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

Technical Field

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

Background Art

[0002] Conventionally, a separation membrane module including a housing and a columnar membrane structure housed in the housing has been known. Examples of the membrane structure include a separation filter configured to separate a predetermined component from a mixed fluid with 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 with a separation membrane (see, for example, Patent Document 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] By the way, since the membrane structure is damaged when it comes into direct contact with the housing, 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 capable of suppressing damage to the membrane structure.

Means for Solving the Problems

[0006] The separation membrane module according to the first aspect includes a cylindrical housing, a columnar membrane structure housed in the housing, an annular first flange surrounding the first end portion of the membrane structure, and a first intermediate portion disposed between the first end surface of the membrane structure and the housing.

[0007] The separation membrane module of the second embodiment according to the first embodiment further comprises a first bonding member interposed between the first flange and the first intermediate portion and the membrane structure, respectively.

[0008] In a third embodiment of the separation membrane module relating to the first or second embodiment, the first intermediate portion is integrated with the first flange.

[0009] In a fourth embodiment of the separation membrane module relating to any of the first to third embodiments, the first intermediate portion and the first flange are each made of a ceramic material.

[0010] A fifth-dimensional separation membrane module relating to any of the first to fourth embodiments comprises an annular second flange surrounding the second end of the membrane structure and a second intermediate portion disposed between the second end face of the membrane structure and the housing.

[0011] The separation membrane module of the sixth embodiment relating to the fifth embodiment further comprises a second bonding member interposed between the second flange and the second intermediate portion and the membrane structure, respectively.

[0012] In the seventh embodiment of the separation membrane module relating to the fifth or sixth embodiment, the second intermediate portion is integrated with the second flange.

[0013] In the eighth embodiment of the separation membrane module relating to any of the fifth to seventh embodiments, the second intermediate portion and the second flange are each made of a ceramic material.

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

[0015] In the separation membrane module of the tenth embodiment relating to any of the first to eighth embodiments, the membrane structure is a separation filter. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a separation membrane module capable of suppressing damage to the membrane structure.

Brief Description of the Drawings

[0017] [Figure 1] FIG. 1 is a cross-sectional view of a separation membrane module according to an embodiment. [Figure 2] FIG. 2 is a partially enlarged view of FIG. 1. [Figure 3] FIG. 3 is a partially enlarged view of FIG. 1. [Figure 4] FIG. 4 is a cross-sectional view of a separation membrane module according to Modification 2. [Figure 5] FIG. 5 is a cross-sectional view taken along the line A-A of FIG. 4. [Figure 6] FIG. 6 is a cross-sectional view taken along the line B-B of FIG. 4. [Figure 7] FIG. 7 is a cross-sectional view of a separation membrane module according to Modification 4. [Figure 8] FIG. 8 is a cross-sectional view of a separation membrane module according to Modification 4. [Figure 9] FIG. 9 is a cross-sectional view of a separation membrane module according to Modification 7. [Figure 10] FIG. 10 is a cross-sectional view of a separation membrane module according to Modification 7. [Figure 11] FIG. 11 is a cross-sectional view of a separation membrane module according to Modification 10. [Figure 12] FIG. 12 is a cross-sectional view of a separation membrane module according to Modification 10. [Figure 13] FIG. 13 is a cross-sectional view of a separation membrane module according to Modification 11. [Figure 14] FIG. 14 is a cross-sectional view of a separation membrane module according to Modification 11. [Figure 15] FIG. 15 is a cross-sectional view of a separation membrane module according to Modification 11. [Figure 16] FIG. 16 is a cross-sectional view of a separation membrane module according to Modification 12. [[ID=�5]] [Figure 17] FIG. 17 is a cross-sectional view of a separation membrane module according to Modification 12. [Figure 18]Figure 18 is a cross-sectional view of a separation membrane module according to modified example 13. [Figure 19] Figure 19 is a cross-sectional view of a separation membrane module according to modified example 13. [Figure 20] Figure 20 is a cross-sectional view of the separation membrane module according to modified example 13. [Modes for carrying out the invention]

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

[0019] As shown in Figure 1, the separation membrane module 1 comprises a reactor 10, a housing 20, a first flange 30, a second flange 40, a first intermediate section 50, a second intermediate section 60, a first joining member 70, and a second joining member 80. The reactor 10 is an example of a "membrane structure" according to the present invention.

