reactor

Abstract

The reactor (1) is provided with a separation membrane (10) through which water vapor is allowed to pass, a non-passing side flow path (30) provided on the non-passing side of the separation membrane (10), and a catalyst (60) filled in the non-passing side flow path (30). The catalyst (60) contains catalyst particles composed of a carrier and a supported catalyst component, and filler particles softer than the catalyst particles.

Description

Technical Field

[0001] This invention relates to reactors. Background Technology

[0002] In recent years, reactors have been developed that can improve conversion efficiency by separating the products from the conversion reaction of feed gas containing hydrogen and carbon oxide to liquid fuels such as methanol and ethanol (specifically, fuels that are in a liquid state at room temperature and pressure).

[0003] For example, Patent Document 1 discloses a reactor comprising a separation membrane through which water vapor, one of the products of the conversion reaction, permeates; a non-permeable flow path for the flow of feed gas; and a catalyst filled within the flow path. The catalyst enables the conversion reaction from feed gas to liquid fuel. Existing technical documents Patent documents

[0004] Patent Document 1: Japanese Patent Application Publication No. 2018-8940 Summary of the Invention The problem that the invention aims to solve

[0005] In the reactor described in Patent Document 1, if the high-temperature feed gas flows in the non-permeable side flow path at the start of operation, not only will the catalyst thermally expand and damage the separation membrane, but the catalyst itself will also pulverize due to the thermal stress generated in the catalyst.

[0006] The purpose of this invention is to provide a reactor that can simultaneously inhibit damage to the separation membrane and inhibit catalyst pulverization. Technical solutions for solving the problem

[0007] The reactor according to a first aspect of the present invention comprises: a separation membrane through which products of a conversion reaction from a feed gas containing at least hydrogen and carbon oxide to a liquid fuel are permeated; a non-permeable side flow path disposed on the non-permeable side of the separation membrane for flow of the feed gas; and a catalyst filled within the non-permeable side flow path to carry out the conversion reaction. The catalyst comprises catalyst particles consisting of a support and catalyst-supported components, and packing particles softer than the catalyst particles.

[0008] The reactor according to the second aspect of the present invention is, based on the first aspect described above, wherein the non-permeable side flow path extends in a generally vertical direction, the catalyst has a first layer and a second layer disposed above the first layer, the first layer containing more packing particles than the catalyst particles contained in the first layer, and the second layer containing more catalyst particles than the packing particles contained in the second layer.

[0009] The reactor according to the third aspect of the present invention is, based on the first or second aspect described above, wherein the non-permeable side flow path extends in a generally vertical direction, the catalyst has a first layer and a second layer disposed above the first layer, and the packing particles include a first packing particle disposed in the first layer and a second packing particle disposed in the second layer, wherein the first packing particle is softer than the second packing particle.

[0010] The fourth aspect of the present invention relates to a reactor in which, based on the third aspect described above, the porosity of the first layer is greater than that of the second layer.

[0011] The reactor according to the fifth aspect of the present invention is such that, based on any one of the second to fourth aspects described above, the first layer is located at the bottom layer of the catalyst.

[0012] The reactor according to the sixth aspect of the present invention is, based on the first aspect described above, wherein the catalyst has a first portion in contact with the separation membrane and a second portion separated from the separation membrane, wherein the first portion contains more packing particles than the catalyst particles contained in the first portion, and the second portion contains more catalyst particles than the packing particles contained in the second portion.

[0013] The reactor according to the seventh aspect of the present invention is, based on the first or sixth aspect described above, wherein the catalyst has a first portion in contact with the separation membrane and a second portion separated from the separation membrane, the packing particles comprising a third packing particle disposed in the first portion and a fourth packing particle disposed in the second portion, the third packing particle being softer than the fourth packing particle.

[0014] The reactor according to the eighth aspect of the present invention is such that, based on the sixth or seventh aspect described above, the porosity of the first part is greater than the porosity of the second part.

[0015] The reactor according to the ninth aspect of the present invention is, based on the first aspect described above, wherein the catalyst has a first portion in contact with the separation membrane and a second portion separated from the separation membrane, wherein the first portion contains more catalyst particles than the first portion contains packing particles, and the second portion contains more packing particles than the second portion contains catalyst particles.

