Separation Membrane Module

Abstract

The separation membrane module (1) includes a cylindrical housing (20), a columnar reactor (10) accommodated in the housing (20), an annular first flange (30) surrounding a first end (10a) of the reactor (10), and a first bonding material (35) interposed between the first flange (30) and the reactor (10). The housing (20) has a first opposing surface (J1) facing an end surface (K1) of the first flange (30) and an inner peripheral surface (G1) facing an outer peripheral surface (L1) of the first flange (30). The thermal expansion coefficient of the first bonding material (35) is smaller than that of the first flange (30). The thermal expansion coefficient of the reactor (10) is smaller than that of the first flange (30).

Description

[Technical field]

[0001] The present invention relates to a separation membrane module. [Background technology]

[0002] Conventionally, there is known a separation membrane module including a housing and a columnar membrane structure accommodated in the housing. Examples of the membrane structure include a separation filter configured to separate a predetermined component from a mixed fluid using a separation membrane (see, for example, Patent Document 1), and a reactor configured to separate a product of a conversion reaction from a raw material gas to a liquid fuel using a separation membrane (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2018 / 180095 [Patent Document 2] JP 2018-008940 A Summary of the Invention [Problem to be solved by the invention]

[0004] Incidentally, since it is necessary to provide a permeate side space between the membrane structure and the housing for recovering the permeated components that have permeated the separation membrane, it is necessary to attach flanges to the ends of the membrane structure using a bonding material.

[0005] However, if distortion occurs in the flange due to differences in the thermal expansion coefficients of the flange, the bonding material, and the membrane structure, the flange may interfere with the housing and be damaged.

[0006] An object of the present invention is to provide a separation membrane module capable of suppressing damage to a flange. [Means for solving the problem]

[0007] A separation membrane module according to a first aspect of the present invention includes a cylindrical housing, a columnar membrane structure accommodated in the housing, an annular first flange surrounding a first end of the membrane structure, and a first bonding material interposed between the first flange and the first end. The housing has a first opposing surface facing the end face of the first flange and an inner peripheral surface facing the outer peripheral surface of the first flange. The thermal expansion coefficient of the first bonding material is smaller than that of the first flange. The thermal expansion coefficient of the membrane structure is smaller than that of the first flange.

[0008] The separation membrane module of the second aspect of the present invention is related to the first aspect and includes an annular second flange surrounding the second end of the membrane structure, and a second bonding material interposed between the second flange and the second end. The housing has a second opposing surface opposing the end face of the second flange. The inner peripheral surface of the housing faces the outer peripheral surface of the second flange. The thermal expansion coefficient of the second bonding material is smaller than the thermal expansion coefficient of the second flange. The thermal expansion coefficient of the membrane structure is smaller than the thermal expansion coefficient of the second flange.

[0009] A third aspect of the separation membrane module of the present invention is related to the second aspect, and the housing has a cylindrical main body having an inner circumferential surface, a first end plate having a first opposing surface, and a second end plate having a second opposing surface.

[0010] A separation membrane module according to a fourth aspect of the present invention relates to the first to third aspects, and the first flange is made of a ceramic material.

[0011] A separation membrane module according to a fifth aspect of the present invention relates to the first to fourth aspects, and the second flange is made of a ceramic material.

[0012] A separation membrane module according to a sixth aspect of the present invention relates to any one of the first to fifth aspects, and the membrane structure is a reactor.

[0013] A separation membrane module according to a seventh aspect of the present invention relates to any one of the first to fifth aspects, and the membrane structure is a separation filter. Effect of the Invention

[0014] According to the present invention, it is possible to provide a separation membrane module capable of suppressing damage to a flange. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 is a cross-sectional view of a separation membrane module according to an embodiment. [Diagram 2] FIG. 2 is a cross-sectional view of a reactor assembly according to an embodiment. [Diagram 3] FIG. 3 is a cross-sectional view of a reactor assembly according to a comparative example. [Figure 4] FIG. 4 is a cross-sectional view of a separation membrane module according to the second modification. [Diagram 5] FIG. 5 is a cross-sectional view taken along line AA of FIG. [Figure 6] FIG. 6 is a cross-sectional view taken along line BB of FIG. [Figure 7] FIG. 7 is a cross-sectional view of a separation membrane module according to the fifth modification. [Figure 8] FIG. 8 is a cross-sectional view of a separation membrane module according to the fifth modification. [Figure 9] FIG. 9 is a cross-sectional view of a separation membrane module according to the sixth modification. [Figure 10] FIG. 10 is a cross-sectional view of a separation membrane module according to the sixth modification. [Figure 11] FIG. 11 is a cross-sectional view of a separation membrane module according to the sixth modification. [Figure 12] FIG. 12 is a cross-sectional view of a separation membrane module according to the seventh modification. [Figure 13] FIG. 13 is a cross-sectional view of a separation membrane module according to the seventh modification. [Figure 14] FIG. 14 is a cross-sectional view of a separation membrane module according to Modification 8. As shown in FIG. [Figure 15] FIG. 15 is a cross-sectional view of a separation membrane module according to Modification 8. As shown in FIG. [Figure 16] FIG. 16 is a cross-sectional view of a separation membrane module according to Modification 8. As shown in FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] (Separation membrane module 1) A separation membrane module 1 according to an embodiment will be described below. Fig. 1 is a cross-sectional view that illustrates a schematic configuration of the separation membrane module 1.

