the inner tube, and the inner tube 21 and the outer tube 22 are filled with inert fillers; the inner tube 21 is a rigid wire mesh; the rigid wire mesh is selected from one of rigid iron wire mesh, rigid titanium wire mesh or rigid steel wire mesh; the outer tube 22 is a pervaporation membrane.

[0050] According to another specific embodiment of the tubular reactor according to the present application, the tubular reactor comprises a reactor tank 1 and a plurality of reaction tubes 2 arranged in the reactor tank 1, the reaction tube 2 comprising an inner tube 21 filled with a catalyst and an outer tube 22 sleeved outside the inner tube, and the inner tube 21 and the outer tube 22 are filled with inert fillers; the inner tube 21 is a rigid wire mesh; the rigid wire mesh is selected from one of rigid iron wire mesh, rigid titanium wire mesh or rigid steel wire mesh; the outer tube 22 is a pervaporation membrane; the ratio of the inner diameter of the inner tube 21 to the inner diameter of the outer tube 22 is 1:2-1.5.

[0051] According to another specific embodiment of the tubular reactor according to the present application, the tubular reactor comprises a reactor tank 1 and a plurality of reaction tubes 2 arranged in the reactor tank 1, the reaction tube 2 comprising an inner tube 21 filled with a catalyst and an outer tube 22 sleeved outside the inner tube, and the inner tube 21 and the outer tube 22 are filled with inert fillers; the inner tube 21 is a rigid wire mesh; the rigid wire mesh is selected from one of rigid iron wire mesh, rigid titanium wire mesh or rigid steel wire mesh; the outer tube 22 is a pervaporation membrane; the pervaporation membrane is selected from one of PVA membrane, PI membrane, PVA / PAN composite membrane; the ratio of the inner diameter of the inner tube 21 to the inner diameter of the outer tube 22 is 1:1.2-1.5.

[0052] According to another specific embodiment of the shell-and-tube reactor, the shell-and-tube reactor comprises a reactor shell 1 and a plurality of reaction tubes 2 arranged in the reactor shell 1, the reaction tube 2 comprises an inner tube 21 filled with a catalyst and an outer tube 22 sleeved outside the inner tube, and inert filler is filled between the inner tube 21 and the outer tube 22; the inner tube 21 is a rigid wire mesh; the rigid wire mesh is selected from one of rigid iron wire mesh, rigid titanium wire mesh or rigid steel wire mesh; the outer tube 22 is a pervaporation membrane; the pervaporation membrane is selected from one of PVA membrane, PI membrane or PVA / PAN composite membrane; the reactor shell 1 comprises an upper head 3, a reactor cylinder 5 and a lower head 4 which are sequentially communicated; the upper head 3 is provided with a raw material inlet 6 for inputting raw materials required for reaction into the shell-and-tube reactor; the lower head 4 is provided with a product outlet 7 for outputting products obtained in the reaction tube 2 and unreacted raw materials; a cooling medium inlet 8 is arranged at the upper part of the reactor cylinder 5 for inputting cooling medium for heat exchange with materials in the reaction tube 2; a cooling medium outlet 9 is arranged at the lower part of the reactor cylinder 5 for outputting the cooling medium after heat exchange; the ratio of the inner diameter of the inner tube 21 to the inner diameter of the outer tube 22 is 1:1.2-1.5.

[0053] The working principle of the shell-and-tube reactor is that the raw materials for reaction are conveyed from the raw material inlet 6 to the upper head 3 and then into the inner tube 21 of the reaction tube 2 for reaction, and the reacted products and unreacted raw materials are conveyed to the lower head 4 and then discharged through the product outlet 7; during the reaction, the cooling medium enters the shell side of the reactor from the cooling medium inlet 8 at the upper part of the reactor cylinder 5 for heat exchange with the materials in the reaction tube 2, and the cooling medium after heat exchange is mixed with the condensed water from the reaction tube 2 into the shell side and then discharged through the cooling medium outlet 9.

[0054] The application further provides an application of the above-mentioned shell-and-tube reactor in the preparation of chemicals by catalytic hydrogenation of carbon dioxide. In a further preferred embodiment, the chemicals are selected from methanol or ethanol.