[0016] The reactor according to the tenth aspect of the present invention is, based on the first or ninth aspect described above, wherein the catalyst has a first portion in contact with the separation membrane and a second portion separated from the separation membrane, and the packing particles include a fifth packing particle disposed in the first portion and a sixth packing particle disposed in the second portion, wherein the sixth packing particle is softer than the fifth packing particle.

[0017] The reactor according to the eleventh aspect of the present invention is such that, based on the ninth or tenth aspect described above, the porosity of the second part is greater than that of the third part.

[0018] The reactor according to the twelfth aspect of the present invention is, based on any one of the first to eleventh aspects described above, wherein the packing particles are composed of a carrier and a catalyst-supported component. Invention Effects

[0019] According to the present invention, a reactor capable of simultaneously suppressing damage to the separation membrane and suppressing catalyst pulverization can be provided. Attached Figure Description

[0020] Figure 1 This is a cross-sectional view of the reactor according to the first embodiment. Figure 2 This is a cross-sectional view of the reactor according to the second embodiment. Figure 3 This is a cross-sectional view of the reactor involved in Comparative Example 2. Figure 4 This is a cross-sectional view of the reactor involved in Comparative Example 2. Figure 5 This is a cross-sectional view of the reactor involved in Comparative Example 3. Detailed Implementation

[0021] Embodiments of the present invention will be described with reference to the accompanying drawings. However, the drawings are schematic and may differ from actual ratios, such as the proportions of various dimensions.

[0022] 1. First Implementation Method Figure 1 This is a cross-sectional view of reactor 1 according to the first embodiment.

[0023] Reactor 1 is a membrane reactor used to convert feed gas into liquid fuel. The structure of reactor 1 can be applied to fixed-bed reactors and monolithic reactors.

[0024] The feed gas contains at least hydrogen and carbon oxide. As the carbon oxide, at least one of carbon monoxide and carbon dioxide can be used. The feed gas can also be a so-called syngas.

[0025] Liquid fuels are fuels that are liquid at room temperature and pressure, or fuels that can be liquefied under pressure at room temperature. Examples of fuels that are liquid at room temperature and pressure include methanol and ethanol. n H 2(m－2n) (m is an integer less than 90, n is an integer less than 30) represents liquid fuels and mixtures thereof. Examples of fuels that can be liquefied under normal temperature and pressure include propane, butane, and mixtures thereof.

[0026] For example, the reaction formula (1) for synthesizing methanol by catalytic hydrogenation of a feed gas containing carbon dioxide and hydrogen in the presence of a catalyst is as follows.

[0027] The above reaction is an equilibrium reaction. To improve both conversion efficiency and reaction rate, it is preferable to carry out the reaction under high temperature and high pressure (e.g., above 180°C and above 2 MPa). The liquid fuel is in a gaseous state at the point of synthesis and is maintained in a gaseous state at least until it flows out of reactor 1. Reactor 1 preferably has heat resistance and pressure resistance suitable for the synthesis conditions of the desired liquid fuel.

[0028] like Figure 1 As shown, reactor 1 includes a separation membrane 10, a porous support 20, a non-permeable side flow path 30, a permeable side flow path 40, an outer tube 50, and a catalyst 60.

[0029] The separation membrane 10 allows water vapor, one of the products of the conversion reaction from feed gas to liquid fuel, to pass through. This allows the reaction equilibrium in equation (1) to shift towards the products side using the equilibrium displacement effect. In this embodiment, the separation membrane 10 is formed in a cylindrical shape.

[0030] The separation membrane 10 preferably has a concentration of 100 nmol / (s·Pa·m). 2 The water vapor transmission coefficient is above 100. The water vapor transmission coefficient can be determined by known methods (see Ind. Eng. Chem. Res., 40, 163-175 (2001)).

[0031] The separation membrane 10 is formed in a cylindrical shape. The separation membrane 10 is disposed inside the cylindrical porous support 20. The separation membrane 10 is in contact with the inner peripheral surface of the porous support 20.

[0032] The separation membrane 10 preferably has a separation coefficient of 100 or higher. The larger the separation coefficient, the easier it is for water vapor to pass through, and the more difficult it is for components other than water vapor (such as hydrogen, carbon dioxide, and liquid fuels) to pass through. The separation coefficient can be determined by known methods (see Fig. 1 of "Separation and Purification Technology 239 (2020) 116533").