[0017] 1, the separation membrane module 1 includes a reactor 10, a housing 20, a first flange 30, and a second flange 40. The reactor 10 is an example of the "membrane structure" according to the present invention.

[0018] [Reactor 10] The reactor 10 is accommodated in a housing 20. The reactor 10 is formed in a columnar shape extending in the longitudinal direction. The outer shape of the reactor 10 is not particularly limited, but may be, for example, a circular cylinder, an elliptical cylinder, or a polygonal cylinder.

[0019] The reactor 10 is a so-called membrane reactor for converting a raw material gas into a liquid fuel. The raw material gas contains at least hydrogen and carbon oxides. At least one of carbon monoxide and carbon dioxide can be used as the carbon oxide. The raw material gas may be a so-called synthetic gas (Syngas). 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 the 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 normal temperature and pressure include propane, butane, and mixtures thereof.

[0020] For example, the reaction formula (1) when methanol is synthesized by catalytic hydrogenation of a raw material gas containing hydrogen and carbon dioxide in the presence of a catalyst is as follows. CO2+3H2⇔CH3OH+H2O (1)

[0021] The above reaction is an equilibrium reaction, and the reactor 10 can shift the reaction equilibrium to the product side by separating water vapor, which is one of the products of the conversion reaction. In order to increase the conversion efficiency and reaction rate, it is preferable to carry out the conversion reaction under high temperature and pressure (e.g., 180°C or higher, 2 MPa or higher). 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 10. The reactor 10 preferably has heat resistance and pressure resistance suitable for the synthesis conditions of the desired liquid fuel.

[0022] The reactor 10 according to the present embodiment is a so-called tubular type. As shown in FIG. 1, the reactor 10 has an outer peripheral surface F1, a first end surface F2, and a second end surface F3. The outer peripheral surface F1 is a side surface of the cylindrical reactor 10. The outer peripheral surface F1 is connected to the first end surface F2 and the second end surface F3. The first end surface F2 is one end surface of the cylindrical reactor 10. A first opening T1 is formed in the first end surface F2. The raw material gas flows into the inside of the reactor 10 from the first opening T1. The second end surface F3 is the other end surface of the cylindrical reactor 10. A second opening T2 is formed in the second end surface F3. The liquid fuel flows out of the reactor 10 from the second opening T2.

[0023] The reactor 10 has a first end 10a and a second end 10b. The first end 10a is one end of the reactor 10 in the longitudinal direction. The first end 10a includes the first end face F2 described above. The second end 10b is the other end of the reactor 10 in the longitudinal direction. The second end 10b includes the second end face F3 described above.

[0024] Here, the reactor 10 is composed of a porous support 11, a separation membrane 12, a catalyst 13, and a catalyst stopper 14.

[0025] The porous support 11 is formed in a cylindrical shape extending in the longitudinal direction. The porous support 11 is made of a porous material. As the porous material, a ceramic material, a metal material, a resin material, or a composite material thereof can be used, and a ceramic material is particularly preferable. As aggregates of the ceramic material, alumina (Al2O3), titania (TiO2), mullite (Al2O3·SiO2), cerium oxide, and cordierite (Mg2Al4Si5O 18 ), and composite materials containing two or more of these can be used, with alumina being preferred in consideration of availability, clay stability, and corrosion resistance. As the inorganic binder for the ceramic material, at least one of titania, mullite, sinterable alumina, silica, glass frit, clay minerals, and sinterable cordierite can be used. However, the ceramic material does not have to contain an inorganic binder.

[0026] The average pore diameter of the porous support 11 can be 5 μm or more and 25 μm or less. The average pore diameter of the porous support 11 can be measured by mercury intrusion porosimetry. The porosity of the porous support 11 can be 25% or more and 50% or less. The average particle diameter of the porous material can be 1 μm or more and 100 μm or less. The average particle diameter is the arithmetic mean value of the maximum diameters of 30 measurement target particles (randomly selected) measured by cross-sectional microstructural observation using a SEM (Scanning Electron Microscope).

[0027] The separation membrane 12 is supported by a porous support 11. The separation membrane 12 is formed in a cylindrical shape extending in the longitudinal direction. The inside of the separation membrane 12 is a non-permeation side space S1 to which a raw material gas is supplied. The non-permeation side space S1 is a space between a first opening T1 and a second opening T2. In this embodiment, the separation membrane 12 is disposed on the inner surface of the porous support 11, but may be disposed on the outer surface of the porous support 11.

[0028] The separation membrane 12 allows the permeation of water vapor, which is one of the products of the conversion reaction from the feed gas to liquid fuel, thereby making it possible to utilize the equilibrium shift effect to shift the reaction equilibrium of the above formula (1) to the product side.

[0029] The separation membrane 12 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)).

[0030] The separation membrane 12 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").

[0031] An inorganic membrane can be used as the separation membrane 12. 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.

[0032] The catalyst 13 is disposed inside the separation membrane 12, i.e., in the non-permeation side space S1. The catalyst 13 is preferably filled in the non-permeation side space S1, but may be disposed in the form of layers or islands on the surface of the separation membrane 12. The catalyst 13 promotes the conversion reaction from the raw material gas to liquid fuel, as shown in the above formula (1).

[0033] Any known catalyst suitable for a conversion reaction from a raw material gas to a liquid fuel can be used as the catalyst 13. Examples of the catalyst 13 include metal catalysts (copper, palladium, etc.), oxide catalysts (zinc oxide, zirconia, gallium oxide, etc.), and catalysts made by combining these (copper-zinc oxide, copper-zinc oxide-alumina, copper-zinc oxide-chromium oxide-alumina, copper-cobalt-titania, and catalysts made by modifying these with palladium, etc.).

