Separation membrane module

Abstract

This separation membrane module comprises a reactor (10) having a columnar shape, a first flange (30) having an annular shape and surrounding a first end part (10a) of the reactor (10), and a first intermediate part (50) disposed between a first end surface (F2) of the reactor 10 and a housing (20).

Description

Separation Membrane Module

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

[0002] Conventionally, separation membrane modules have been known that include a housing and a columnar membrane structure housed 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 feed gas to a liquid fuel using a separation membrane (see, for example, Patent Document 2).

[0003] International Publication No. 2018 / 180095 Japanese Patent Application Laid-Open No. 2018-008940

[0004] However, if the membrane structure comes into direct contact with the housing, the membrane structure will be damaged, so it is desirable to adopt a configuration in which the membrane structure does not come into direct contact with the housing.

[0005] An object of the present invention is to provide a separation membrane module that can suppress damage to the membrane structure.

[0006] The separation membrane module of the first aspect comprises a cylindrical housing, a columnar membrane structure accommodated in the housing, a first annular flange surrounding a first end of the membrane structure, and a first intermediate portion disposed between the first end face of the membrane structure and the housing.

[0007] The separation membrane module of the second aspect according to the first aspect further includes a first bonding material interposed between the first flange and the membrane structure and between the first intermediate portion and the membrane structure.

[0008] In the separation membrane module of a third aspect related to the first or second aspect, the first intermediate portion is integral with the first flange.

[0009] In the separation membrane module of a fourth aspect related to any one of the first to third aspects, each of the first intermediate portion and the first flange is made of a ceramic material.

[0010] The separation membrane module of a fifth aspect relating to any of the first to fourth aspects comprises a second annular flange surrounding the second end of the membrane structure, and a second intermediate portion arranged between the second end face of the membrane structure and the housing.

[0011] The separation membrane module of a sixth aspect related to the fifth aspect further includes a second bonding material interposed between the second flange and the membrane structure and between the second intermediate portion and the membrane structure.

[0012] In the separation membrane module of a seventh aspect related to the fifth or sixth aspect, the second intermediate portion is integral with the second flange.

[0013] In the separation membrane module of an eighth aspect related to any one of the fifth to seventh aspects, each of the second intermediate portion and the second flange is made of a ceramic material.

[0014] In the separation membrane module of a ninth aspect related to any one of the first to eighth aspects, the membrane structure is a reactor.

[0015] In the separation membrane module of a tenth aspect related to any one of the first to eighth aspects, the membrane structure is a separation filter.

[0016] According to the present invention, it is possible to provide a separation membrane module that can suppress damage to the membrane structure.

[0017] FIG. 1 is a cross-sectional view of a separation membrane module according to an embodiment. FIG. 2 is a partially enlarged view of FIG. 1. FIG. 3 is a partially enlarged view of FIG. 1. FIG. 4 is a cross-sectional view of a separation membrane module according to Modification 2. FIG. 5 is a cross-sectional view taken along line A-A in FIG. 4. FIG. 6 is a cross-sectional view taken along line B-B in FIG. 4. FIG. 7 is a cross-sectional view of a separation membrane module according to Modification 4. FIG. 8 is a cross-sectional view of a separation membrane module according to Modification 4. FIG. 9 is a cross-sectional view of a separation membrane module according to Modification 7. FIG. 10 is a cross-sectional view of a separation membrane module according to Modification 7. FIG. 11 is a cross-sectional view of a separation membrane module according to Modification 10. FIG. 12 is a cross-sectional view of a separation membrane module according to Modification 10. FIG. 13 is a cross-sectional view of a separation membrane module according to Modification 11. FIG. 14 is a cross-sectional view of a separation membrane module according to Modification 11. FIG. 15 is a cross-sectional view of a separation membrane module according to Modification 11. FIG. 16 is a cross-sectional view of a separation membrane module according to Modification 12. FIG. 17 is a cross-sectional view of a separation membrane module according to Modification 12. FIG. 18 is a cross-sectional view of a separation membrane module according to Modification 13. 19 is a cross-sectional view of a separation membrane module according to Modification 13. FIG. 20 is a cross-sectional view of a separation membrane module according to Modification 13.

[0018] (Separation membrane module 1) A separation membrane module 1 according to an embodiment will be described. Fig. 1 is a cross-sectional view schematically showing the configuration of the separation membrane module 1.

[0019] 1 , the separation membrane module 1 includes a reactor 10, a housing 20, a first flange 30, a second flange 40, a first intermediate portion 50, a second intermediate portion 60, a first bonding material 70, and a second bonding material 80. The reactor 10 is an example of the “membrane structure” according to the present invention.