[0020] [Reactor 10] The reactor 10 is housed within the housing 20. The reactor 10 is formed in a columnar shape extending in the longitudinal direction. The external shape of the reactor 10 is not particularly limited, but can be cylindrical, elliptical, or polygonal.

[0021] Reactor 10 is a so-called membrane reactor for converting the raw material gas into 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 so-called synthesis gas. The liquid fuel is a fuel that is in a liquid state at room temperature and pressure, or a fuel that can be liquefied at room temperature and pressure. Examples of fuels that are in a liquid state at room temperature and pressure include methanol, ethanol, and C2. n H 2(m-2n) Examples include liquid fuels represented by (m being an integer less than 90, and n being an integer less than 30), and mixtures thereof. Examples of fuels that can be liquefied at room temperature and under pressure include propane, butane, and mixtures thereof.

[0022] For example, the reaction equation (1) for synthesizing methanol by catalytic hydrogenation of a source gas containing hydrogen and carbon dioxide in the presence of a catalyst is as follows: CO2 + 3H2 ⇔ CH3OH + H2O (1)

[0023] The above reaction is an equilibrium reaction, and the reactor 10 can shift the reaction equilibrium to the product side by separating the water vapor, which is a product of the conversion reaction. To increase the conversion efficiency and reaction rate, it is preferable to carry out the conversion reaction under high temperature and high pressure (for example, 180°C or higher, 2 MPa or higher). The liquid fuel is in a gaseous state at the time of synthesis and is maintained in a gaseous state at least until it flows out of the reactor 10. It is preferable that the reactor 10 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 Figure 1, the reactor 10 has an outer circumferential surface F1, a first end surface F2, and a second end surface F3. The outer circumferential surface F1 is a side surface of the columnar reactor 10. The outer circumferential surface F1 is connected to the first end surface F2 and the second end surface F3, respectively. The first end surface F2 is one end surface of the columnar reactor 10. A first opening T1 is formed on 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 columnar reactor 10. A second opening T2 is formed on the second end surface F3. The liquid fuel flows out of the reactor 10 from 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 composed of a porous material. As the porous material, ceramic materials, metal materials, resin materials, and composites thereof can be used, with ceramic materials being particularly preferred. As aggregates for the ceramic material, alumina (Al2O3), titania (TiO2), mullite (Al2O3·SiO2), celben and cordierite (Mg2Al4Si5O 18 ), and composite materials containing two or more of these can be used, and alumina is preferred considering availability, soil stability and corrosion resistance. As an inorganic binder for the ceramic material, at least one of titania, mullite, easily sintered alumina, silica, glass frit, clay minerals, and easily sintered cordierite can be used. However, the ceramic material does not need to contain an inorganic binder.

[0028] The average pore diameter of the porous support 11 can be between 5 μm and 25 μm. The average pore diameter of the porous support 11 can be measured by the mercury intrusion method. The porosity of the porous support 11 can be between 25% and 50%. The average particle size of the porous material can be between 1 μm and 100 μm. The average particle size is the arithmetic mean of the maximum diameter of 30 measured 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. The inside of the separation membrane 12 is an impermeable space S1 to which the raw material gas is supplied. The impermeable space S1 is the space between the first opening T1 and the second opening T2. In this embodiment, the separation membrane 12 is located on the inner surface of the porous support 11, but it may also be located on the outer surface of the porous support 11.

[0030] The separation membrane 12 allows water vapor, a product of the conversion reaction from the raw material gas to liquid fuel, to pass through. This allows the reaction equilibrium in equation (1) to be shifted towards the product side by utilizing the equilibrium shift effect.

[0031] The separation membrane 12 has a density of 100 nmol / (s·Pa·m). 2 It is preferable to have a water vapor permeability coefficient of ) or higher. The water vapor permeability coefficient can be determined by known methods (see Ind.Eng.Chem.Res.,40,163-175(2001)).

[0032] The separation membrane 12 preferably has a separation coefficient of 100 or more. The larger the separation coefficient, the easier it is for water vapor to permeate, and the less likely it is for components other than water vapor (such as hydrogen, carbon dioxide, and liquid fuel) to permeate. The separation coefficient 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, or composite membranes thereof. In particular, LTA-type zeolite membranes with a molar ratio (Si / Al) of silicon (Si) to aluminum (Al) of 1.0 to 3.0 are preferred because they have excellent water vapor permeability.