[0034] The catalyst stopper 14 is attached to the second end face F3. The catalyst stopper 14 is disposed so as to cover the second opening T2 formed in the second end face F3. The catalyst stopper 14 stops the catalyst 13 from leaking out from the second opening T2. The catalyst stopper 14 has a configuration that stops the catalyst 13 from leaking out while not impeding the outflow of liquid fuel. For example, a mesh member, a perforated plate, or the like can be used as the catalyst stopper 14.

[0035] However, in cases where leakage of the catalyst 13 is unlikely to occur (for example, when the catalyst 13 is arranged in a layer or island form on the surface of the separation membrane 12), the reactor 10 does not need to have the catalyst stopper 14.

[0036] In the reactor 10, the raw material gas supplied to the non-permeation side space S1 is converted into liquid fuel by the action of the catalyst 13, and water vapor, which is one of the products of the conversion reaction, passes through the separation membrane 12 and the porous support 11 and is separated into the permeation side space S2 described later.

[0037] [Housing 20] The housing 20 is formed into a cylindrical shape as a whole. The housing 20 accommodates the reactor 10. The housing 20 has a structure capable of withstanding a conversion reaction under high temperature and high pressure (e.g., 180°C or higher, 2 MPa or higher). When the raw material gas and / or the sweep gas contains hydrogen, it is preferable that the material of the housing 20 is resistant to hydrogen embrittlement. The housing 20 can be mainly made of a metal material (stainless steel, etc.).

[0038] As shown in FIG. 1, the housing 20 is composed of a cylindrical main body 21, a first end plate 22, and a second end plate .

[0039] The tube body 21 is formed in a cylindrical shape extending in the longitudinal direction. Both ends of the tube body 21 are expanded in diameter in the form of flanges.

[0040] The cylindrical body 21 has an inner circumferential surface G1, a first end surface G2, a second end surface G3, a sweep gas supply port T3, and a sweep gas exhaust port T4.

[0041] The inner circumferential surface G1 faces the outer circumferential surface F1 of the reactor 10, and is spaced apart from the outer circumferential surface F1. The gap between the inner circumferential surface G1 and the outer circumferential surface F1 is a permeation side space S2 for recovering water vapor, which is one of the products of the conversion reaction.

[0042] An annular first notch H1 is formed at one end of the inner circumferential surface G1. An annular first elastic member 26a is disposed in the first notch H1. For example, an O-ring made of expanded graphite or rubber can be used as the first elastic member 26a. The first elastic member 26a is pressed by the first pressing member 24 inserted into the first notch H1 and comes into close contact with the first flange 30 described below. This seals the gap between the tube main body 21 and the first flange 30. The first pressing member 24 is fixed to the first end surface G2 of the tube main body 21 by a bolt or the like. In this embodiment, the first pressing member 24 has an L-shaped cross section.

[0043] At the other end of the inner circumferential surface G1, an annular second notch H2 is formed. An annular second elastic member 26b is disposed in the second notch H2. For example, an O-ring made of expanded graphite or rubber can be used as the second elastic member 26b. The second elastic member 26b is pressed by the second pressing member 25 inserted into the second notch H2 and comes into close contact with the second flange 40 described below. This seals the gap between the tube main body 21 and the second flange 40. The second pressing member 25 is fixed to the second end surface G3 of the tube main body 21 by a bolt or the like. In this embodiment, the second pressing member 25 has an L-shaped cross section.

[0044] The first end face G2 has a first recess H3 formed therein. The third elastic member 26c is disposed in the first recess H3. For example, an O-ring made of expanded graphite or rubber can be used as the third elastic member 26c. The third elastic member 26c is in close contact with the first end plate 22.

[0045] A ring-shaped second recess H4 is formed in the second end face G3. A fourth elastic member 26d is disposed in the second recess H4. For example, an O-ring made of expanded graphite or rubber can be used as the fourth elastic member 26d. The fourth elastic member 26d is in close contact with the second end plate 23.

[0046] The sweep gas supply port T3 and the sweep gas outlet T4 are connected to the permeate side space S2. The sweep gas is supplied from the sweep gas supply port T3 to the permeate side space S2. The sweep gas takes in water vapor in the permeate side space S2 and absorbs reaction heat accompanying the conversion reaction. The sweep gas is discharged from the sweep gas outlet T4 together with water vapor. The sweep gas may be hydrogen and / or carbon oxide. In addition, the sweep gas may be an inert gas (e.g., nitrogen) or air. In this embodiment, the sweep gas supply port T3 and the sweep gas outlet T4 are diagonally opposed to each other in a cross-sectional view, but the positions of the sweep gas supply port T3 and the sweep gas outlet T4 can be changed as appropriate.

[0047] The first end plate 22 is an annular plate member. The central portion of the first end plate 22 has a diameter enlarged in the shape of a flange. The first end plate 22 has a first opposing surface J1. The first opposing surface J1 faces a first end surface F2 of the reactor 10 and an end surface K1 of a first flange 30 described later.

[0048] In this specification, when two surfaces are "opposed" it means that at least a portion of each of the two surfaces directly faces each other without any other member therebetween.