[0033] Inorganic membranes can be used as the separation membrane 10. Inorganic membranes are preferred because they possess heat resistance, pressure resistance, and water vapor resistance. Examples of inorganic membranes include zeolite membranes, silica membranes, alumina membranes, and composite membranes thereof. In particular, LTA-type zeolite membranes with a silicon (Si) to aluminum (Al) molar ratio (Si / Al) of 1.0 or more and 3.0 or less are preferred due to their excellent water vapor permeability. However, inorganic membranes are prone to breakage due to thermal shock.

[0034] A porous support 20 supports the separation membrane 10. The porous support 20 is made of a porous material. In this embodiment, the porous support 20 is formed in a cylindrical shape.

[0035] As a porous material, ceramic materials, metallic materials, and resin materials can be used, with ceramic materials being particularly preferred. As aggregates for ceramic materials, materials such as alumina (Al2O3), titanium dioxide (TiO2), mullite (Al2O3·SiO2), ceramic fragments, and cordierite (Mg2Al4Si5O3) can be used. 18 At least one of the following can be used as the inorganic binder in ceramic materials: titanium dioxide, mullite, easily sinterable alumina, silica, glass frit, clay minerals, and easily sinterable cordierite. However, ceramic materials may also not contain an inorganic binder.

[0036] The porous support 20 is formed in a cylindrical shape. The porous support 20 surrounds the separation membrane 10. A non-permeable side flow path 30 is provided on the non-permeable side of the separation membrane 10. In this embodiment, the non-permeable side flow path 30 is a columnar space inside the separation membrane 10.

[0037] In this embodiment, the non-permeable side flow path 30 extends in a generally vertical direction. The term "generally vertical direction" means not only the direction aligned with the direction of gravity, but also the direction that is slightly inclined (±15 degrees) relative to the direction of gravity.

[0038] The feed gas flows in the non-permeable side flow path 30. In this embodiment, the feed gas flows downward within the non-permeable side flow path 30. Therefore, the feed gas flows in from the upper opening 30a of the non-permeable side flow path 30, and the liquid fuel flows out from the lower opening 30b of the non-permeable side flow path 30. However, the feed gas may also flow upward within the non-permeable side flow path 30. Residual feed gas may also be mixed into the liquid fuel flowing out from the lower opening 30b.

[0039] A permeable side flow path 40 is provided on the non-permeable side of the separation membrane 10. In this embodiment, the permeable side flow path 40 is an annular space between the separation membrane 10 and the outer tube 50. Water vapor that has permeated through the separation membrane 10 flows into the permeable side flow path 40.

[0040] In this embodiment, the purge gas used to purge water vapor flows in the permeable side flow path 40. Inert gases (such as nitrogen) or air can be used as the purge gas. In this embodiment, the purge gas flows upward (i.e., in the opposite direction to the feed gas) within the permeable side flow path 40. Therefore, the purge gas, having absorbed water vapor, flows in from the lower opening 40a of the permeable side flow path 40 and flows out from the upper opening 40b of the permeable side flow path 40. However, the purge gas may also flow downward (i.e., in the same direction as the feed gas) within the permeable side flow path 40.

[0041] Catalyst 60 is packed within the non-permeable side flow path 30. Catalyst 60 facilitates the conversion reaction from feed gas to liquid fuel. Catalyst 60 is in direct contact with the separation membrane 10.

[0042] Catalyst 60 consists of multiple catalyst particles and multiple packing particles.

[0043] The catalyst particles consist of a support and a supported catalyst component that performs the catalytic action. Examples of supports that can be used include, but are not limited to, alumina, titanium dioxide, silica, cerium dioxide, and zeolite. The supported catalyst component is supported on the surface of the support. Examples of supported catalyst components that can be used include, but are not limited to, metal catalyst components (copper, palladium, etc.), oxide catalyst components (zinc oxide, amorphous zirconium oxide, gallium oxide, etc.), and their composites.

[0044] The shape of the catalyst particles is not particularly limited and can be, for example, spherical, ellipsoidal, cylindrical, elliptical cylindrical, disc-shaped, scale-shaped, needle-shaped, polygonal prism-shaped, and plate-shaped.