[0020] [Reactor 10] The reactor 10 is housed 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.

[0021] 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 dioxide. The raw material gas may contain carbon monoxide. The raw material gas may be a so-called synthesis gas (Syngas). The liquid fuel is a fuel that is in a liquid state at room temperature and atmospheric pressure, or a fuel that can be liquefied under pressure at room temperature. Examples of fuels that are in a liquid state at room temperature and atmospheric 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.

[0022] 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: ２ +3H ２ ⇔ CH ３ OH+H ２ O (1)

[0023] The above reaction is an equilibrium reaction, and the reactor 10 can shift the reaction equilibrium toward the product by separating the water vapor, which is the product of the conversion reaction. To increase the conversion efficiency and reaction rate, the conversion reaction is preferably carried out 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 remains in this state at least until it leaves the reactor 10. The reactor 10 preferably has heat resistance and pressure resistance suitable for the synthesis conditions of the desired liquid fuel.

[0024] The reactor 10 according to this 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. A raw material gas flows into the reactor 10 through 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. A liquid fuel flows out of the reactor 10 through the second opening T2.

[0025] 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.

[0026] Here, the reactor 10 is composed of a porous support 11, a separation membrane 12, a catalyst 13, and a catalyst stopper 14.

[0027] 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 suitable. As the aggregate of the ceramic material, alumina (Al ２ O ３ ), titania (TiO ２ ), mullite (Al ２ O ３ SiO ２ ), cervenite and cordierite (Mg ２ Al ４ Si ５ O 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 necessarily need to contain an inorganic binder.

[0028] 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 particles (randomly selected) measured by cross-sectional microstructure observation using a scanning electron microscope (SEM).

[0029] 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. Inside 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 also be disposed on the outer surface of the porous support 11.

[0030] The separation membrane 12 allows water vapor, which is a product of the conversion reaction from the feed gas to liquid fuel, to pass through, thereby utilizing the equilibrium shift effect to shift the reaction equilibrium of the above formula (1) to the product side.

[0031] The separation membrane 12 has a specific resistance 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)).

[0032] 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 less permeable it is for components other than water vapor (such as hydrogen, carbon dioxide, and liquid fuel). 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 12. Inorganic membranes are preferred 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 preferred because of its excellent water vapor permeability.

[0034] The catalyst 13 is disposed inside the separation membrane 12, i.e., in the non-permeation side space S1. The catalyst 13 is preferably packed in the non-permeation side space S1, but may also 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 feed gas to the liquid fuel shown in formula (1) above.

[0035] Any known catalyst suitable for the 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.).

[0036] 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 prevents the catalyst 13 from leaking out through the second opening T2. The catalyst stopper 14 has a configuration that prevents the catalyst 13 from leaking out while not hindering the outflow of liquid fuel. For example, a mesh member or a perforated plate can be used as the catalyst stopper 14. Note that in this embodiment, the catalyst stopper 14 is fixed by being sandwiched between the housing 20 and the second flange 40, but it may also be attached to the second end face F3 of the reactor 10.

[0037] However, if leakage of the catalyst 13 is unlikely to occur (for example, if 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.

[0038] 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 the water vapor that is the product 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 below.

[0039] [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 that can withstand a conversion reaction under high temperature and high pressure (e.g., 180°C or higher, 2 MPa or higher). When the source gas and / or sweep gas contains hydrogen, the material of the housing 20 is preferably resistant to hydrogen embrittlement. The housing 20 can be mainly made of a metal material (stainless steel, etc.).

[0040] 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 23 .

[0041] The cylindrical body 21 is formed in a cylindrical shape extending in the longitudinal direction, and both ends of the cylindrical body 21 are expanded in diameter in the form of flanges.

[0042] 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 discharge port T4.

[0043] The inner circumferential surface G1 faces the outer circumferential surface F1 of the reactor 10, but 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 a product of the conversion reaction.

[0044] An annular first recess H1 is formed at one end of the inner circumferential surface G1. An annular first elastic member 26a is disposed in the first recess H1. The first elastic member 26a may be made of, for example, expanded graphite or a rubber O-ring. The first elastic member 26a is in close contact with a first flange 30, which will be described later. This provides a seal between the tube main body 21 and the first flange 30.

[0045] An annular second recess H2 is formed at the other end of the inner circumferential surface G1. An annular second elastic member 26b is disposed in the second recess H2. The second elastic member 26b may be made of, for example, expanded graphite or a rubber O-ring. The second elastic member 26b is in close contact with the second flange 40, which will be described later. This provides a seal between the tube main body 21 and the second flange 40.