[0049] However, the first opposing surface J1 does not have to face the first end surface F2 of the reactor 10. The first opposing surface J1 abuts against the first end surface G2 of the tube main body 21. An annular third recess H5 is formed in the first opposing surface J1. A portion of the first pressing member 24 protruding from the first end surface G2 is housed in the third recess H5.

[0050] The first end plate 22 is connected to the tube main body 21 by a plurality of fixing members 27. The fixing members 27 are formed of, for example, bolts and nuts. The first end plate 22 is in close contact with the third elastic member 26c. This provides a seal between the tube main body 21 and the first end plate 22.

[0051] The second end plate 23 is an annular plate member. The central portion of the second end plate 23 is expanded in diameter in a flange shape. The second end plate 23 has a second opposing surface J2. The second opposing surface J2 faces the second end surface F3 of the reactor 10 and the end surface K2 of the second flange 40 described later. However, the second opposing surface J2 does not have to face the second end surface F3 of the reactor 10. The second opposing surface J2 abuts against the second end surface G3 of the tube main body 21. The second opposing surface J2 is formed with an annular fourth recess H6. The fourth recess H6 accommodates a portion of the second pressing member 25 protruding from the second end surface G3.

[0052] The second end plate 23 is connected to the tube main body 21 by a plurality of fixing members 28. The fixing members 28 are formed of, for example, bolts and nuts. The second end plate 23 is in close contact with the fourth elastic member 26d. This provides a seal between the tube main body 21 and the second end plate 23.

[0053] [First flange 30] The first flange 30 is attached to the reactor 10. The first flange 30 functions as a spacer for forming a permeate side space S2 between the reactor 10 and the tube main body 21. The first flange 30 is formed in an annular shape. The first flange 30 surrounds the first end 10a of the reactor 10. The first flange 30 is fitted into one end of the tube main body 21. The first flange 30 supports the first end 10a of the reactor 10 at a position away from the tube main body 21. This forms a permeate side space S2 between the reactor 10 and the tube main body 21.

[0054] The first flange 30 has an end face K1 and an outer peripheral surface L1. The end face K1 is the longitudinally outer surface of the first flange 30. The end face K1 faces the first opposing surface J1 of the first end plate 22. At least a portion of the end face K1 may abut against the first opposing surface J1. In this embodiment, the end face K1 is flat. The outer peripheral surface L1 is the radially outer surface of the first flange 30. The outer peripheral surface L1 faces the inner peripheral surface G1 of the tube main body 21 and is in close contact with the first elastic member 26a. The outer peripheral surface L1 may abut against the inner peripheral surface G1.

[0055] The first flange 30 is made of a dense ceramic material. Examples of the ceramic material that can be used include alumina, zirconia, silicon carbide, aluminum nitride, cordierite, and composite materials containing two or more of these. The first flange 30 needs to be airtight and liquidtight. Therefore, the porosity of the first flange 30 is preferably 10.0% or less, and more preferably 5.0% or less.

[0056] A first bonding material 35 is inserted in the gap between the first flange 30 and the reactor 10. The first bonding material 35 bonds the first flange 30 and the reactor 10. The first bonding material 35 only needs to ensure the bonding strength between the first flange 30 and the reactor 10, and is disposed in at least a part of the gap between the first flange 30 and the reactor 10.

[0057] As the first bonding material 35, crystallized glass, amorphous glass, brazing material, ceramics, or the like can be used, and in consideration of heat resistance and pressure resistance, crystallized glass is particularly preferable.

[0058] As the crystallized glass, for example, SiO2-B2O3-based, SiO2-CaO-based, SiO2-Al2O3-based, SiO2-MgO-based, SiO2-ZnO-BaO-based, SiO2-B2O3-CaO-based, or SiO2-MgO-CaO-based, SiO2-Al2O3-B2O3-based, SiO2-MgO-Al2O3-based crystallized glass can be used. In this specification, crystallized glass means glass in which the ratio of the "volume occupied by the crystalline phase" to the total volume (degree of crystallinity) is 60% or more, and the ratio of the "volume occupied by the amorphous phase and impurities" to the total volume is less than 40%.

[0059] [Second flange 40] The second flange 40 is attached to the reactor 10. The second flange 40 is disposed on the opposite side of the first flange 30. The second flange 40 functions as a spacer for forming a permeate side space S2 between the reactor 10 and the cylindrical body 21. The second flange 40 is formed in an annular shape. The second flange 40 surrounds the second end 10b of the reactor 10. The second flange 40 is fitted into the other end of the cylindrical body 21. The second flange 40 supports the second end 10b of the reactor 10 at a position away from the cylindrical body 21.

[0060] The second flange 40 has an end face K2 and an outer peripheral surface L2. The end face K2 is the longitudinally outer surface of the second flange 40. The end face K2 faces the second opposing surface J2 of the second end plate 23. At least a portion of the end face K2 may abut against the second opposing surface J2. In this embodiment, the end face K2 is flat. The outer peripheral surface L2 is the radially outer surface of the second flange 40. The outer peripheral surface L2 faces the inner peripheral surface G1 of the tube main body 21 and is in close contact with the second elastic member 26b. The outer peripheral surface L2 may abut against the inner peripheral surface G1.