[0045] The filler particles are made of materials that are softer than catalyst particles. Examples of materials that are softer than catalyst particles include alumina, titanium dioxide, silicon dioxide, cerium dioxide, and zeolite, but are not limited to these.

[0046] The filler particles can also consist of a support and a supported catalyst component that functions as a catalyst. This improves the catalytic activity of the catalyst 60 as a whole. As a support, materials such as alumina, titanium dioxide, silicon dioxide, cerium dioxide, and zeolite can be used, but are not limited to these. The supported catalyst component can be any of the aforementioned substances, but is not limited to these.

[0047] In this specification, "softer than catalyst particles" means that the hardness of the filler particles is less than that of the catalyst particles. The hardness of both the filler particles and the catalyst particles was measured using a Shimadzu Micro Autograph MST-I instrument and samples dried at 130°C for 2 hours. The test speed was set to 0.10 mm / s.

[0048] The catalyst 60 has a multilayer structure with multiple layers stacked in a generally vertical direction. In this embodiment, the catalyst 60 is composed of a two-layer structure having a first layer 61 and a second layer 62.

[0049] The first layer 61 is located at the bottom of the catalyst 60. The first layer 61 is disposed at the lower end of the non-permeable side flow path 30. The lower end of the non-permeable side flow path 30 refers to the region below the center of the non-permeable side flow path 30 in the generally vertical direction. The upper end of the first layer 61 may be located at a position below the center of the non-permeable side flow path 30 in the generally vertical direction.

[0050] The second layer 62 is disposed above the first layer 61. In this embodiment, the catalyst 60 has a two-layer structure, therefore the second layer 62 is disposed on top of the first layer 61. The second layer 62 is disposed in the region of the non-permeable side flow path 30 where the first layer 61 is not disposed.

[0051] Here, the first layer 61 contains more packing particles than catalyst particles. That is, the content of packing particles in the first layer 61 is greater than the content of catalyst particles. Therefore, the first layer 61 is flexible. Thus, at the start of operation of the reactor 1, even if the high-temperature feed gas flows in the non-permeable side flow path 30 and the first layer 61 thermally expands, the force exerted on the separation membrane 10 from the first layer 61 can be reduced. In addition, the weight of the second layer 62 exerted on the first layer 61 can be absorbed inside the first layer 61, thus reducing the force exerted on the separation membrane 10 from the first layer 61. As a result, damage to the separation membrane 10 can be suppressed.

[0052] Furthermore, the second layer 62 contains more catalyst particles than the second layer 62 contains filler particles. That is, in the second layer 62, the content of catalyst particles is greater than the content of filler particles. The catalyst particles are made of a material that is harder than the filler particles, thus suppressing the pulverization of catalyst particles due to thermal stress.

[0053] As described above, the catalyst 60 according to this embodiment can simultaneously achieve damage suppression of the separation membrane 10 and pulverization suppression of the catalyst 60.

[0054] The situation where the first layer 61 contains more filler particles than the first layer 61 contains catalyst particles can be confirmed as follows.

[0055] First, after the resin (e.g., epoxy resin) flows into the non-permeable side flow path 30 and is cured, the catalyst 60 is cut off in a generally vertical direction.

[0056] Next, a cross-sectional image of the first layer 61 is obtained using a SEM (scanning electron microscope). The SEM magnification is selected from a range of 1x to 100x, such that more than 10 (preferably more than 100) filler particles can be observed in one field of view. In this case, when the two cross-sections of the separation membrane (the cross-sections on both sides of the non-permeable side flow path 30 in the horizontal direction) do not converge within one field of view, it can be divided into two fields of view that can observe the cross-section of the separation membrane and one or more fields of view between the two fields of view. In the cross-sectional image, by classifying the image brightness into 256 gray levels, it is possible to create a difference in brightness between the catalyst particles, filler particles, and voids.

[0057] Next, the cross-sectional images were analyzed using HALCON image analysis software manufactured by MVTec (Germany), thereby determining the total area of ​​the catalyst particles, filler particles, and voids. Furthermore, if the total area of ​​the filler particles is larger than the total area of ​​the catalyst particles, it can be said that the first layer 61 contains more filler particles than the first layer 61 contains catalyst particles.

