Reactor

Abstract

This reactor (1) comprises a separation membrane (10) that allows water vapor to permeate, a non-permeated-side flow path (30) that is provided on a non-permeated side of the separation membrane (10), and a catalyst (60) that fills the inside of the non-permeated side flow path (30). The catalyst (60) includes catalyst particles which are formed from a support and a supported catalyst component, and filler particles which are softer than the catalyst particles.

Description

[Technical field]

[0001] The present invention relates to a reactor. [Background technology]

[0002] In recent years, reactors have been developed that can improve the efficiency of conversion by separating the products in the conversion reaction from a feed gas containing hydrogen and carbon oxides 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 that includes a separation membrane that allows the permeation of water vapor, which is one of the products of the conversion reaction, a non-permeation side flow path through which the raw material gas flows, and a catalyst packed in the flow path. The catalyst promotes the conversion reaction from the raw material gas to liquid fuel. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2018-8940 A Summary of the Invention [Problem to be solved by the invention]

[0005] In the reactor described in Patent Document 1, when high-temperature feed gas flows through the non-permeation side flow path at the start of operation, not only does the catalyst thermally expand, damaging the separation membrane, but the catalyst itself is also powdered due to the thermal stress generated in the catalyst.

[0006] An object of the present invention is to provide a reactor capable of suppressing both damage to a separation membrane and powdering of a catalyst. [Means for solving the problem]

[0007] The reactor according to a first aspect of the present invention comprises a separation membrane that allows permeation of a product of a conversion reaction from a feed gas containing at least hydrogen and carbon oxides to a liquid fuel, a non-permeation side flow path provided on the non-permeation side of the separation membrane and through which the feed gas flows, and a catalyst filled in the non-permeation side flow path and causing the conversion reaction to proceed. The catalyst includes catalyst particles constituted by a carrier and a supported catalyst component, and filler particles that are softer than the catalyst particles.

[0008] A reactor according to a second aspect of the present invention is related to the first aspect, wherein the non-permeation side flow path extends in a substantially vertical direction, the catalyst has a first layer and a second layer disposed above the first layer, the first layer contains more of the filler particles than the catalyst particles, and the second layer contains more of the catalyst particles than the filler particles.

[0009] A reactor according to a third aspect of the present invention is related to the first or second aspect, wherein the non-permeation side flow path extends in a substantially vertical direction, the catalyst has a first layer and a second layer disposed above the first layer, the filler particles include first filler particles disposed in the first layer and second filler particles disposed in the second layer, and the first filler particles are softer than the second filler particles.

[0010] A reactor according to a fourth aspect of the present invention is related to the third aspect, wherein the porosity of the first layer is greater than the porosity of the second layer.

[0011] A reactor according to a fifth aspect of the present invention is related to any one of the second to fourth aspects, wherein the first layer is located at the bottommost layer of the catalyst.

[0012] A reactor according to a sixth aspect of the present invention is related to the first aspect above, wherein the catalyst has a first portion in contact with the separation membrane and a second portion away from the separation membrane, the first portion containing more of the filler particles than the catalyst particles, and the second portion containing more of the catalyst particles than the filler particles.

[0013] A reactor according to a seventh aspect of the present invention is related to the first or sixth aspect above, wherein the catalyst has a first portion in contact with the separation membrane and a second portion away from the separation membrane, and the filler particles include third filler particles arranged in the first portion and fourth filler particles arranged in the second portion, and the third filler particles are softer than the fourth filler particles.

[0014] A reactor according to an eighth aspect of the present invention is related to the sixth or seventh aspect, wherein the porosity of the first portion is greater than the porosity of the second portion.

[0015] A reactor according to a ninth aspect of the present invention is related to the first aspect above, wherein the catalyst has a first portion in contact with the separation membrane and a second portion away from the separation membrane, the first portion containing more catalyst particles than the filler particles, and the second portion containing more filler particles than the catalyst particles.

[0016] A reactor according to a tenth aspect of the present invention is related to the first or ninth aspect above, wherein the catalyst has a first portion in contact with the separation membrane and a second portion away from the separation membrane, and the filler particles include fifth filler particles arranged in the first portion and sixth filler particles arranged in the second portion, and the sixth filler particles are softer than the fifth filler particles.