[0034] The catalyst 13 is placed inside the separation membrane 12, i.e., in the impermeable space S1. Preferably, the catalyst 13 is filled in the impermeable space S1, but it may also be arranged in layers or in islands on the surface of the separation membrane 12. The catalyst 13 promotes the conversion reaction from the raw material gas to the liquid fuel shown in formula (1) above.

[0035] For catalyst 13, any known catalyst suitable for the conversion reaction from raw material gas to liquid fuel can be used. Examples of catalyst 13 include metal catalysts (copper, palladium, etc.), oxide catalysts (zinc oxide, zirconia, gallium oxide, etc.), and catalysts that combine these (copper-zinc oxide, copper-zinc oxide-alumina, copper-zinc oxide-chromium oxide-alumina, copper-cobalt-titania, and catalysts modified with palladium).

[0036] The catalyst stopper 14 is positioned to cover the second opening T2 formed on 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 without obstructing the outflow of liquid fuel. For example, a mesh member or a perforated plate can be used as the catalyst stopper 14. 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 layers or in island-like formations on the surface of the separation membrane 12), the reactor 10 does not need to have a catalyst stopper 14.

[0038] In the reactor 10, the raw material gas supplied to the impermeable space S1 is converted into liquid fuel by the action of the catalyst 13, and the water vapor, which is a product of the conversion reaction, is separated into the permeable space S2, which will be described later, by passing through the separation membrane 12 and the porous support 11.

[0039] [Housing 20] The housing 20 is formed in a cylindrical shape overall. The housing 20 houses the reactor 10. The housing 20 has a structure that can withstand the conversion reaction under high temperature and high pressure (e.g., 180°C or higher, 2 MPa or higher). If the source gas and / or sweep gas contains hydrogen, it is preferable that the constituent materials of the housing 20 are resistant to hydrogen embrittlement. The housing 20 can be made mainly of metallic materials (such as stainless steel).

[0040] As shown in Figure 1, the housing 20 is composed of a cylindrical body 21, a first end plate 22, and a second end plate 23.

[0041] The cylindrical body 21 is formed in a cylindrical shape that extends in the longitudinal direction. Both ends of the cylindrical body 21 are widened in a flange-like manner.

[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 outlet T4.

[0043] The inner circumferential surface G1 faces the outer circumferential surface F1 of the reactor 10 and is separated from the outer circumferential surface F1. The gap between the inner circumferential surface G1 and the outer circumferential surface F1 is a permeable 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 placed in the first recess H1. For example, the first elastic member 26a can be made of expanded graphite or a rubber O-ring. The first elastic member 26a is in close contact with the first flange 30, which will be described later. This seals the space between the cylindrical 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 placed in the second recess H2. For example, the second elastic member 26b can be made of 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 seals the space between the cylinder body 21 and the second flange 40.

[0046] An annular first recess H3 is formed on the first end face G2. A third elastic member 26c is placed in the first recess H3. For example, the third elastic member 26c can be 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 space between the cylindrical body 21 and the first end plate 22.

[0047] An annular second recess H4 is formed on the second end face G3. A fourth elastic member 26d is placed in the second recess H4. For example, the fourth elastic member 26d can be expanded graphite or a rubber O-ring. The fourth elastic member 26d is in close contact with the second end plate 23. This seals the space between the cylindrical body 21 and the second end plate 23.

[0048] The sweep gas supply port T3 and the sweep gas outlet T4 are each connected to the permeate space S2. The sweep gas is supplied from the sweep gas supply port T3 to the permeate space S2. In the permeate space S2, the sweep gas takes in water vapor and absorbs the reaction heat associated with the conversion reaction. The sweep gas is discharged together with the 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 supply port T3 and the sweep gas outlet T4 are diagonally opposite each other in cross-sectional view, but the positions of the sweep gas supply port T3 and the sweep gas outlet T4 can be changed as appropriate.

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

[0050] The central portion of the first end plate 22 is enlarged in a flange-like shape. 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, which will be described later. In this embodiment, the first opposing surface J1 is separated from 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 body 21.

[0051] The first end plate 22 is connected to the cylindrical body 21 by a plurality of fixing members 27. The fixing members 27 are, 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. The second end plate 23 has an outlet 23a through which liquid fuel flows out. The liquid fuel is discharged to the outside from the impermeable side space S1 of the reactor 10 through the outlet 23a.

[0053] The central portion of the second end plate 23 is enlarged in a flange-like shape. 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, which will be described later. In this embodiment, the second opposing surface J2 is separated from 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 body 21.