[0058] The content of packing particles is calculated by dividing the total area of ​​the packing particles by the total area of ​​the catalyst particles, packing particles, and voids. The content of catalyst particles is calculated by dividing the total area of ​​the catalyst particles by the total area of ​​the catalyst particles, packing particles, and voids.

[0059] However, the first layer 61 may substantially not contain catalyst particles. Therefore, the total area of ​​the catalyst particles in the first layer 61 can be "0", and in this case, the content of catalyst particles in the first layer 61 is also "0".

[0060] By performing image analysis on the second layer 62 using the method described above, it can be confirmed that the second layer 62 contains more catalyst particles than filler particles. The SEM magnification is selected such that at least 10 (preferably at least 100) catalyst particles can be observed in one field of view. The catalyst particle content is calculated by dividing the total area of ​​the catalyst particles by the total area of ​​the catalyst particles, filler particles, and voids. The filler particle content is calculated by dividing the total area of ​​the filler particles by the total area of ​​the catalyst particles, filler particles, and voids.

[0061] However, the second layer 62 may also substantially not contain any filler particles. Therefore, the total area of ​​the filler particles in the second layer 62 can be "0", and in this case, the content of filler particles in the second layer 62 is also "0".

[0062] The porosity of the first layer 61 is preferably greater than that of the second layer 62. This makes it easier for the interior of the first layer 61 to absorb the weight of the second layer 62 applied to it, thus further reducing the force exerted on the separation membrane 10 from the first layer 61. Consequently, damage to the separation membrane 10 can be further suppressed.

[0063] The porosity of the first layer 61 and the second layer 62 is obtained by dividing the total area of ​​the porosity obtained from the above image analysis by the total area.

[0064] The porosity value of the first layer 61 is not particularly limited, but can be set to, for example, 30% or more and 60% or less. The porosity value of the second layer 62 is not particularly limited, but can be set to, for example, 20% or more and 50% or less.

[0065] 2. Second Implementation Method Figure 2 This is a cross-sectional view of reactor 2 according to the second embodiment. Figure 2 In the middle, to and Figure 1 Same component labeling and Figure 1 Same number. For example... Figure 2 As shown, the catalyst 70 in the reactor 2 according to the second embodiment is different from the catalyst 60 in the reactor 1 according to the first embodiment. Therefore, the following mainly describes this difference. It should be noted that in this embodiment, the non-permeable side flow path 30 does not need to extend in a generally vertical direction.

[0066] Catalyst 70 is packed within the non-permeable side flow path 30. Catalyst 70 facilitates (promotes) the conversion reaction from feed gas to liquid fuel. Catalyst 70 is in direct contact with the separation membrane 10.

[0067] The catalyst 70 consists of multiple catalyst particles and multiple packing particles. The structures of the catalyst particles and the packing particles are as described in the first embodiment above. The packing particles are made of a material that is softer than the catalyst particles.

[0068] Catalyst 70 has a first part 71 and a second part 72.

[0069] The first portion 71 is in contact with the separation membrane 10. The first portion 71 corresponds to the outer periphery of the catalyst 70 in the radial direction of the non-permeable side flow path 30. In this embodiment, the first portion 71 is formed in a cylindrical shape.

[0070] The second portion 72 is separated from the separation membrane 10. The second portion 72 is surrounded by the first portion 71. The second portion 72 does not contact the separation membrane 10. The second portion 72 corresponds to the central portion of the catalyst 70 in the radial direction of the non-permeable side flow path 30. In this embodiment, the second portion 72 is formed in a cylindrical shape.

[0071] However, the first portion 71 may not cover the entire outer periphery of the second portion 72. The first portion 71 only needs to cover at least a portion of the outer periphery of the second portion 72. In this case, the second portion 72 is disposed in the area of ​​the non-permeable side flow path 30 where the first portion 71 is not disposed.

[0072] The radial thickness of the first part 71 is not particularly limited, but can be set to, for example, 500 μm or more and 5000 μm or less.

[0073] Here, the first section 71 contains more packing particles than catalyst particles. That is, the content of packing particles in the first section 71 is greater than the content of catalyst particles. Therefore, the first section 71 is flexible. Thus, at the start of operation of the reactor 1, even if the high-temperature feed gas flows in the non-permeable side flow path 30 and the catalyst 70 thermally expands as a whole, the force exerted on the separation membrane 10 from the first section 71 can be reduced. As a result, damage to the separation membrane 10 can be suppressed.