[0017] A reactor according to an eleventh aspect of the present invention is related to the ninth or tenth aspect, wherein the porosity of the second portion is greater than the porosity of the third portion.

[0018] A reactor according to a twelfth aspect of the present invention is related to any one of the first to eleventh aspects, wherein the filler particles are constituted by a support and a supported catalyst component. Effect of the Invention

[0019] According to the present invention, it is possible to provide a reactor capable of suppressing both damage to a separation membrane and powdering of a catalyst. [Brief description of the drawings]

[0020] [Figure 1] 1 is a cross-sectional view of a reactor according to a first embodiment; [Diagram 2] 1 is a cross-sectional view of a reactor according to a second embodiment. [Diagram 3] Cross-sectional view of a reactor according to Comparative Example 2 [Figure 4] Cross-sectional view of a reactor according to Comparative Example 2 [Diagram 5] Cross-sectional view of a reactor according to Comparative Example 3 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The embodiments of the present invention will be described with reference to the drawings. However, the drawings are schematic and the ratios of dimensions may differ from the actual ones.

[0022] 1. First embodiment FIG. 1 is a cross-sectional view of a reactor 1 according to a first embodiment.

[0023] The reactor 1 is a so-called membrane reactor for converting a raw gas into a liquid fuel. The configuration of the reactor 1 can be applied to a fixed bed reactor or a monolith reactor.

[0024] The raw material 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 raw material gas may be so-called synthesis gas (Syngas).

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

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

[0027] CO2+3H2⇔CH3OH+H2O (1) The above reaction is an equilibrium reaction, and is preferably carried out under high temperature and pressure (e.g., 180°C or higher, 2 MPa or higher) in order to increase both the conversion efficiency and the reaction rate. The liquid fuel is in a gaseous state when synthesized, and is maintained in this state at least until it flows out of the reactor 1. The reactor 1 preferably has heat resistance and pressure resistance suitable for the synthesis conditions of the desired liquid fuel.

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

[0029] The separation membrane 10 allows the permeation of water vapor, which is one of the products of the conversion reaction from the raw material gas to liquid fuel. This makes it possible to shift the reaction equilibrium of the above formula (1) to the product side by utilizing the equilibrium shift effect. In this embodiment, the separation membrane 10 is formed in a cylindrical shape.

[0030] The separation membrane 10 has a molecular weight of 100 nmol / (s·Pa·m 2 The water vapor permeability coefficient can be determined by a known method (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 a cylindrical porous support 20. The separation membrane 10 contacts the inner peripheral surface of the porous support 20.

[0032] The separation membrane 10 preferably has a separation factor of 100 or more. The larger the separation factor, the easier it is for water vapor to permeate and the harder it is for components other than water vapor (such as hydrogen, carbon oxides, and liquid fuels) to permeate. The separation factor can be determined by a known method (see FIG. 1 in "Separation and Purification Technology 239 (2020) 116533").

[0033] An inorganic membrane can be used as the separation membrane 10. Inorganic membranes are preferable because they have heat resistance, pressure resistance, and water vapor resistance. Examples of inorganic membranes include zeolite membranes, silica membranes, alumina membranes, and composite membranes of these. In particular, an LTA-type zeolite membrane, in which the molar ratio (Si / Al) of silicon element (Si) to aluminum element (Al) is 1.0 or more and 3.0 or less, is preferable because it has excellent water vapor permeability. However, inorganic membranes have the characteristic of being easily damaged by thermal shock.

[0034] The 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 the porous material, a ceramic material, a metal material, a resin material, etc. can be used, and a ceramic material is particularly suitable. Examples of aggregates for ceramic materials include alumina (Al2O3), titania (TiO2), mullite (Al2O3·SiO2), cerium oxide, and cordierite (Mg2Al4Si5O 18 ) can be used. As the inorganic binder for the ceramic material, for example, at least one of titania, mullite, sinterable alumina, silica, glass frit, clay mineral, and sinterable cordierite can be used. However, the ceramic material does not have to contain an inorganic binder.

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

[0037] In this embodiment, the non-permeation side channel 30 extends in a substantially vertical direction. The term "substantially vertical direction" refers not only to a direction that coincides with the direction of gravity, but also to a direction that is slightly inclined (±15 degrees) relative to the direction of gravity.