[0046] An annular first recess H3 is formed in the first end surface G2. A third elastic member 26c is disposed in the first recess H3. The third elastic member 26c may be made of, for example, expanded graphite or a rubber O-ring. The third elastic member 26c is in close contact with the first end plate 22. This seals the gap between the tube main body 21 and the first end plate 22.

[0047] A ring-shaped second recess H4 is formed in the second end surface G3. A fourth elastic member 26d is disposed in the second recess H4. The fourth elastic member 26d may be, for example, an O-ring made of expanded graphite or rubber. The fourth elastic member 26d is in close contact with the second end plate 23. This seals the gap between the tube main body 21 and the second end plate 23.

[0048] The sweep gas inlet T3 and the sweep gas outlet T4 are connected to the permeate side space S2. The sweep gas is supplied from the sweep gas inlet T3 to the permeate side space S2. The sweep gas takes in water vapor in the permeate side space S2 and absorbs the reaction heat associated with the conversion reaction. The sweep gas is discharged together with water vapor from the sweep gas outlet T4. Hydrogen and / or carbon dioxide can be used as the sweep gas. Alternatively, an inert gas (e.g., nitrogen) or air may be used as the sweep gas. In this embodiment, the sweep gas inlet T3 and the sweep gas outlet T4 are diagonally opposed to each other in a cross-sectional view, but the respective positions of the sweep gas inlet T3 and the sweep gas outlet T4 can be changed as appropriate.

[0049] The first end plate 22 is an annular plate member and has an inlet 22a through which the raw material gas flows in. The raw material gas is supplied to the non-permeation side space S1 of the reactor 10 through the inlet 22a.

[0050] The central portion of the first end plate 22 has an expanded diameter like a flange. The first end plate 22 has a first opposing surface J1. The first opposing surface J1 faces the first end face F2 of the reactor 10 and the end face K1 of the first flange 30 (described later). In this embodiment, the first opposing surface J1 is spaced apart from both the first end face F2 of the reactor 10 and the end face K1 of the first flange 30. The first opposing surface J1 abuts against the first end face G2 of the cylindrical main body 21.

[0051] The first end plate 22 is connected to the tube 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.

[0052] The second end plate 23 is an annular plate member and has an outlet 23a through which the liquid fuel flows out. The liquid fuel is discharged from the non-permeation side space S1 of the reactor 10 to the outside via the outlet 23a.

[0053] The central portion of the second end plate 23 has an expanded diameter like a flange. The second end plate 23 has a second opposing surface J2. The second opposing surface J2 faces the second end face F3 of the reactor 10 and the end face K2 of the second flange 40 (described later). In this embodiment, the second opposing surface J2 is spaced apart from both the second end face F3 of the reactor 10 and the end face K2 of the second flange 40. The second opposing surface J2 abuts against the second end face G3 of the cylindrical main body 21.

[0054] 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.

[0055] [First flange 30] The first flange 30 is attached to the reactor 10. The first flange 30 is bonded to the reactor 10 by a first bonding material 70. The first flange 30 functions as a spacer for forming a permeate-side space S2 between the reactor 10 and the cylindrical 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 cylindrical main body 21. The first flange 30 supports the first end 10a of the reactor 10 at a position separated from the cylindrical main body 21. This forms a permeate-side space S2 between the reactor 10 and the cylindrical main body 21.

[0056] The first flange 30 has an end surface K1, an outer peripheral surface L1, and an inner peripheral surface M1. The end surface K1 is the longitudinally outer surface of the first flange 30. The end surface K1 faces the first opposing surface J1 of the first end plate 22. At least a portion of the end surface K1 may abut against the first opposing surface J1. In the present embodiment, the end surface 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 cylindrical 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. The inner peripheral surface M1 is provided on the opposite side of the outer peripheral surface L1. The inner peripheral surface M1 faces the outer peripheral surface F1 of the reactor 10 via the first bonding material 70. The inner peripheral surface M1 may abut against the first intermediate portion 50 described below.

[0057] The first flange 30 is made of a dense ceramic material. Examples of ceramic materials 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 must 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.

[0058] [Second flange 40] The second flange 40 is attached to the reactor 10. The second flange 40 is bonded to the reactor 10 by a second bonding material 80. 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 main 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 main body 21. The second flange 40 supports the second end 10b of the reactor 10 at a position spaced apart from the cylindrical main body 21.