[0074] Furthermore, the second part 72 contains more catalyst particles than the second part 72 contains filler particles. The catalyst particles are made of a material that is harder than the filler particles, thus preventing the catalyst particles from pulverizing due to thermal stress.

[0075] As described above, the catalyst 70 according to this embodiment can simultaneously achieve damage suppression of the separation membrane 10 and pulverization suppression of the catalyst 70.

[0076] The image analysis described in the above embodiments can confirm whether the first part 71 contains more filler particles than the catalyst particles contained in the first part 71, and whether the second part 72 contains more catalyst particles than the filler particles contained in the second part 72.

[0077] The porosity of the first part 71 is preferably greater than that of the second part 72. This improves the flexibility of the first part 71, thereby further suppressing damage to the separation membrane 10 due to the thermal expansion of the catalyst 70.

[0078] The porosity of each of Part 71 and Part 72 is obtained by dividing the total area of ​​the voids obtained from the above image analysis by the total area.

[0079] The porosity value of Part 1 71 is not particularly limited, but can be set to, for example, 30% or more and 60% or less. The porosity value of Part 2 72 is not particularly limited, but can be set to, for example, 20% or more and 50% or less.

[0080] (Modifications of the implementation method) The embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the invention.

[0081] (Variation Example 1) In the first and second embodiments described above, the inner side of the separation membrane 10 is used as the non-permeable side flow path 30, and the outer side of the separation membrane 10 is used as the permeable side flow path 40. However, it is also possible to use the outer side of the separation membrane 10 as the non-permeable side flow path 30 and the inner side of the separation membrane 10 as the permeable side flow path 40. In this case, it is preferable to form the separation membrane 10 in a manner that surrounds the outer side of the porous support 20.

[0082] (Variation Example 2) In the first embodiment described above, the catalyst 60 has a two-layer structure having a first layer 61 and a second layer 62, but it can also have a structure with three or more layers. For example, as... Figure 3 and Figure 4 As shown, the catalyst 60 can be configured as a three-layer structure having a third layer 63 in addition to the first layer 61 and the second layer 62.

[0083] exist Figure 3 In this configuration, the third layer 63 is vertically disposed between the first layer 61 and the second layer 62. The content of packing particles in the third layer 63 is preferably higher than that in the second layer 62. This expands the range within which damage to the separation membrane 10 can be suppressed. The content of packing particles in the third layer 63 may be higher or lower than that in the first layer 61.

[0084] exist Figure 4 In this membrane, the third layer 63 is disposed below the first layer 61 in a generally vertical direction. The third layer 63 contains at least one of catalyst particles and packing particles. The third layer 63 may contain more packing particles than catalyst particles, or more catalyst particles than packing particles. In this way, even if the first layer 61 is not disposed at the bottom, damage to the portion of the separation membrane 10 in contact with the first layer 61 can be suppressed. However, if the third layer 63 contains a large number of catalyst particles, damage may occur to the portion of the separation membrane 10 in contact with the third layer 63, therefore it is preferable that the first layer 61 is disposed at the bottom.

[0085] (Variation Example 3) In the first embodiment described above, in order to suppress damage to the separation membrane 10, the first layer 61 contains more filler particles than the catalyst particles contained in the first layer 61. However, it is also possible to replace or, based on this, make the first layer 61 contain filler particles that are softer than the second layer 62.

[0086] Specifically, among the packing particles included in the catalyst 60, the packing particles disposed in the first layer 61 (the "first packing particles" according to the present invention) are softer than the packing particles disposed in the second layer 62 (the "second packing particles" according to the present invention). This reduces the force exerted on the separation membrane 10 from the thermally expanded first layer 61, and also allows the weight of the second layer 62 to be absorbed within the first layer 61, thus suppressing damage to the separation membrane 10. The first packing particles being softer than the second packing particles means that the hardness of the first packing particles is less than that of the second packing particles. The method for measuring hardness is as described in the first embodiment.