[0038] A raw material gas is flowed through the non-permeate side flow passage 30. In this embodiment, the raw material gas is flowed downward within the non-permeate side flow passage 30. Therefore, the raw material gas flows in from the upper end opening 30a of the non-permeate side flow passage 30, and the liquid fuel flows out from the lower end opening 30b of the non-permeate side flow passage 30. However, the raw material gas may be flowed upward within the non-permeate side flow passage 30. The liquid fuel flowing out from the lower end opening 30b may contain residual raw material gas.

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

[0040] In this embodiment, a sweep gas for sweeping water vapor is flowed through the permeation side flow passage 40. As the sweep gas, an inert gas (e.g., nitrogen) or air can be used. In this embodiment, the sweep gas flows upward (i.e., in the opposite direction to the raw material gas) through the permeation side flow passage 40. Therefore, the sweep gas flows in from the lower end opening 40a of the permeation side flow passage 40, and the sweep gas that has taken in water vapor flows out from the upper end opening 40b of the permeation side flow passage 40. However, the sweep gas may also flow downward (i.e., in the same direction as the raw material gas) through the permeation side flow passage 40.

[0041] The catalyst 60 is filled in the non-permeation side flow passage 30. The catalyst 60 advances (promotes) the conversion reaction from the raw material gas to liquid fuel. The catalyst 60 is in direct contact with the separation membrane 10.

[0042] The catalyst 60 is composed of a plurality of catalyst particles and a plurality of filler particles.

[0043] The catalyst particles are composed of a carrier and a supported catalyst component that exerts a catalytic action. Examples of the carrier that can be used include, but are not limited to, alumina, titania, silica, ceria, and zeolite. The supported catalyst component is supported on the surface of the carrier. Examples of the supported catalyst component that can be used include, but are not limited to, metal catalyst components (copper, palladium, etc.), oxide catalyst components (zinc oxide, amorphous zirconia, gallium oxide, etc.), and composites thereof.

[0044] The shape of the catalyst particles is not particularly limited, and may be, for example, a sphere, an ellipsoid, a cylinder, an elliptical cylinder, a disk, a scale, a needle, a polygonal cylinder, or a sheet.

[0045] The filler particles are made of a material softer than the catalyst particles, such as, but not limited to, alumina, titania, silica, ceria, and zeolite.

[0046] The filler particles may be composed of a carrier and a supported catalyst component that exerts catalytic action. This can improve the catalytic action of the catalyst 60 as a whole. The carrier can be, for example, alumina, titania, silica, ceria, zeolite, etc., but is not limited to these. The supported catalyst component can be, for example, the above-mentioned, but is not limited to these.

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

[0048] The catalyst 60 has a multi-layer structure in which a plurality of layers are stacked in a substantially vertical direction. In this embodiment, the catalyst 60 has a two-layer structure having a first layer 61 and a second layer 62.

[0049] The first layer 61 is located at the bottommost layer of the catalyst 60. The first layer 61 is disposed at the lower end of the non-permeation side flow path 30. The lower end of the non-permeation side flow path 30 is a region below the center of the non-permeation side flow path 30 in the approximately vertical direction. The upper end of the first layer 61 may be located below the center of the non-permeation side flow path 30 in the approximately vertical direction.

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

[0051] Here, the first layer 61 contains more filler particles than catalyst particles. That is, in the first layer 61, the content of filler particles is greater than the content of catalyst particles. Therefore, the first layer 61 is flexible. Therefore, even if the high-temperature raw material gas flows through the non-permeation side flow path 30 and the first layer 61 thermally expands when the reactor 1 starts to operate, the force applied from the first layer 61 to the separation membrane 10 can be reduced. In addition, the weight of the second layer 62 applied to the first layer 61 can be absorbed inside the first layer 61, so the force applied from the first layer 61 to the separation membrane 10 can be reduced. As a result, damage to the separation membrane 10 can be suppressed.

[0052] The second layer 62 contains more catalyst particles than filler particles. That is, the content of catalyst particles is greater than the content of filler particles in the second layer 62. The catalyst particles are made of a harder material than the filler particles, so that the catalyst particles can be prevented from being powdered due to thermal stress.

[0053] As described above, the catalyst 60 according to this embodiment can suppress both damage to the separation membrane 10 and powdering of the catalyst 60.