[0061] The second flange 40 is made of a dense ceramic material. Examples of the ceramic material that can be used include alumina, zirconia, silicon carbide, aluminum nitride, cordierite, and composite materials containing two or more of these. The second flange 40 needs to be airtight and liquidtight. Therefore, the porosity of the second flange 40 is preferably 10.0% or less, and more preferably 5.0% or less. A second bonding material 45 is inserted in the gap between the second flange 40 and the reactor 10. The second bonding material 45 bonds the second flange 40 and the reactor 10. The second bonding material 45 is required only to ensure the bonding strength between the second flange 40 and the reactor 10, and is disposed in at least a part of the gap between the second flange 40 and the reactor 10. As the second bonding material 45, crystallized glass, amorphous glass, brazing material, ceramics, or the like can be used, and crystallized glass is particularly preferable in consideration of heat resistance and pressure resistance.

[0062] [Relationship between thermal expansion coefficients] The thermal expansion coefficient of the first bonding material 35 is smaller than that of the first flange 30, and the thermal expansion coefficient of the reactor 10 is smaller than that of the first flange 30. In other words, the thermal expansion coefficient of the first flange 30 is larger than the thermal expansion coefficients of the first bonding material 35 and the reactor 10. Therefore, in the assembly process of the separation membrane module 1, it is possible to suppress damage to the first flange 30 due to interference with the housing 20. Specifically, this is as follows.

[0063] The process of assembling the separation membrane module 1 includes a step of preparing a reactor assembly in which the first and second flanges 30, 40 are joined to the reactor 10, and a step of housing the reactor assembly in the housing 20.

[0064] The process of producing the reactor assembly includes a first step of forming a molded body of the bonding material, a second step of attaching a flange, and a third step of heating the molded body of the bonding material. In the first step, a molded body of the first bonding material 35 is formed at the first end 10a of the reactor 10, and a molded body of the second bonding material 45 is formed at the second end 10b of the reactor 10. In the second step, the first flange 30 is attached so as to surround the molded body of the first bonding material 35, and the second flange 40 is attached so as to surround the molded body of the second bonding material 45. In the third step, the molded bodies of the first and second bonding materials 35, 45 are heated to cause crystal growth or melting, and then cooled to room temperature to form the first and second bonding materials 35, 45. As a result, a reactor assembly in which the first and second flanges 30, 40 are joined to the reactor 10 via the first and second bonding materials 35, 45 is completed.

[0065] Here, when the temperature of the first bonding material 35 is lowered in the third step, the first flange 30 contracts more than the first bonding material 35 and the reactor 10 because the thermal expansion coefficient of the first bonding material 35 is smaller than that of the first flange 30 and the reactor 10 is smaller than that of the first flange 30. At this time, the inner circumferential side of the first flange 30 cannot contract much because it is restrained by the first bonding material 35, whereas the outer circumferential side of the first flange 30 contracts more because it is not restrained. Therefore, as shown in FIG. 2, the first flange 30 is distorted so that the inner circumferential side bulges in the longitudinal direction compared to the outer circumferential side, and thus has a shape that does not protrude toward the first end plate 22 side.

[0066] Next, the process of accommodating the reactor assembly includes a fourth step of inserting the reactor assembly, a fifth step of attaching the elastic members, and a sixth step of connecting the end plates. In the fourth step, the reactor assembly is inserted into the cylindrical body 21, and then both ends of the reactor assembly are aligned. In the fifth step, the first and second elastic members 26a and 26b fitted into the first and second notches H1 and H2 of the cylindrical body 21 are pressed by the first and second pressing members 24 and 25, and the third and fourth elastic members 26c and 26d are fitted into the first and second recesses H3 and H4 of the cylindrical body 21. In the sixth step, the first end plate 22 is connected to the cylindrical body 21 by the fixing member 27, and the second end plate 23 is connected to the cylindrical body 21 by the fixing member 28. With the above steps, the separation membrane module 1 in which the reactor assembly is accommodated in the housing 20 is completed.

[0067] 2, the outer circumferential side of the first flange 30 is shrunk. Therefore, when connecting the first end plate 22 to the tube main body 21 in the sixth step, the outer circumferential side of the first flange 30 can be prevented from coming into contact with the first end plate 22. Therefore, the outer circumferential side of the first flange 30 can be prevented from being pressed by the first end plate 22 and being damaged.

[0068] Assuming that the thermal expansion coefficient of the first bonding material 35 is larger than that of the first flange 30, or that the thermal expansion coefficient of the reactor 10 is larger than that of the first flange 30, the contraction amount of the first flange 30 in the third step is smaller than the contraction amount of the first bonding material 35 and the reactor 10. At this time, the inner periphery side of the first flange 30 is pulled by the first bonding material 35 and the reactor 10 and contracts significantly, whereas the outer periphery side of the first flange 30 does not contract significantly. Therefore, as shown in FIG. 3, the outer periphery side of the first flange 30 is distorted so as to bulge in the longitudinal direction compared to the inner periphery side, and thus has a shape protruding toward the first end plate 22 side. Then, when the first end plate 22 is connected to the tube main body 21 in the sixth step, the outer periphery side of the first flange 30 comes into contact with the first end plate 22, and the outer periphery side of the first flange 30 is damaged.

[0069] The thermal expansion coefficient of the first bonding material 35 may be larger or smaller than that of the reactor 10, or may be equal to that of the reactor 10, but is preferably smaller than that of the reactor 10. In other words, it is preferable that the relationship of the thermal expansion coefficient is first flange 30>reactor 10>first bonding material 35. This makes it possible to minimize the clearance between the first flange 30 and the first end plate 22.