[0059] The second flange 40 has an end surface K2, an outer peripheral surface L2, and an inner peripheral surface M2. The end surface K2 is the longitudinally outer surface of the second flange 40. The end surface K2 faces the second opposing surface J2 of the second end plate 23. At least a portion of the end surface K2 may abut against the second opposing surface J2. In the present embodiment, the end surface 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 cylindrical 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. The inner peripheral surface M2 is provided on the opposite side of the outer peripheral surface L2. The inner peripheral surface M2 faces the outer peripheral surface F1 of the reactor 10 via the second bonding material 80. The inner peripheral surface M2 may abut against the second intermediate portion 60, which will be described later.

[0060] The second flange 40 is made of a dense ceramic material. Examples of ceramic materials 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 must 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.

[0061] [First Intermediate Section 50] The first intermediate section 50 is an annular thin plate member. The first intermediate section 50 is disposed between the reactor 10 and the housing 20. Specifically, the first intermediate section 50 is disposed between the first end face F2 of the reactor 10 and the first opposing surface J1 of the first end plate 22. In this manner, by interposing the first intermediate section 50 between the reactor 10 and the housing 20, direct contact between the reactor 10 and the first end plate 22 can be prevented. Therefore, damage (such as chipping or cracking) to the reactor 10 can be prevented.

[0062] 1 , the first intermediate section 50 is preferably bonded to the reactor 10 by a first bonding material 70. This allows the first intermediate section 50 to be substantially integrated with the reactor 10, thereby further suppressing damage to the reactor 10.

[0063] The first intermediate section 50 can be made of a ceramic material, a resin material, or a metal material. The ceramic material used to make the first flange 30 can be used as the ceramic material. The first intermediate section 50 is preferably harder than the porous support 11 of the reactor 10. This allows the reactor 10 to be better protected by the first intermediate section 50, thereby further reducing damage to the reactor 10.

[0064] Here, Fig. 2 is a partially enlarged view of Fig. 1. As shown in Fig. 2, the first intermediate portion 50 has an opposing surface P1, an abutting surface Q1, a joining surface R1, and an inner circumferential surface U1.

[0065] The opposing surface P1 faces the housing 20. The opposing surface P1 may abut against the opposing surface J1 of the first end plate 22. In this embodiment, the opposing surface P1 is flush with the end surface K1 of the first flange 30, but a step may be formed between the opposing surface P1 and the end surface K1. The abutting surface Q1 abuts against the inner circumferential surface M1 of the first flange 30. The joining surface R1 is joined to the first joining material 70. In this embodiment, the inner circumferential surface U1 is flush with the inner circumferential surface U2 of the first end plate 22, but it does not have to be flush with the inner circumferential surface U2. In this embodiment, the opposing surface P1, the abutting surface Q1, and the joining surface R1 are each flat, but at least one of them may be wholly or partially curved or bent.

[0066] [Second Intermediate Section 60] The second intermediate section 60 is an annular thin plate member. The second intermediate section 60 is disposed between the reactor 10 and the housing 20. Specifically, the second intermediate section 60 is disposed between the second end face F3 of the reactor 10 and the second opposing surface J2 of the second end plate 23. In this manner, by interposing the second intermediate section 60 between the reactor 10 and the second end plate 23, direct contact between the reactor 10 and the housing 20 can be prevented. Therefore, damage (such as chipping or cracking) to the reactor 10 can be prevented.

[0067] 1, the second intermediate section 60 is preferably bonded to the reactor 10 by the second bonding material 80. This allows the second intermediate section 60 to be substantially integrated with the reactor 10, thereby further suppressing damage to the reactor 10.

[0068] The second intermediate section 60 can be made of a ceramic material, a resin material, or a metal material. The ceramic material used to make the second flange 40 can be used as the ceramic material. The second intermediate section 60 is preferably harder than the porous support 11 of the reactor 10. This allows the reactor 10 to be better protected by the second intermediate section 60, thereby further reducing damage to the reactor 10.

[0069] Here, Fig. 3 is a partially enlarged view of Fig. 1. As shown in Fig. 3, the second intermediate portion 60 has an opposing surface P2, an abutting surface Q2, a joining surface R2, and an inner circumferential surface U3.