[0087] It should be noted that, similar to Modification 2, in this modification, a third layer 63 may also be disposed below the first layer 61. The third layer 63 comprises at least one of catalyst particles and packing particles. When the third layer 63 comprises packing particles, the packing particles of the third layer 63 may be softer or harder than the packing particles of the first layer 61, or they may have the same hardness as the packing particles of the first layer 61. However, if the packing particles of the third layer 63 are hard, damage may occur in the portion of the separation membrane 10 that comes into contact with the third layer 63; therefore, it is preferable that the first layer 61 is disposed at the bottom.

[0088] (Variation Example 4) In the second embodiment described above, the catalyst 70 has a first portion 71 and a second portion 72, but other portions may also exist between the first portion 71 and the second portion 72. For example, as... Figure 5As shown, catalyst 70 may also have a third part 73 in addition to the first part 71 and the second part 72.

[0089] The third part 73 is radially disposed between the first part 71 and the second part 72. The content of packing particles in the third part 73 is preferably higher than that in the second part 72. This expands the range within which damage to the separation membrane 10 can be suppressed. The content of packing particles in the third part 73 may be higher or lower than that in the first part 71.

[0090] (Variation Example 5) In the second embodiment described above, in order to suppress damage to the separation membrane 10, the first part 71 contains more filler particles than the catalyst particles contained in the first part 71. Alternatively, or on this basis, the first part 71 may contain filler particles that are softer than the second part 72.

[0091] Specifically, among the packing particles included in the catalyst 70, the packing particles disposed in the first portion 71 (the "third packing particles" according to the present invention) are softer than the packing particles disposed in the second portion 72 (the "fourth packing particles" according to the present invention). This reduces the force exerted on the separation membrane 10 from the first portion 71 during the thermal expansion of the catalyst 70, thus suppressing damage to the separation membrane 10. The third packing particle being softer than the fourth packing particle means that the hardness of the third packing particle is less than that of the fourth packing particle. The method for measuring hardness is as described in the first embodiment.

[0092] (Variation Example 6) In the second embodiment described above, in order to suppress damage to the separation membrane 10, the first portion 71 contains more packing particles than the catalyst particles contained in the first portion 71, and the second portion 72 contains more catalyst particles than the packing particles contained in the second portion 72, but this is not a limitation. The first portion 71 may also contain more catalyst particles than packing particles, and the second portion 72 may also contain more packing particles than catalyst particles. Even in this case, the flexible second portion 72 can absorb the thermal expansion force of the catalyst 70 as a whole, thus reducing the force applied to the separation membrane 10 from the first portion 71. As a result, damage to the separation membrane 10 can be suppressed.

[0093] Furthermore, if the first portion 71 contains more catalyst particles than the first portion 71 contains more packing particles, and the second portion 72 contains more packing particles than the second portion 72 contains more catalyst particles, the second portion 72 may also contain packing particles that are softer than the first portion 71. Specifically, among the packing particles contained in the catalyst 70, the packing particles disposed in the second portion 72 (the "sixth packing particle" according to the present invention) are softer than the packing particles disposed in the first portion 71 (the "fifth packing particle" according to the present invention). Therefore, the second portion 72 can further absorb the overall thermal expansion force of the catalyst 70, thus further suppressing damage to the separation membrane 10. The sixth packing particle being softer than the fifth packing particle means that the hardness of the sixth packing particle is less than the hardness of the fifth packing particle. The method for measuring hardness is as described in the first embodiment.

[0094] Furthermore, when the first portion 71 contains more catalyst particles than the packing particles contained in the first portion 71, and the second portion 72 contains more packing particles than the catalyst particles contained in the second portion 72, the porosity of the second portion can be greater than that of the first portion. Therefore, the second portion 72 can further absorb the overall thermal expansion force of the catalyst 70, thus further suppressing damage to the separation membrane 10.

[0095] (Variation Example 7) In the above embodiment, the separation membrane 10 allows water vapor, which is one of the products in the conversion reaction from feed gas to liquid fuel, to pass through, but it is not limited to this. The separation membrane 10 may also allow liquid fuel itself, which is a product in the conversion reaction from feed gas to liquid fuel, to pass through. In this case, the reaction equilibrium of the above formula (1) can also be shifted to the product side.