[0054] The fact that the first layer 61 contains a larger amount of filler particles than catalyst particles can be confirmed as follows.

[0055] First, a resin (for example, epoxy) is poured into the non-permeation side channel 30 and cured, and then the catalyst 60 is cut substantially vertically.

[0056] Next, a cross-sectional image of the first layer 61 is obtained using a SEM (scanning electron microscope). The magnification of the SEM is selected from the range of 1x to 100x so that 10 or more (preferably 100 or more) filler particles can be observed in one field of view. In this case, when both cross sections of the separation membrane (cross sections on both horizontal sides of the non-permeation side flow path 30) cannot be accommodated in one field of view, the field of view may be divided into two fields in which the cross sections of the separation membrane can be observed and one or more fields of view between the two fields of view. In the cross-sectional image, the brightness of the image can be classified into 256 gradations to produce a contrast between light and dark in the catalyst particles, filler particles, and voids.

[0057] Next, the total areas of the catalyst particles, filler particles, and voids are determined by analyzing each cross-sectional image using image analysis software HALCON manufactured by MVTec (Germany). If the total area of ​​the filler particles is greater than the total area of ​​the catalyst particles, it can be said that the first layer 61 contains more filler particles than catalyst particles.

[0058] The filler particle content is determined by dividing the total area of ​​the filler particles by the total area of ​​the catalyst particles, the filler particles, and the voids. The catalyst particle content is determined by dividing the total area of ​​the catalyst particles by the total area of ​​the catalyst particles, the filler particles, and the voids.

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

[0060] The fact that the second layer 62 contains more catalyst particles than filler particles can be confirmed by image analysis of the second layer 62 using the above-mentioned method. The magnification of the SEM is selected so that 10 or more (preferably 100 or more) catalyst particles can be observed in one field of view. The catalyst particle content is determined 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 determined 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 not substantially contain filler particles. Therefore, the total area of ​​the filler particles in the second layer 62 may be "0", and in this case, the content of the filler particles in the second layer 62 is also "0".

[0062] The porosity of the first layer 61 is preferably greater than the porosity of the second layer 61. This makes it easier for the weight of the second layer 62 applied to the first layer 61 to be absorbed inside the first layer 61, thereby further reducing the force applied to the separation membrane 10 from the first layer 61. As a result, damage to the separation membrane 10 can be further suppressed.

[0063] The porosity of each of the first layer 61 and the second layer 61 is calculated by dividing the total area of ​​the voids calculated by the image analysis described above by the total area.

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

[0065] 2. Second embodiment Fig. 2 is a cross-sectional view of the reactor 2 according to the second embodiment. In Fig. 2, the same members as those in Fig. 1 are denoted by the same numbers as those in Fig. 1. As shown in Fig. 2, the catalyst 70 included in the reactor 2 according to the second embodiment is different from the catalyst 60 of the reactor 1 according to the first embodiment. Therefore, the following mainly describes this difference. Note that in this embodiment, the non-permeation side flow path 30 does not need to extend in a substantially vertical direction.

[0066] The catalyst 70 is filled in the non-permeation side flow passage 30. The catalyst 70 advances (promotes) the conversion reaction from the raw material gas to liquid fuel. The catalyst 70 is in direct contact with the separation membrane 10.

[0067] The catalyst 70 is composed of a plurality of catalyst particles and a plurality of filler particles. The configurations of the catalyst particles and the filler particles are as described in the first embodiment. The filler particles are composed of a material that is softer than the catalyst particles.

[0068] The catalyst 70 has a first portion 71 and a second portion 72 .

[0069] The first portion 71 contacts the separation membrane 10. The first portion 71 corresponds to the outer periphery of the catalyst 70 in the radial direction of the non-permeation 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 a central portion of the catalyst 70 in the radial direction of the non-permeation side channel 30. In this embodiment, the second portion 72 is formed in a cylindrical shape.

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

[0072] The thickness of the first portion 71 in the radial direction is not particularly limited, but may be, for example, not less than 500 μm and not more than 5000 μm.

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

[0074] Further, the second portion 72 contains more catalyst particles than filler particles. The catalyst particles are made of a harder material than the filler particles, so that the catalyst particles can be prevented from being powdered due to thermal stress.

[0075] As described above, the catalyst 70 according to this embodiment can suppress both damage to the separation membrane 10 and powdering of the catalyst 70.