[0070] The opposing surface P2 faces the housing 20. The opposing surface P2 may abut against the opposing surface J2 of the second end plate 23. In this embodiment, the opposing surface P2 is flush with the end surface K2 of the second flange 40, but a step may be formed between the opposing surface P2 and the end surface K2. The abutting surface Q2 abuts against the second flange 40. The abutting surface Q2 abuts against the inner circumferential surface M2 of the second flange 40. The joining surface R2 is joined to the second joining material 80. In this embodiment, the inner circumferential surface U3 is flush with the inner circumferential surface U4 of the second end plate 23, but does not have to be flush with the inner circumferential surface U4. In this embodiment, the opposing surface P2, the abutting surface Q2, and the joining surface R2 are each flat, but at least one of them may be wholly or partially curved or bent.

[0071] [First bonding material 70] The first bonding material 70 is interposed between the first flange 30 and the reactor 10, and between the first intermediate portion 50 and the reactor 10. The first bonding material 70 bonds the first flange 30 to the reactor 10 and also bonds the first intermediate portion 50 to the reactor 10. The first bonding material 70 is disposed in at least a part of the gap between the first flange 30 and the reactor 10 and in at least a part of the gap between the first intermediate portion 50 and the reactor 10. As shown in FIG. 2 , the cross section of the first bonding material 70 is L-shaped.

[0072] The assembly of the first flange 30 and the reactor 10 joined by the first bonding material 70 is the "separation membrane assembly" according to the present invention.

[0073] The first bonding material 70 may be crystallized glass, amorphous glass, brazing material, or ceramics, and in consideration of heat resistance and pressure resistance, crystallized glass is particularly preferable.

[0074] Examples of the crystallized glass include SiO ２ -B ２ O ３ system, SiO ２ -CaO system, SiO ２ -Al２ O ３ system, SiO ２ -MgO-based, SiO ２ -ZnO-BaO system, SiO ２ -B ２ O ３ -CaO-based or SiO ２ -MgO-CaO system, SiO ２ -Al ２ O ３ -B ２ O ３ system, SiO ２ -MgO-Al ２ O ３ In this specification, the term "crystallized glass" refers to glass in which the ratio of the "volume occupied by the crystalline phase" to the total volume (degree of crystallization) 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%.

[0075] [Second bonding material 80] The second bonding material 80 is interposed between the second flange 40 and the reactor 10, and between the second intermediate portion 60 and the reactor 10. The second bonding material 80 bonds the second flange 40 to the reactor 10 and also bonds the second intermediate portion 60 to the reactor 10. The second bonding material 80 is disposed in at least a part of the gap between the second flange 40 and the reactor 10 and in at least a part of the gap between the second intermediate portion 60 and the reactor 10. As shown in FIG. 3 , the cross section of the second bonding material 80 is L-shaped.

[0076] The assembly of the second flange 40 and the reactor 10 joined by the second bonding material 80 is the "separation membrane assembly" according to the present invention.

[0077] The second bonding material 80 may be made of crystallized glass, amorphous glass, brazing material, or ceramics, and in consideration of heat resistance and pressure resistance, crystallized glass is particularly preferable.

[0078] [Assembly of Separation Membrane Module 1] The assembly process of the separation membrane module 1 includes a step of producing a reactor assembly in which the first and second flanges 30, 40 and the first and second intermediate portions 50, 60 are joined to the reactor 10, and a step of accommodating the reactor assembly in the housing 20.

[0079] The process for fabricating the reactor assembly includes a first step of forming a green body of the bonding material, a second step of attaching the flanges and intermediate portions, and a third step of heating the green body of the bonding material. In the first step, a green body of the first bonding material 70 is formed at the first end 10a of the reactor 10, and a green body of the second bonding material 80 is formed at the second end 10b of the reactor 10. In the second step, the first flange 30 and the first intermediate portion 50 are attached to surround the green body of the first bonding material 70, and the second flange 40 and the second intermediate portion 60 are attached to surround the green body of the second bonding material 80. In the third step, the green bodies of the first and second bonding materials 70, 80 are heated to cause crystal growth or melting, and then cooled to room temperature to form the first and second bonding materials 70, 80. As a result of the above, the reactor assembly is completed in which the first and second flanges 30, 40 and the first and second intermediate portions 50, 60 are joined to the reactor 10 via the first and second joining materials 70, 80.

[0080] 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 to fourth elastic members 26a to 26d are fitted into the first to fourth recesses H1 to 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. This completes the separation membrane module 1 in which the reactor assembly is accommodated in the housing 20.

[0081] Because the first intermediate portion 50 is interposed between the reactor 10 and the first end plate 22, direct contact between the first end plate 22 and the reactor 10 can be prevented in the sixth step, thereby preventing damage to the reactor 10. Similarly, because the second intermediate portion 60 is interposed between the reactor 10 and the second end plate 23, direct contact between the second end plate 23 and the reactor 10 can be prevented in the sixth step, thereby preventing damage to the reactor 10.