[0096] Furthermore, even when liquid fuel permeates through the separation membrane 10, it can still pass through reactions that do not generate water vapor (e.g., When liquid fuels are generated, the reaction equilibrium can also shift towards the products side. Symbol Explanation

[0097] 1: Reactor 10: Separation membrane 20: Porous support 30: Non-permeable side flow path 30a: Open at the top 30b: Open at the bottom 40: Through the side flow path 40a: Open at the bottom 40b: Open at the top 50: External Management 60: Catalyst 61: First floor 62: Second layer 63: Third layer 70: Catalyst 71: Part One 72: Part Two 73: Part Three.

Claims

1. A reactor comprising: A separation membrane that allows the products of a conversion reaction from a feed gas containing at least hydrogen and carbon oxide to a liquid fuel to pass through; A non-permeable side flow path, disposed on the non-permeable side of the separation membrane, is provided for the flow of the feed gas; and A catalyst, which is filled within the non-permeable side flow path, enables the conversion reaction to proceed. The carbon oxide is at least one of carbon monoxide and carbon dioxide. The catalyst comprises catalyst particles consisting of a support and supported catalyst components, and filler particles that are softer than the catalyst particles. The non-permeable side flow path extends in a generally vertical direction, which is not only consistent with the direction of gravity, but also slightly inclined relative to the direction of gravity, i.e., inclined at ±15 degrees. The catalyst has a first layer and a second layer disposed above the first layer. The first layer contains more filler particles than the first layer contains catalyst particles. The second layer contains more catalyst particles than the second layer contains filler particles. The statement that the first layer contains more filler particles than the first layer contains catalyst particles means that, in a cross-sectional image of the first layer, the total area of ​​the filler particles is larger than the total area of ​​the catalyst particles. The second layer contains more catalyst particles than the second layer contains filler particles, meaning that the total area of ​​the catalyst particles in the cross-sectional image of the second layer is larger than the total area of ​​the filler particles.

2. The reactor according to claim 1, wherein, The filler particles include first filler particles disposed in the first layer and second filler particles disposed in the second layer. The first filler particle is softer than the second filler particle.

3. The reactor according to claim 2, wherein, The porosity of the first layer is greater than that of the second layer.

4. The reactor according to claim 1, wherein, The first layer is located at the bottom of the catalyst.

5. The reactor according to claim 1, wherein, The catalyst has a first portion that contacts the separation membrane and a second portion that is separated from the separation membrane. The first part contains more filler particles than the first part contains catalyst particles. The second part contains more catalyst particles than the second part contains filler particles. The statement that the first part contains more filler particles than the first part contains catalyst particles means that the total area of ​​the filler particles in the cross-sectional image of the first part is larger than the total area of ​​the catalyst particles. The second part contains more catalyst particles than the second part contains filler particles, meaning that the total area of ​​the catalyst particles in the cross-sectional image of the second part is larger than the total area of ​​the filler particles.

6. The reactor according to claim 1 or 5, wherein, The catalyst has a first portion that contacts the separation membrane and a second portion that is separated from the separation membrane. The filler particles include a third filler particle disposed in the first portion and a fourth filler particle disposed in the second portion. The third filler particle is softer than the fourth filler particle.

7. The reactor according to claim 5, wherein, The porosity of the first part is greater than that of the second part.

8. The reactor according to claim 1, wherein, The catalyst has a first portion that contacts the separation membrane and a second portion that is separated from the separation membrane. The first part contains more catalyst particles than the first part contains filler particles. The second part contains more filler particles than the second part contains catalyst particles. The statement that the first part contains more catalyst particles than the first part contains filler particles means that the total area of ​​the catalyst particles in the cross-sectional image of the first part is larger than the total area of ​​the filler particles. The second part contains more filler particles than the second part contains catalyst particles, meaning that the total area of ​​the filler particles in the cross-sectional image of the second part is larger than the total area of ​​the catalyst particles.

9. The reactor according to claim 1 or 8, wherein, The catalyst has a first portion that contacts the separation membrane and a second portion that is separated from the separation membrane. The filler particles include a fifth filler particle disposed in the first part and a sixth filler particle disposed in the second part. The sixth filler particle is softer than the fifth filler particle.

10. The reactor according to claim 8, wherein, The porosity of the second part is greater than that of the first part.

11. The reactor according to claim 1, wherein, The filler particles consist of a support and a supported catalyst component.

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