[0054] The second end plate 23 is connected to the cylindrical body 21 by a plurality of fixing members 28. The fixing members 28 are, 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 mounted on the reactor 10. The first flange 30 is joined to the reactor 10 by the first joining member 70. The first flange 30 functions as a spacer to form a permeable space S2 between the reactor 10 and the cylindrical 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 onto one end of the cylindrical body 21. The first flange 30 supports the first end 10a of the reactor 10 at a position away from the cylindrical body 21. This forms a permeable space S2 between the reactor 10 and the cylindrical body 21.

[0056] The first flange 30 has an end face K1, an outer circumferential surface L1, and an inner circumferential surface M1. 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 planar. The outer circumferential surface L1 is the radially outer surface of the first flange 30. The outer circumferential surface L1 faces the inner circumferential surface G1 of the cylindrical body 21 and is in close contact with the first elastic member 26a. The outer circumferential surface L1 may abut against the inner circumferential surface G1. The inner circumferential surface M1 is provided on the opposite side of the outer circumferential surface L1. The inner circumferential surface M1 faces the outer circumferential surface F1 of the reactor 10 via the first joining member 70. The inner circumferential surface M1 may abut against the first intermediate portion 50, which will be described later.

[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 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.

[0058] [Second flange 40] The second flange 40 is mounted on the reactor 10. The second flange 40 is joined to the reactor 10 by the second connecting member 80. The second flange 40 is positioned on the opposite side of the first flange 30. The second flange 40 functions as a spacer to form a permeable 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 onto 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.

[0059] The second flange 40 has an end face K2, an outer circumferential surface L2, and an inner circumferential surface M2. 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 planar. The outer circumferential surface L2 is the radially outer surface of the second flange 40. The outer circumferential surface L2 faces the inner circumferential surface G1 of the cylindrical body 21 and is in close contact with the second elastic member 26b. The outer circumferential surface L2 may abut against the inner circumferential surface G1. The inner circumferential surface M2 is provided on the opposite side of the outer circumferential surface L2. The inner circumferential surface M2 faces the outer circumferential surface F1 of the reactor 10 via the second joining member 80. The inner circumferential 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 needs to be airtight and liquid-tight. 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 portion 50 is an annular thin plate member. The first intermediate portion 50 is positioned between the reactor 10 and the housing 20. Specifically, the first intermediate portion 50 is positioned between the first end face F2 of the reactor 10 and the first opposing surface J1 of the first end plate 22. By interposing the first intermediate portion 50 between the reactor 10 and the housing 20 in this way, direct contact between the reactor 10 and the first end plate 22 can be suppressed. Therefore, damage (such as chipping or cracking) to the reactor 10 can be suppressed.

[0062] As shown in Figure 1, it is preferable that the first intermediate portion 50 is joined to the reactor 10 by the first joining material 70. This allows the first intermediate portion 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. As the ceramic material, the ceramic material that constitutes the first flange 30 described above can be used. Preferably, the first intermediate section 50 is 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 suppressing damage to the reactor 10.

[0064] Here, Figure 2 is a partially enlarged view of Figure 1. As shown in Figure 2, the first intermediate portion 50 has an opposing surface P1, a contact 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 face K1 of the first flange 30, but a step may be formed between the opposing surface P1 and the end face 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 all planar, but at least one of them may be curved or bent in whole or in part.

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

[0067] As shown in Figure 1, it is preferable that the second intermediate portion 60 is joined to the reactor 10 by the second joining material 80. This allows the second intermediate portion 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. As the ceramic material, the ceramic material that constitutes the second flange 40 described above can be used. Preferably, the second intermediate section 60 is 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 suppressing damage to the reactor 10.

[0069] Here, Figure 3 is a partially enlarged view of Figure 1. As shown in Figure 3, the second intermediate portion 60 has an opposing surface P2, a contact 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 face K2 of the second flange 40, but a step may be formed between the opposing surface P2 and the end face K2. The abutment surface Q2 abuts against the second flange 40. The abutment 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 it does not have to be flush with the inner circumferential surface U4. In this embodiment, the opposing surface P2, the abutment surface Q2, and the joining surface R2 are all planar, but at least one of them may be curved or bent in whole or in part.

[0071] [First bonding material 70] The first joining member 70 is interposed between the first flange 30 and the first intermediate portion 50 and the reactor 10, respectively. The first joining member 70 joins the first flange 30 to the reactor 10 and also joins the first intermediate portion 50 to the reactor 10. The first joining member 70 is positioned in at least a portion of the gap between the first flange 30 and the reactor 10, and in at least a portion of the gap between the first intermediate portion 50 and the reactor 10. As shown in Figure 2, the cross-section of the first joining member 70 is L-shaped.