[0076] It can be confirmed by the image analysis described in the above embodiment that the first portion 71 contains more filler particles than catalyst particles, and that the second portion 72 contains more catalyst particles than filler particles.

[0077] The porosity of the first portion 71 is preferably greater than the porosity of the second layer 71. This can improve the flexibility of the first portion 71, thereby further preventing the separation membrane 10 from being damaged by thermal expansion of the catalyst 70.

[0078] The porosity of each of the first portion 71 and the second layer 71 is determined by dividing the total area of ​​the voids determined by the image analysis described above by the total area.

[0079] The porosity value of the first portion 71 is not particularly limited, but may be, for example, 30% or more and 60% or less. The porosity value of the second portion 72 is not particularly limited, but may be, for example, 20% or more and 50% or less.

[0080] (Modification of the embodiment) Although the embodiment of the present invention has been described above, the present invention is not limited to the above embodiment, and various modifications are possible without departing from the gist of the invention.

[0081] (Variation 1) In the above first and second embodiments, the inside of the separation membrane 10 is the non-permeate side flow path 30 and the outside of the separation membrane 10 is the permeate side flow path 40, but the outside of the separation membrane 10 may be the non-permeate side flow path 30 and the inside of the separation membrane 10 may be the permeate side flow path 40. In this case, it is preferable to form the separation membrane 10 so as to surround the outside of the porous support 20.

[0082] (Variation 2) In the first embodiment, the catalyst 60 has a two-layer structure having a first layer 61 and a second layer 62, but may have a structure having three or more layers. For example, as shown in Figures 3 and 4, the catalyst 60 may have a three-layer structure having a third layer 63 in addition to the first layer 61 and the second layer 62.

[0083] 3, the third layer 63 is disposed between the first layer 61 and the second layer 62 in the vertical direction. The filler particle content in the third layer 63 is preferably higher than the filler particle content in the second layer 62. This makes it possible to widen the range in which damage to the separation membrane 10 can be suppressed. The filler particle content in the third layer 63 may be higher or lower than the filler particle content in the first layer 61.

[0084] In FIG. 4, the third layer 63 is disposed below the first layer 61 in the substantially vertical direction. The third layer 63 includes at least one of catalyst particles and filler particles. The third layer 63 may include more filler particles than catalyst particles, or may include more catalyst particles than filler particles. In this way, even if the first layer 61 is not disposed at the bottom layer, damage to the portion of the separation membrane 10 that contacts the first layer 61 can be suppressed. However, if the third layer 63 includes a large amount of catalyst particles, there is a risk of damage to the portion of the separation membrane 10 that contacts the third layer 63, so it is preferable that the first layer 61 is disposed at the bottom layer.

[0085] (Variation 3) In the above first embodiment, in order to prevent damage to the separation membrane 10, the first layer 61 contains more filler particles than catalyst particles, but instead of or in addition to this, the first layer 61 may contain filler particles that are softer than the second layer 62.

[0086] Specifically, among the filler particles contained in the catalyst 60, the filler particles arranged in the first layer 61 ("first filler particles" according to the present invention) are softer than the filler particles arranged in the second layer 62 ("second filler particles" according to the present invention). This reduces the force applied to the separation membrane 10 from the thermally expanded first layer 61, and also allows the weight of the second layer 62 to be absorbed inside the first layer 61, thereby preventing the separation membrane 10 from being damaged. The first filler particles being softer than the second filler particles means that the hardness of the first filler particles is smaller than the hardness of the second filler particles. The method for measuring the hardness is as described in the first embodiment.

[0087] As in the second modification, in this modification, a third layer 63 may be disposed below the first layer 61. The third layer 63 includes at least one of catalyst particles and filler particles. When the third layer 63 includes filler particles, the filler particles of the third layer 63 may be softer or harder than the filler particles of the first layer 61, or may have the same hardness. However, if the filler particles of the third layer 63 are hard, there is a risk of damage occurring to the portion of the separation membrane 10 that comes into contact with the third layer 63, so it is preferable that the first layer 61 is disposed as the lowest layer.

[0088] (Variation 4) In the second embodiment described above, the catalyst 70 has the first portion 71 and the second portion 72, but there may be another portion between the first portion 71 and the second portion 72. For example, as shown in Fig. 5, the catalyst 70 may further have a third portion 73 in addition to the first portion 71 and the second portion 72.