[0082] (Modifications 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.

[0083] [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 the catalyst 13. Furthermore, 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.

[0084] When a separation filter is used as the membrane structure, no reaction heat is generated and there is little need for temperature control. Therefore, the pressure on the sweep gas outlet T4 side may be reduced more than that on the sweep gas supply port T3 side, thereby allowing the components that have permeated the separation membrane to be discharged from the sweep gas outlet T4.

[0085] [Modification 2] In the above embodiment, the reactor 10, which is an example of a membrane structure, is a tubular type, but it may also be a monolith type. Furthermore, when a separation filter is used as the membrane structure, the separation filter may be a tubular type or a monolith type. The monolith type refers to a shape having multiple cells that penetrate in the longitudinal direction, and is a concept that includes a honeycomb type.

[0086] Fig. 4 is a cross-sectional view that schematically shows the configuration of a separation membrane module 1a that includes a monolithic reactor 100. However, in Fig. 4, only the reactor 100 is shown in side view.

[0087] 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 90 and a reactor 100 instead of the reactor 10. Note that the catalyst stopper 14 is also an optional configuration in the reactor 100.

[0088] The flow stopper 90 is formed in an annular shape. The flow stopper 90 is disposed between the reactor 100 and the housing 20. The flow stopper 90 divides the gap between the reactor 100 and the housing 20 into a sweep gas exhaust space S21 and a sweep gas supply space S22. The flow stopper 90 prevents the sweep gas from flowing directly between the sweep gas exhaust space S21 and the sweep gas supply space S22. The flow stopper 90 need not seal the space between the reactor 100 and the housing 20 as long as it can directly prevent the flow of the sweep gas. The flow stopper 90 can be made of, for example, expanded graphite, rubber, resin, metal, etc.

[0089] 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 18 .

[0090] 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 separation membrane 12 described above 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 catalyst 13 described above is disposed in the non-permeation side space S1.

[0091] The second flow path 16 is formed inside the reactor 100. The second flow path 16 extends along the longitudinal direction. The second flow path 16 is closed at the first and second end faces F2, F3.

[0092] The first slits 17 are formed at the first end 100a of the reactor 100. The first slits 17 radially penetrate each second flow path 16 and open to the outer circumferential surface F1. Therefore, the first slits 17 communicate with each second flow path 16 and the sweep gas exhaust space S21.

[0093] The second slits 18 are formed at 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 sweep gas supply space S22.

[0094] When the raw material gas is supplied to the first flow path 15, the raw material gas is converted into liquid fuel by the action of the catalyst 13, and water vapor, which is a product of the conversion reaction, passes through the separation membrane 12 and flows into the second flow path 16. The water vapor that has flowed into the second flow path 16 is taken in by the sweep gas that flows from the sweep gas supply port T3 through the sweep gas supply space S22 and the second slit 18 into the second flow path 16, and then passes through the first slit 17 and the sweep gas discharge space S21 and is discharged to the outside from the sweep gas discharge port T4.

[0095] In this modification, the sweep gas supply port T3 and the sweep gas exhaust port T4 are arranged on a straight line intersecting the axis of the reactor 10 in a cross-sectional view. This allows the flow path length of the sweep gas in the sweep gas exhaust space S21 to be equal to the flow path length of the sweep gas in the sweep gas supply space S22, thereby preventing the flow of the sweep gas from becoming biased. However, the relative positions of the sweep gas supply port T3 and the sweep gas exhaust port T4 can be changed as appropriate.

[0096] 5 is a cross-sectional view taken along line A-A in FIG. 4. As shown in FIG. 5, the first slit 17 penetrates the interior 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 peripheral surface F1. The sweep gas that flows out from each of the two openings of the first slit 17 into the sweep gas exhaust space S21 passes through the sweep gas exhaust space S21 and is exhausted to the outside from the sweep gas exhaust port T4.

[0097] 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 sweep gas discharge space S21.

[0098] 6 is a cross-sectional view taken along the line B-B in FIG. 4. As shown in FIG. 6, the second slit 18 penetrates the interior 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 peripheral surface F1. The sweep gas supplied from the sweep gas supply port T3 to the sweep gas supply space S22 passes through the sweep gas supply space S22 and flows into each of the two openings of the second slit 18.

[0099] Here, the second extension direction in which the second slits 18 extend 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 sweep gas supply 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 slits 18, thereby suppressing bias in the sweep gas flow in the sweep gas supply space S22.