[0072] The joint between the first flange 30 and the reactor 10, joined by the first joining material 70, is a "separation membrane assembly" according to the present invention.

[0073] As the first bonding material 70, crystallized glass, amorphous glass, brazing material, or ceramics can be used, and crystallized glass is particularly preferred when considering heat resistance and pressure resistance.

[0074] As crystallized glass, for example, SiO2-B2O3 system, SiO2-CaO system, SiO2-Al2O3 system, SiO2-MgO system, SiO2-ZnO-BaO system, SiO2-B2O3-CaO system, or SiO2-MgO-CaO system, SiO2-Al2O3-B2O3 system, and SiO2-MgO-Al2O3 system 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%.

[0075] [Second bonding material 80] The second joining member 80 is interposed between the second flange 40 and the second intermediate portion 60 and the reactor 10, respectively. The second joining member 80 joins the second flange 40 to the reactor 10 and also joins the second intermediate portion 60 to the reactor 10. The second joining member 80 is positioned in at least a portion of the gap between the second flange 40 and the reactor 10, and in at least a portion of the gap between the second intermediate portion 60 and the reactor 10. As shown in Figure 3, the cross-section of the second joining member 80 is L-shaped.

[0076] Furthermore, the joint between the second flange 40 and the reactor 10, joined by the second joining material 80, is the "separation membrane assembly" according to the present invention.

[0077] As the second bonding material 80, crystallized glass, amorphous glass, brazing material, or ceramics can be used, and crystallized glass is particularly preferred when considering heat resistance and pressure resistance.

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

[0079] The process for manufacturing the reactor assembly comprises a first step of forming a molded body of the joining material, a second step of attaching the flange and intermediate section, and a third step of heating the molded body of the joining material. In the first step, a molded body of the first joining material 70 is formed on the first end 10a of the reactor 10, and a molded body of the second joining material 80 is formed on the second end 10b of the reactor 10. In the second step, a first flange 30 and a first intermediate section 50 are attached so as to surround the molded body of the first joining material 70, and a second flange 40 and a second intermediate section 60 are attached so as to surround the molded body of the second joining material 80. In the third step, the molded bodies of the first and second joining materials 70 and 80 are heated to grow crystals or melt, and then cooled to room temperature to form the first and second joining materials 70 and 80. As a result, a reactor assembly is completed in which the first and second flanges 30 and 40 and the first and second intermediate sections 50 and 60 are joined to the reactor 10 via the first and second joining members 70 and 80.

[0080] Next, the process of housing 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, after inserting the reactor assembly into the cylindrical body 21, the 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 a fixing member 27, and the second end plate 23 is connected to the cylindrical body 21 by a fixing member 28. With these steps completed, the separation membrane module 1 with the reactor assembly housed in the housing 20 is completed.

[0081] Since 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 suppressed in the sixth step. Therefore, damage to the reactor 10 can be suppressed. Similarly, since 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 suppressed in the sixth step. Therefore, damage to the reactor 10 can be suppressed.

[0082] (Modified examples of the embodiment) Although embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, and various modifications are possible without departing from the spirit of the invention.

[0083] [Example 1] In the above embodiment, the case in which a reactor 10 is used as the membrane structure was described, but a separation filter can be used as the membrane structure. The separation filter has the same configuration as the reactor 10, except that instead of a separation membrane 12 that allows water vapor to pass through, a separation membrane that allows desired components contained in the mixed fluid to pass through is used, and that it does not have a catalyst 13. Furthermore, even when a separation filter is used as the membrane structure in the present invention, it is assumed that it will be used under high temperature and high pressure conditions.

[0084] Furthermore, 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 compared to the sweep gas supply outlet T3 side.

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

[0086] Figure 4 is a schematic cross-sectional view showing the configuration of a separation membrane module 1a equipped with a monolithic reactor 100. However, in Figure 4, only the reactor 100 is shown in a 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-stopping section 90 and replaces the reactor 10 with a reactor 100. In the reactor 100 as well, the catalyst stopper 14 can be configured arbitrarily.