[0070] The thermal expansion coefficient of the first flange 30 can be adjusted by changing the material, combining the material, changing the material composition, and changing the porosity. The thermal expansion coefficient of the first bonding material 35 can be adjusted by changing the material, combining the material, changing the material composition, and changing the porosity. The thermal expansion coefficient of the reactor 10 can be adjusted by changing the material, combining the material, changing the material composition, and changing the porosity.

[0071] Moreover, it is preferable that the thermal expansion coefficient of the second bonding material 45 is smaller than that of the second flange 40, and that the thermal expansion coefficient of the reactor 10 is smaller than that of the second flange 40. In other words, it is preferable that the thermal expansion coefficient of the second flange 40 is larger than the thermal expansion coefficients of the second bonding material 45 and the reactor 10. This makes it possible to prevent the second flange 40 from being damaged due to interference with the housing 20, similar to the above-mentioned case of the first flange 30.

[0072] The thermal expansion coefficient of the second bonding material 45 may be larger or smaller than that of the reactor 10, or may be equal to that of the reactor 10, but is preferably smaller than that of the reactor 10. That is, it is preferable that the relationship of the thermal expansion coefficient is second flange 40>reactor 10>second bonding material 45. This makes it possible to minimize the clearance between the second flange 40 and the second end plate 23.

[0073] The thermal expansion coefficient of the second flange 40 can be adjusted by changing the material, combining the material, changing the material composition, and changing the porosity. The thermal expansion coefficient of the second bonding material 45 can be adjusted by changing the material, combining the material, changing the material composition, and changing the porosity. The thermal expansion coefficient of the reactor 10 can be adjusted by changing the material, combining the material, changing the material composition, and changing the porosity.

[0074] The thermal expansion coefficient is the ratio of the length of expansion or contraction specific to a material to a temperature change. The thermal expansion coefficient can be measured, for example, by a method conforming to JIS R 1618:1994. The unit of the thermal expansion coefficient is ppm / K. In this specification, the thermal expansion coefficient means the thermal expansion coefficient at 40°C to 800°C. The higher temperature (i.e., 800°C) may be changed according to the crystallization temperature of the first bonding material 35 or the second bonding material 45. The crystallization temperature of the first bonding material 35 or the second bonding material 45 can be changed as appropriate.

[0075] (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.

[0076] [Variation 1] In the above embodiment, the reactor 10 is used as the membrane structure, but a separation filter can be used as the membrane structure. The separation filter has the same configuration as the reactor 10, except that a separation membrane that allows the permeation of a desired component contained in a mixed fluid is used instead of the separation membrane 12 that allows the permeation of water vapor, and that the separation filter does not include a catalyst 13. In addition, in the present invention, even if a separation filter is used as the membrane structure, it is assumed that it will be used under high temperature and high pressure conditions.

[0077] In addition, when a separation filter is used as the membrane structure, since no reaction heat is generated and there is little need for temperature control, the components that have permeated the separation membrane may be discharged from the sweep gas outlet T4 by reducing the pressure on the sweep gas outlet T4 side more than on the sweep gas supply port T3 side.

[0078] [Variation 2] In the above embodiment, the reactor 10, which is an example of a membrane structure, is a tubular type, but it may be a monolith type. The monolith type refers to a shape having a plurality of cells penetrating in the longitudinal direction, and is a concept including a honeycomb type.

[0079] Fig. 4 is a cross-sectional view that illustrates a schematic configuration of a separation membrane module 1a that includes a monolithic reactor 100. However, in Fig. 4, only the reactor 100 is illustrated in side view.

[0080] The separation membrane module 1a is the same as the separation membrane module 1 according to the above embodiment, except that it further includes a flow stopper 50 and includes a reactor 100 instead of the reactor 10. Note that the catalyst stopper 14 is also an optional configuration in the reactor 100.

[0081] The flow stopper 50 is formed in an annular shape. The flow stopper 50 is disposed between the reactor 100 and the housing 20. The flow stopper 50 divides the gap between the reactor 100 and the housing 20 into a first permeate side space S21 and a second permeate side space S22. The flow stopper 50 suppresses the sweep gas from directly flowing between the first permeate side space S21 and the second permeate side space S22. The flow stopper 50 only needs to be able to directly suppress the flow of the sweep gas, and does not need to seal between the reactor 100 and the housing 20. The flow stopper 50 can be made of, for example, expanded graphite, rubber, resin, metal, or the like.

[0082] The reactor 100 has a plurality of first flow paths 15, a plurality of second flow paths 16, a first slit 17, and a second slit .

[0083] The first flow path 15 penetrates the reactor 100 in the longitudinal direction. The first flow path 15 opens to the first and second end faces F2, F3. The above-mentioned separation membrane 12 is formed on the inner surface of the first flow path 15. The inside of the separation membrane 12 is the non-permeation side space S1. The above-mentioned catalyst 13 is disposed in the non-permeation side space S1.

[0084] The second flow passage 16 is formed inside the reactor 100. The second flow passage 16 extends along the longitudinal direction. The second flow passage 16 is closed at the first and second end faces F2, F3.

[0085] The first slits 17 are formed in the first end 100a of the reactor 100. The first slits 17 radially penetrate each of the second flow paths 16 and open to the outer circumferential surface F1. Therefore, the first slits 17 communicate with each of the second flow paths 16 and the first permeate side space S21.

[0086] The second slits 18 are formed in the second end 100b of the reactor 100. The second slits 18 radially penetrate each second flow path 16 and open to the outer circumferential surface F1. Therefore, the second slits 18 communicate with each second flow path 16 and the second permeate side space S22.