[0100] [Variation 3] In the above embodiment, the separation membrane 12 is in contact with the catalyst 13. However, 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 the heat of reaction. The buffer layer may be made of a ceramic material or an organic polymer material. Examples of ceramic materials that can be used include silica, alumina, and chromia. Examples of organic polymer materials that can be used include PTFE, PVA, and PEG.

[0101] [Variation 4] In the above embodiment, the first flange 30 is separate from the first intermediate section 50. However, as shown in Fig. 7, the first flange 30 may be integral with the first intermediate section 50. When the first flange 30 is integral with the first intermediate section 50, handling during the assembly process of the separation membrane module 1 can be improved.

[0102] Similarly, in the above embodiment, the second flange 40 is separate from the second intermediate portion 60, but as shown in Figure 7, the second flange 40 may be integral with the second intermediate portion 60.

[0103] Furthermore, as shown in Figure 8, even when using the monolithic membrane structure described in the above variant example 2, the first flange 30 may be integral with the first intermediate portion 50, and the second flange 40 may be integral with the second intermediate portion 60.

[0104] [Variation 5] In the above embodiment, the first intermediate section 50 is arranged in the entire gap between the reactor 10 and the first end plate 22. However, the first intermediate section 50 may be arranged in only a part of the gap. In this case, the first intermediate section 50 may be a C-shaped thin plate member or a plurality of thin plate members arranged circumferentially spaced apart from one another.

[0105] Similarly, in the above embodiment, the second intermediate portion 60 is arranged in the entire gap between the reactor 10 and the second end plate 23, but it may be arranged in only a part of the gap.

[0106] [Variation 6] In the above embodiment, the first bonding material 70 is interposed between the first flange 30 and the reactor 10 and between the first intermediate portion 50 and the reactor 10, respectively. However, the first bonding material 70 does not have to be interposed between the first intermediate portion 50 and the reactor 10. In this case, the first intermediate portion 50 may be in direct contact with the reactor 10.

[0107] Similarly, in the above embodiment, the second bonding material 80 is interposed between the second flange 40 and the reactor 10 and between the second intermediate portion 60 and the reactor 10, respectively. However, the second bonding material 80 does not have to be interposed between the second intermediate portion 60 and the reactor 10. In this case, the second intermediate portion 60 may be in direct contact with the reactor 10.

[0108] [Variation 7] In the above embodiment, as shown in Fig. 2, the inner circumferential surface U1 of the first intermediate portion 50 is flush with the inner circumferential surface U2 of the first end plate 22. However, this is not limited to this. As shown in Fig. 9, the inner circumferential surface U1 of the first intermediate portion 50 may be located radially inward of the inner circumferential surface U2 of the first end plate 22. Alternatively, as shown in Fig. 10, the inner circumferential surface U1 of the first intermediate portion 50 may be located radially outward of the inner circumferential surface U2 of the first end plate 22.

[0109] 3 , the inner circumferential surface U3 of the second intermediate portion 60 is flush with the inner circumferential surface U4 of the second end plate 23. However, this is not limited to this. Although not shown, the inner circumferential surface U3 of the second intermediate portion 60 may be located radially inward from the inner circumferential surface U4 of the second end plate 23, or may be located radially outward from the inner circumferential surface U4 of the second end plate 23.

[0110] [Variation 8] In the above embodiment, the separation membrane 12 is permeable to water vapor, which is a product of the conversion reaction from the feed gas to the liquid fuel. However, this is not limited to this. The separation membrane 12 may also be permeable to the liquid fuel itself, which is a product of the conversion reaction from the feed gas to the liquid fuel. In this case, too, the reaction equilibrium of the above formula (1) can be shifted toward the product side.

[0111] In addition, when the separation membrane 12 is permeable to liquid fuel, the reaction does not produce water vapor as a by-product (for example, H ２ +CO ⇔ CH ３ Even when producing liquid fuels using methyl methyl hydroxybenzoate (Methyl hydroxybenzoate), the reaction equilibrium can be shifted to the product side.

[0112] [Variation 9] In the separation membrane module 1 according to the above embodiment (see FIG. 1), the sweep gas supply port T3 and the sweep gas outlet T4 are arranged diagonally opposite each other in a side view, and the sweep gas flows from the sweep gas supply port T3 toward the sweep gas outlet T4, but this is not limited to this.

[0113] For example, as shown in Fig. 11 , the sweep gas supply port T3 and the sweep gas exhaust port T4 may be arranged on the same side of the reactor 10 in a side view, or a rectifying plate 20a may be provided to close a part of the gap between the reactor 10 and the housing 20. Although three rectifying plates 20a are provided in Fig. 11 , the number of the rectifying plates 20a may be one, two, or four or more. The position of the rectifying plate 20a can be set as appropriate.