[0089] The third portion 73 is disposed between the first portion 71 and the second portion 72 in the radial direction. The content of filler particles in the third layer 73 is preferably higher than the content of filler particles in the second portion 72. This makes it possible to widen the range in which damage to the separation membrane 10 can be suppressed. The content of filler particles in the third portion 73 may be higher or lower than the content of filler particles in the first portion 71.

[0090] (Variation 5) In the above second embodiment, in order to prevent damage to the separation membrane 10, the first portion 71 contains more filler particles than catalyst particles. However, instead of or in addition to this, the first portion 71 may contain filler particles that are softer than the second portion 72.

[0091] Specifically, among the filler particles contained in the catalyst 70, the filler particles arranged in the first portion 71 (the "third filler particles" according to the present invention) are softer than the filler particles arranged in the second portion 72 (the "fourth filler particles" according to the present invention). This reduces the force applied to the separation membrane 10 from the first portion 71 when the catalyst 70 thermally expands, thereby preventing the separation membrane 10 from being damaged. The third filler particles being softer than the fourth filler particles means that the hardness of the third filler particles is smaller than the hardness of the fourth filler particles. The method for measuring the hardness is as described in the first embodiment.

[0092] (Variation 6) In the second embodiment, in order to prevent the separation membrane 10 from being damaged, the first portion 71 contains more filler particles than catalyst particles, and the second portion 72 contains more catalyst particles than filler particles, but this is not limited to the above. The first portion 71 may contain more catalyst particles than filler particles, and the second portion 72 may contain more filler particles than catalyst particles. Even in this case, the flexible second portion 72 can absorb the thermal expansion force of the entire catalyst 70, so that the force applied from the first portion 71 to the separation membrane 10 can be reduced. As a result, the separation membrane 10 can be prevented from being damaged.

[0093] In addition, when the first portion 71 contains more catalyst particles than the filler particles and the second portion 72 contains more filler particles than the catalyst particles, the second portion 72 may contain filler particles that are softer than the first portion 71. Specifically, among the filler particles contained in the catalyst 70, the filler particles arranged in the second portion 72 (the "sixth filler particles" according to the present invention) are softer than the filler particles arranged in the first portion 71 (the "fifth filler particles" according to the present invention). This allows the second portion 72 to absorb more of the thermal expansion force of the entire catalyst 70, so that damage to the separation membrane 10 can be more effectively prevented. The sixth filler particles being softer than the fifth filler particles means that the hardness of the sixth filler particles is smaller than the hardness of the fifth filler particles. The method for measuring the hardness is as described in the first embodiment.

[0094] Furthermore, when the first portion 71 contains more catalyst particles than filler particles and the second portion 72 contains more filler particles than catalyst particles, the porosity of the second portion may be greater than the porosity of the first portion, which allows the second portion 72 to absorb more of the thermal expansion force of the entire catalyst 70, thereby further preventing the separation membrane 10 from being damaged.

[0095] (Variation 7) In the above embodiment, the separation membrane 10 is permeable to water vapor, which is one of the products in the conversion reaction from the raw material gas to liquid fuel, but this is not limited to this. The separation membrane 10 may also be permeable to liquid fuel itself, which is the product in the conversion reaction from the raw material gas to liquid fuel. In this case as well, the reaction equilibrium of the above formula (1) can be shifted to the product side.

[0096] In addition, when the separation membrane 10 allows liquid fuel to permeate, even when the liquid fuel is produced by a reaction that does not produce water vapor (for example, 2H2+CO⇔CH3OH), the reaction equilibrium can be shifted to the product side. [Explanation of symbols]

[0097] 1. Reactor 10 Separation membrane 20 Porous support 30 Non-permeation side flow path 30a top opening 30b Bottom opening 40 Permeate side flow path 40a Bottom opening 40b Top opening 50 outer tube 60 Catalyst 61 1st layer 62 2nd layer 63 3rd layer 70 Catalyst 71 Part 1 72 Part 2 73 Part 3

Claims

1. a separation membrane that allows permeation of a product of a conversion reaction from a feed gas containing at least hydrogen and carbon oxides to a liquid fuel; a non-permeation side flow path provided on a non-permeation side of the separation membrane and through which the raw material gas flows; A catalyst filled in the non-permeation side flow path for promoting the conversion reaction; Equipped with The catalyst includes catalyst particles and filler particles that are softer than the catalyst particles, The catalyst particles are composed of a carrier and a supported catalyst component, The filler particles are composed of a carrier and the supported catalyst component. Reactor.