[0087] When the raw material gas is supplied to the first flow passage 15, the raw material gas is converted into liquid fuel by the action of the catalyst 13, and water vapor, which is one of the products of the conversion reaction, passes through the separation membrane 12 and flows into the second flow passage 16. The water vapor that has flowed into the second flow passage 16 is taken in by the sweep gas that flows into the second flow passage 16 from the sweep gas supply port T3 through the second permeate side space S22 and the second slit 18, and then is discharged to the outside from the sweep gas discharge port T4 through the first slit 17 and the first permeate side space S21.

[0088] Here, Fig. 5 is a cross-sectional view taken along line AA in Fig. 4. As shown in Fig. 5, the first slit 17 penetrates the inside of the reactor 100 in a straight line and opens to both sides of the reactor 100. The first slit 17 has two openings formed in the outer circumferential surface F1. The sweep gas flowing out from each of the two openings of the first slit 17 into the first permeate side space S21 passes through the first permeate side space S21 and is discharged to the outside from the sweep gas outlet T4.

[0089] Here, the first extension direction in which the first slits 17 extend inside the reactor 100 is preferably inclined or perpendicular to the discharge direction of the sweep gas discharged from the sweep gas discharge port T4 to the outside. Specifically, the angle θ1 of the first extension direction with respect to the discharge direction is preferably 45 degrees or more and 135 degrees or less. This makes it possible to suppress bias in the gas flow from each opening of the first slits 17 to the sweep gas discharge port T4, thereby suppressing bias in the sweep gas flow in the first permeation side space S21.

[0090] Fig. 6 is a cross-sectional view taken along line BB in Fig. 4. As shown in Fig. 6, the second slit 18 penetrates the inside of the reactor 100 in a straight line and opens to both sides of the reactor 100. The second slit 18 has two openings formed in the outer circumferential surface F1. The sweep gas supplied from the sweep gas supply port T3 to the second permeate side space S22 passes through the second permeate side space S22 and flows into each of the two openings of the second slit 18.

[0091] Here, the second extension direction in which the second slit 18 extends inside the reactor 100 is preferably inclined or perpendicular to the supply direction of the sweep gas supplied from the sweep gas supply port T3 to the second permeate side space S22. Specifically, the angle θ2 of the second extension direction with respect to the supply direction is preferably 45 degrees or more and 135 degrees or less. This makes it possible to suppress bias in the gas flow from the sweep gas supply port T3 to each opening of the second slit 18, thereby suppressing bias in the sweep gas flow in the second permeate side space S22.

[0092] [Variation 3] In the above embodiment, the separation membrane 12 is in contact with the catalyst 13, but a buffer layer may be interposed between the separation membrane 12 and the catalyst 13. The buffer layer physically isolates the catalyst 13 from the separation membrane 12, thereby preventing cracks from occurring in the separation membrane 12 originating from the contact point with the catalyst 13 when the catalyst becomes hot due to reaction heat. The buffer layer may be made of a ceramic material or an organic polymer material. Examples of the ceramic material that may be used include silica, alumina, and chromia. Examples of the organic polymer material that may be used include PTFE, PVA, and PEG.

[0093] [Variation 4] In the above embodiment, the separation membrane 12 is permeable to water vapor, which is one of the products of the conversion reaction from the raw material gas to liquid fuel, but this is not limited to this. The separation membrane 12 may also be permeable to the liquid fuel itself, which is produced by 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.

[0094] In addition, when the separation membrane 12 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.

[0095] [Variation 5] In the separation membrane module 1 according to the above embodiment (see FIG. 1), the sweep gas supply port T3 and the sweep gas exhaust port T4 are diagonally opposed to each other in a side view, and the sweep gas flows from the sweep gas supply port T3 to the sweep gas exhaust port T4, but this is not limited to this.

[0096] For example, as shown in Fig. 7, the sweep gas supply port T3 and the sweep gas exhaust port T4 may be disposed on the same side of the reactor 10 in a side view, and a straightening plate 20a may be provided to close a part of the gap between the reactor 10 and the housing 20. In Fig. 7, three straightening plates 20a are provided, but the number of the straightening plates 20a may be one, two, or four or more. The position of the straightening plate 20a can be set appropriately.

[0097] 8, the housing 20 does not have a sweep gas supply port T3, and a sweep gas does not have to be supplied into the housing 20. In this case, the product separated by the separation membrane 12 of the reactor 10 flows out of the housing 20 from the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set appropriately.

[0098] The configurations of FIG. 7 and FIG. 8 are also applicable to the case where a separation filter is used as the membrane structure instead of the reactor 10.

[0099] [Variation 6] In the separation membrane module 1 according to the above embodiment (see FIG. 1), only one reactor 10 is accommodated in the housing 20, but this is not limiting.

[0100] For example, as shown in FIG. 9, a plurality of reactors 10 may be housed within a housing 20.

[0101] Also, as shown in Fig. 10, a straightening plate 20a may be provided to close a part of the gap between the reactor 10 and the housing 20. In Fig. 10, three straightening plates 20a are provided, but the number of the straightening plates 20a may be one, two, or four or more. The position of the straightening plate 20a can be set appropriately. Note that, as shown in Fig. 10, the sweep gas supply port T3 and the sweep gas exhaust port T4 may be disposed on the same side of the reactor 10 in a side view.