[0055] In specific implementations, the commonly used catalyst systems in the catalytic hydrogenation of carbon dioxide to prepare chemicals are oxide-supported active metal catalysts, such as Cu / ZnO / Al2O3 catalysts. During the catalytic hydrogenation of carbon dioxide, carbon dioxide first removes an oxygen atom from its molecule to obtain an intermediate substance. This intermediate substance then reacts with hydrogen to prepare chemicals such as alcohols. Similarly, the oxygen atom removed from carbon dioxide during the reaction combines with hydrogen to form water molecules. Therefore, a large amount of water vapor is generated during the catalytic hydrogenation of carbon dioxide to prepare chemicals. If this generated water vapor is not properly controlled... Removing the catalyst from the reaction system in a timely manner would increase the specific surface area of ​​the oxides in the catalyst system. Therefore, in the tubular reactor described in this invention, the water vapor obtained from the reaction in the reaction tube 2 can be driven by the temperature difference between the tube side and the shell side to pass through the rigid wire mesh, inert packing, and pervaporation membrane into the shell side of the reactor. After condensing into liquid water, it is then mixed with the cooling medium in the shell side and discharged from the reactor. This ensures that the activity of the catalyst system in the tubular reactor is not affected, and also ensures the normal operation of the tubular reactor, thereby improving the yield of the catalytic hydrogenation of carbon dioxide to produce chemicals.

[0056] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited thereto.

[0057] The following examples are as follows Figure 1 Implemented in the tubular reactor shown, such as Figure 1 As shown, the tubular reactor includes a reactor housing 1 and several ( Figure 1 (Only 4 are visible in the middle) The reaction tubes 2 are arranged in the reactor box 1. The reaction tubes 2 include an inner tube 21 and an outer tube 22 sleeved on the outside of the inner tube. The inner tube 21 is filled with catalyst, and the space between the inner tube 21 and the outer tube 22 is filled with inert packing.

[0058] The reactor housing includes an upper end cap 3, a reactor cylinder 5, and a lower end cap 4 connected in sequence; the reaction tubes 2 are fixed vertically and parallelly spaced in the reactor cylinder 5 by the upper end cap 3 and the lower end cap 4 respectively; the top of the reactor 2 is higher than the bottom of the upper end cap 3, and the bottom of the reactor 2 is lower than the top of the lower end cap 4;

[0059] The upper end cap 3 is provided with a raw material inlet 6; the lower end cap 4 is provided with a product outlet 7; a cooling medium inlet 8 is provided at the upper part of the reactor body 5; and a cooling medium outlet 9 is provided at the lower part of the reactor body 5.

[0060] Example 1

[0061] The mixed gas of carbon dioxide and hydrogen (temperature 200℃) is transported from the raw material inlet 6 to the upper head 3 and then into the inner tube 21 of the reaction tube 2 to carry out the carbon dioxide catalytic hydrogenation reaction to prepare methanol, and the methanol product and the unreacted raw material are transported to the lower head 4 and then discharged through the product outlet 7; during the reaction process, the cooling medium water enters the shell side of the reactor from the cooling medium inlet 8 at the upper part of the reactor cylinder 5 to exchange heat with the materials in the reaction tube 2, and the water after heat exchange is mixed with the condensed water from the inner tube 21 of the reaction tube 2 into the shell side and then discharged through the cooling medium outlet 9;

[0062] The inner tube 21 of the tube reactor is a rigid titanium wire mesh; the outer tube 22 is a PVA film; the inert filler is SiO2; the ratio of the inner diameter of the inner tube 21 to the inner diameter of the outer tube 22 is 1:1.2.

[0063] Example 2

[0064] The mixed gas of carbon dioxide and hydrogen (temperature 200℃) is transported from the raw material inlet 6 to the upper head 3 and then into the inner tube 21 of the reaction tube 2 to carry out the carbon dioxide catalytic hydrogenation reaction to prepare methanol, and the methanol product and the unreacted raw material are transported to the lower head 4 and then discharged through the product outlet 7; during the reaction process, the cooling medium water enters the shell side of the reactor from the cooling medium inlet 8 at the upper part of the reactor cylinder 5 to exchange heat with the materials in the reaction tube 2, and the water after heat exchange is mixed with the condensed water from the inner tube 21 of the reaction tube 2 into the shell side and then discharged through the cooling medium outlet 9;

[0065] The inner tube 21 of the tube reactor is a rigid titanium wire mesh; the outer tube 22 is a PVA film; the inert filler is SiO2; the ratio of the inner diameter of the inner tube 21 to the inner diameter of the outer tube 22 is 1:1.2.