[0114] 12, 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 through a sweep gas outlet T4. The position of the sweep gas outlet T4 can be set as appropriate.

[0115] The configurations of FIGS. 11 and 12 can also be applied to a case where a separation filter is used as the membrane structure instead of the reactor 10.

[0116] [Modification 10] In the separation membrane module 1 (see FIG. 1) according to the above embodiment, only one reactor 10 is accommodated in the housing 20, but the present invention is not limited to this.

[0117] For example, as shown in FIG. 13, a plurality of reactors 10 may be housed within a housing 20.

[0118] 14, a straightening plate 20a may be provided to close a part of the gap between each reactor 10 and the housing 20. In FIG. 14, three straightening plates 20a are provided, but the number of 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. 14, the sweep gas supply port T3 and the sweep gas exhaust port T4 may be arranged on the same side of the reactor 10 in a side view.

[0119] 15, 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 through a sweep gas outlet T4. The position of the sweep gas outlet T4 can be set as appropriate.

[0120] The configurations of FIGS. 13 to 15 can also be applied to a case where a separation filter is used as the membrane structure instead of the reactor 10.

[0121] [Modification 11] In the separation membrane module 1a according to Modification 2 (see FIG. 4), the sweep gas supply port T3 and the sweep gas discharge port T4 are arranged diagonally opposite each other in a side view, but this is not limiting.

[0122] For example, as shown in FIG. 16 , the sweep gas supply port T3 and the sweep gas exhaust port T4 may be arranged on the same side of the reactor 100 in a side view, or a rectifying plate 20b may be provided to block a portion of the gap between the reactor 100 and the housing 20. In FIG. 16 , one rectifying plate 20b is provided on each side of the flow stopper 90. The rectifying 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 rectifying 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 rectifying plates 20b can be set as appropriate. Also, a portion of the sweep gas may pass through the inside of the flow stopper 90 .

[0123] 17, 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 through a sweep gas outlet T4. The position of the sweep gas outlet T4 can be set as appropriate.

[0124] The configurations of FIGS. 16 and 17 can also be applied to a case where a separation filter is used as the membrane structure instead of the reactor 100.

[0125] [Modification 12] In the separation membrane module 1a according to the above-described modification 2 (see FIG. 4), only one reactor 100 is accommodated in the housing 20, but the present invention is not limited to this.

[0126] For example, as shown in FIG. 18, a plurality of reactors 100 may be housed within the housing 20 .

[0127] 19, a straightening plate 20b may be provided to block a portion of the gap between the reactor 100 and the housing 20. In FIG. 19, 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 as appropriate. Furthermore, a portion of the sweep gas may pass through the inside of the flow stopper 90. As shown in FIG. 19, 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.

[0128] 20, 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 through a sweep gas outlet T4. The position of the sweep gas outlet T4 can be set as appropriate.

[0129] 18 to 20 can also be applied to a case where a separation filter is used as the membrane structure instead of the reactor 100.

[0130] REFERENCE SIGNS LIST 1 Separation membrane module 10 Reactor 10a First end 10b Second end F1 Outer circumferential surface F2 First end surface F3 Second end surface 20 Housing 21 Cylindrical body 22 First end plate 23 Second end plate 30 First flange 40 Second flange 50 First intermediate portion 60 Second intermediate portion 70 First bonding material 80 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 intermediate portion disposed between a first end face of the membrane structure and the housing; a first bonding material interposed between the first flange and the membrane structure, and between the first intermediate portion and the membrane structure; A separation membrane module comprising:

2. the first intermediate portion is integral with the first flange; The separation membrane module according to claim 1 .

3. The first intermediate portion and the first flange are each made of a ceramic material. The separation membrane module according to claim 1 .

4. a second annular flange surrounding a second end of the membrane structure; a second intermediate portion disposed between a second end surface of the membrane structure and the housing; The separation membrane module according to claim 1 , further comprising:

5. Further comprising a second bonding material interposed between the second flange and the membrane structure and between the second intermediate portion and the membrane structure. The separation membrane module according to claim 4.

6. the second intermediate portion is integral with the second flange; The separation membrane module according to claim 4.

7. The second intermediate portion and the second flange are each made of a ceramic material. The separation membrane module according to claim 4.

8. The membrane structure is a reactor. The separation membrane module according to claim 1 .

9. The membrane structure is a separation filter. The separation membrane module according to claim 1 .