[0102] 11, the housing 20 does not have a sweep gas supply port T3, and a sweep gas does not have to be supplied into the housing 20. In this case, the product separated by the separation membrane 12 of the reactor 10 flows out of the housing 20 from the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set appropriately.

[0103] The configurations of FIGS. 9 to 11 are also applicable to the case where a separation filter is used as the membrane structure instead of the reactor 10.

[0104] [Variation 7] In the separation membrane module 1a according to the above-described modified example 2 (see FIG. 4), the sweep gas supply port T3 and the sweep gas exhaust port T4 are arranged diagonally opposite each other in a side view, but this is not limiting.

[0105] For example, as shown in FIG. 12, the sweep gas supply port T3 and the sweep gas exhaust port T4 may be disposed on the same side of the reactor 100 in a side view, or a straightening plate 20b may be provided to block a part of the gap between the reactor 100 and the housing 20. In FIG. 12, one straightening plate 20b is provided on each side of the flow stopper 90. The straightening plate 20b on the sweep gas supply port T3 side divides the space on the sweep gas supply port T3 side into a space where the sweep gas mainly flows into the second slit 18 of the reactor 100 and a space where the sweep gas flows in from the side of the reactor 100. The straightening plate 20b on the sweep gas exhaust port T4 side divides the space on the sweep gas exhaust port T4 side into a space where the sweep gas mainly flows out from the first slit 17 of the reactor 100 and a space where the sweep gas flows out from the side of the reactor 100. However, the number and positions of the straightening plates 20b can be set appropriately. Also, a portion of the sweep gas may pass through the interior of the flow stopper 90 .

[0106] 13, the housing 20 does not have a sweep gas supply port T3, and a sweep gas does not have to be supplied into the housing 20. In this case, the product separated by the separation membrane 12 of the reactor 100 flows out of the housing 20 from the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set appropriately.

[0107] 12 and 13 can also be applied to a case where a separation filter is used as the membrane structure instead of the reactor 100.

[0108] [Variation 8] In the separation membrane module 1a according to the above-mentioned modified example 2 (see FIG. 4), only one reactor 100 is accommodated in the housing 20, but this is not limiting.

[0109] For example, as shown in FIG. 14, a plurality of reactors 100 may be housed within the housing 20.

[0110] 15, a straightening plate 20b may be provided to block a part of the gap between the reactor 100 and the housing 20. In FIG. 15, one straightening plate 20b is provided on each side of the flow stopper 90. The straightening plate 20b on the sweep gas supply port T3 side divides the space on the sweep gas supply port T3 side into a space where the sweep gas mainly flows into the second slit 18 of the reactor 100 and a space where the sweep gas flows in from the side of the reactor 100. The straightening plate 20b on the sweep gas exhaust port T4 side divides the space on the sweep gas exhaust port T4 side into a space where the sweep gas mainly flows out from the first slit 17 of the reactor 100 and a space where the sweep gas flows out from the side of the reactor 100. However, the number and positions of the straightening plates 20b can be set appropriately. Also, a part of the sweep gas may pass through the inside of the flow stopper 90. As shown in FIG. 15, the sweep gas supply port T3 and the sweep gas exhaust port T4 may be disposed on the same side of the reactor 100 in a side view.

[0111] 16, the housing 20 does not have a sweep gas supply port T3, and a sweep gas does not have to be supplied into the housing 20. In this case, the product separated by the separation membrane 12 of the reactor 100 flows out of the housing 20 from the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set appropriately.

[0112] 14 to 16 can also be applied to a case where a separation filter is used as the membrane structure instead of the reactor 100. [Explanation of symbols]

[0113] 1. Separation membrane module 10 Reactor 10a 1st end 10b 2nd end 20. Housing G1 Inner surface J1 First opposing surface J2 2nd facing surface 21 Cylinder body 22 First end plate 23 Second end plate 30 First flange K1 end face L1 Inner surface 40 Second flange K2 end face L2 outer surface 35 First bonding material 45 Second bonding material

Claims

1. A cylindrical housing; A columnar membrane structure accommodated in the housing; a first annular flange surrounding a first end of the membrane structure; a first bonding material interposed between the first flange and the membrane structure; Equipped with the housing has a first opposing surface that faces an end surface of the first flange, and an inner circumferential surface that faces an outer circumferential surface of the first flange, The thermal expansion coefficient of the first bonding material is smaller than the thermal expansion coefficient of the first flange, The thermal expansion coefficient of the membrane structure is smaller than the thermal expansion coefficient of the first flange. Separation membrane module.

2. a second annular flange surrounding a second end of the membrane structure; A second bonding material interposed between the second flange and the membrane structure; Equipped with the housing has a second opposing surface that faces an end surface of the second flange, The inner circumferential surface of the housing faces an outer circumferential surface of the second flange, The thermal expansion coefficient of the second bonding material is smaller than the thermal expansion coefficient of the second flange, The thermal expansion coefficient of the membrane structure is smaller than the thermal expansion coefficient of the second flange. The separation membrane module according to claim 1 .

3. The housing includes a cylindrical main body having the inner circumferential surface, a first end plate having the first opposing surface, and a second end plate having the second opposing surface. The separation membrane module according to claim 2 .

4. The first flange is made of a ceramic material. The separation membrane module according to claim 1 .

5. The second flange is made of a ceramic material. The separation membrane module according to claim 3 .

6. The membrane structure is a reactor. The separation membrane module according to any one of claims 1 to 5.

7. The membrane structure is a separation filter. The separation membrane module according to any one of claims 1 to 5.

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