[0066] Example 3

[0067] The mixed gas of carbon dioxide and hydrogen (temperature 200℃) is transported from the raw material inlet 6 to the upper head 3 and then into the inner tube 21 of the reaction tube 2 to carry out the carbon dioxide catalytic hydrogenation reaction to prepare methanol, and the methanol product and the unreacted raw material are transported to the lower head 4 and then discharged through the product outlet 7; during the reaction process, the cooling medium water enters the shell side of the reactor from the cooling medium inlet 8 at the upper part of the reactor cylinder 5 to exchange heat with the materials in the reaction tube 2, and the water after heat exchange is mixed with the condensed water from the inner tube 21 of the reaction tube 2 into the shell side and then discharged through the cooling medium outlet 9;

[0068] The inner tube 21 of the shell-and-tube reactor is a rigid titanium wire mesh; the outer tube 22 is a PVA / PAN composite membrane; the inert filler is Al2O3; the ratio of the inner diameter of the inner tube 21 to the inner diameter of the outer tube 22 is 1:4.

[0069] Example 4

[0070] The method of Example 1 is followed, except that the ratio of the inner diameter of the inner tube 21 to the inner diameter of the outer tube 22 in the shell-and-tube reactor is 1:2.5.

[0071] Comparative Example 1

[0072] The method of Example 1 is followed, except that a conventional shell-and-tube reactor (provided by Yongda Petrochemical Equipment Co., Ltd.) is used for the reaction of carbon dioxide hydrogenation to prepare methanol.

[0073] Test Example

[0074] The conversion rate of the raw material and the catalyst activity retention time of the final raw material of Test Examples 1-4 and Comparative Example 1 are shown in Table 1, wherein the calculation formula of the conversion rate of the raw material is:

[0075]

[0076] Table 1

[0077] Example No. Conversion of raw material / % Catalyst activity retention time / h Example 1 39 1000 Example 2 36 920 Example 3 32 840 Example 4 30 600 Comparative Example 1 Comparative Example 2 15 200

[0078] As can be seen from the results in Table 1, the shell-and-tube reactor of the present application can well avoid the problems of catalyst deactivation caused by water produced during the reaction, and the shell-and-tube reactor of the present application can make the catalyst activity retention time longer and ensure the conversion rate of the raw material higher, thereby further improving the utilization rate of the raw material, and having great application prospects.

[0079] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A shell-and-tube reactor for the catalytic hydrogenation of carbon dioxide to produce methanol or ethanol, characterized in that, The column-tube reactor comprises a reactor box (1) and a plurality of reaction tubes (2) arranged in the reactor box (1), the reaction tube (2) comprises an inner tube (21) and an outer tube (22) sleeved outside the inner tube, the inner tube (21) is filled with a catalyst, the inner tube (21) and the outer tube (22) are filled with inert fillers, and the inner tube (21) is in communication with the outer tube (22). The inner tube (21) is a rigid wire mesh, the outer tube (22) is a pervaporation membrane, and the ratio of the inner diameter of the inner tube (21) to the inner diameter of the outer tube (22) is 1:1.1-2.

2. The shell-and-tube reactor according to claim 1, characterized in that The rigid wire mesh is selected from one of rigid iron wire mesh, rigid titanium wire mesh or rigid steel wire mesh.

3. The shell-and-tube reactor of claim 1, wherein, The pervaporation membrane is selected from one of PVA membrane, PI membrane and PVA / PAN composite membrane.

4. The shell-and-tube reactor of claim 1, wherein, The reactor box (1) comprises an upper head (3), a reactor cylinder (5) and a lower head (4) in sequence. The upper head (3) is provided with a raw material inlet (6) for inputting raw materials required for reaction into the column-tube reactor. The lower head (4) is provided with a product outlet (7) for outputting products obtained in the reaction tube (2) and unreacted raw materials. A cooling medium inlet (8) is arranged at the upper portion of the reactor cylinder (5) for inputting cooling medium for heat exchange with materials in the reaction tube (2). A cooling medium outlet (9) is arranged at the lower portion of the reactor cylinder (5) for outputting the cooling medium after heat exchange.

5. The shell-and-tube reactor of claim 1, wherein, The ratio of the inner diameter of the inner tube (21) to the inner diameter of the outer tube (22) is 1:1.2-1.

5.

6. The column-tube reactor according to any one of claims 1-5 is applied to preparation of methanol or ethanol by catalytic hydrogenation of carbon dioxide.

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