2. The non-permeation side flow path extends in a substantially vertical direction, The catalyst has a first layer and a second layer disposed above the first layer, the first layer contains a larger amount of the filler particles than the catalyst particles, The second layer contains a larger amount of the catalyst particles than the filler particles.

10. The reactor of claim 1.

3. The non-permeation side flow path extends in a substantially vertical direction, The catalyst has a first layer and a second layer disposed above the first layer, the filler particles include first filler particles disposed in the first layer and second filler particles disposed in the second layer; the first filler particles are softer than the second filler particles; The reactor of claim 1 or 2.

4. The porosity of the first layer is greater than the porosity of the second layer. The reactor of claim 3.

5. The first layer is located at the bottom of the catalyst. The reactor of claim 2.

6. the catalyst has a first portion in contact with the separation membrane and a second portion remote from the separation membrane; The first portion contains a larger amount of the filler particles than the catalyst particles, The second portion contains a larger amount of the catalyst particles than the filler particles.

10. The reactor of claim 1.

7. the catalyst has a first portion in contact with the separation membrane and a second portion remote from the separation membrane; the filler particles include third filler particles disposed in the first portion and fourth filler particles disposed in the second portion; the third filler particles are softer than the fourth filler particles; The reactor of claim 1 or 6.

8. The porosity of the first portion is greater than the porosity of the second portion. The reactor of claim 6.

9. the catalyst has a first portion in contact with the separation membrane and a second portion remote from the separation membrane; the first portion contains a larger amount of the catalyst particles than the filler particles; The second portion contains a larger amount of the filler particles than the catalyst particles.

10. The reactor of claim 1.

10. the catalyst has a first portion in contact with the separation membrane and a second portion remote from the separation membrane; the filler particles include fifth filler particles disposed in the first portion and sixth filler particles disposed in the second portion; the sixth filler particles are softer than the fifth filler particles; The reactor of claim 1 or 9.

11. The porosity of the second portion is greater than the porosity of the first portion. The reactor of claim 9.

12. a separation membrane that allows permeation of a product of a conversion reaction from a feed gas containing at least hydrogen and carbon oxides to a liquid fuel; a non-permeation side flow path provided on a non-permeation side of the separation membrane and through which the raw material gas flows; A catalyst filled in the non-permeation side flow path for promoting the conversion reaction; Equipped with The catalyst includes catalyst particles and filler particles that are softer than the catalyst particles, The catalyst particles are composed of a carrier and a supported catalyst component, The filler particles are composed of a carrier and a supported catalyst component different from a metal catalyst component. Reactor.

13. The non-permeation side flow path extends in a substantially vertical direction, The catalyst has a first layer and a second layer disposed above the first layer, the first layer contains a larger amount of the filler particles than the catalyst particles, The second layer contains a larger amount of the catalyst particles than the filler particles. The reactor of claim 12.

14. The non-permeation side flow path extends in a substantially vertical direction, The catalyst has a first layer and a second layer disposed above the first layer, the filler particles include first filler particles disposed in the first layer and second filler particles disposed in the second layer; the first filler particles are softer than the second filler particles; A reactor according to claim 12 or 13.

15. The porosity of the first layer is greater than the porosity of the second layer. The reactor of claim 14.

16. The first layer is located at the bottom of the catalyst. The reactor of claim 13.

17. the catalyst has a first portion in contact with the separation membrane and a second portion remote from the separation membrane; The first portion contains a larger amount of the filler particles than the catalyst particles, The second portion contains a larger amount of the catalyst particles than the filler particles. The reactor of claim 12.

18. the catalyst has a first portion in contact with the separation membrane and a second portion remote from the separation membrane; the filler particles include third filler particles disposed in the first portion and fourth filler particles disposed in the second portion; the third filler particles are softer than the fourth filler particles; 18. The reactor of claim 12 or 17.

19. The porosity of the first portion is greater than the porosity of the second portion.

20. The reactor of claim 17.

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