[0088] The flow-stopping section 90 is formed in an annular shape. The flow-stopping section 90 is positioned between the reactor 100 and the housing 20. The flow-stopping section 90 divides the gap between the reactor 100 and the housing 20 into a sweep gas discharge space S21 and a sweep gas supply space S22. The flow-stopping section 90 suppresses the direct flow of sweep gas between the sweep gas discharge space S21 and the sweep gas supply space S22. The flow-stopping section 90 only needs to be able to directly suppress the flow of sweep gas and does not need to seal the space between the reactor 100 and the housing 20. The flow-stopping section 90 can be made of, for example, expanded graphite, rubber, resin, metal, etc.

[0089] The reactor 100 has a plurality of first channels 15, a plurality of second channels 16, a first slit 17, and a second slit 18.

[0090] The first channel 15 penetrates the reactor 100 in the longitudinal direction. The first channel 15 opens to the first and second end faces F2 and F3. The separation membrane 12 described above is formed on the inner surface of the first channel 15. Inside the separation membrane 12 is an impermeable space S1. The catalyst 13 described above is placed in the impermeable space S1.

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

[0092] The first slit 17 is formed at the first end 100a of the reactor 100. The first slit 17 penetrates each second flow path 16 radially and opens to the outer surface F1. Thus, the first slit 17 communicates with each second flow path 16 and the swept gas discharge space S21.

[0093] The second slit 18 is formed at the second end 100b of the reactor 100. The second slit 18 penetrates each second flow path 16 radially and opens to the outer surface F1. Thus, the second slit 18 communicates each second flow path 16 with the sweep gas supply space S22.

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

[0095] In this modified example, the sweep gas supply port T3 and the sweep gas outlet T4 are arranged on a straight line that intersects the axis of the reactor 10 in a cross-sectional view. This makes it possible to make the flow path length of the sweep gas in the sweep gas outlet space S21 and the flow path length of the sweep gas in the sweep gas supply space S22 equal, thereby suppressing uneven flow of the sweep gas. However, the relative positions of the sweep gas supply port T3 and the sweep gas outlet T4 can be changed as appropriate.

[0096] Figure 5 is a cross-sectional view of AA in Figure 4. As shown in Figure 5, the first slit 17 penetrates the interior of the reactor 100 in a straight line and opens on both sides of the reactor 100. The first slit 17 has two openings formed on the outer circumferential surface F1. The swept gas that flows out from each of the two openings of the first slit 17 into the swept gas discharge space S21 passes through the swept gas discharge space S21 and is discharged to the outside from the swept gas outlet T4.

[0097] Here, it is preferable that the first extending direction in which the first slit 17 extends inside the reactor 100 is inclined or perpendicular to the discharge direction of the swept gas discharged to the outside from the swept gas outlet T4. Specifically, the angle θ1 of the first extending direction with respect to the discharge direction is preferably 45 degrees or more and 135 degrees or less. This suppresses the uneven flow of gas from each opening of the first slit 17 to the swept gas outlet T4, and thus suppresses uneven flow of swept gas in the swept gas discharge space S21.

[0098] Figure 6 is a cross-sectional view of BB in Figure 4. As shown in Figure 6, the second slit 18 penetrates the interior of the reactor 100 in a straight line and opens on both sides of the reactor 100. The second slit 18 has two openings formed on the outer 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, it is preferable that the second extending direction in which the second slit 18 extends inside the reactor 100 is 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 extending direction with respect to the supply direction is preferably 45 degrees or more and 135 degrees or less. This suppresses the uneven flow of gas from the sweep gas supply port T3 to each opening of the second slit 18, and thus suppresses uneven flow of sweep gas in the sweep gas supply space S22.

[0100] [Difference 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 suppressing the formation of cracks in the separation membrane 12 that originate from the contact point with the catalyst 13 when the catalyst becomes hot due to the reaction heat. The buffer layer can be made of a ceramic material or an organic polymer material. Examples of ceramic materials include silica, alumina, and chromia. Examples of organic polymer materials include PTFE, PVA, and PEG.

[0101] [Differentiation Example 4] In the above embodiment, the first flange 30 is separate from the first intermediate portion 50, but as shown in Figure 7, the first flange 30 may be integrated with the first intermediate portion 50. When the first flange 30 is integrated with the first intermediate portion 50, the handling of the separation membrane module 1 during the assembly process 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 integrated with the second intermediate portion 60.

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

[0104] [Difference 5] In the above embodiment, the first intermediate portion 50 is positioned across the entire gap between the reactor 10 and the first end plate 22, but it may also be positioned across only a portion of the gap. In this case, the first intermediate portion 50 can be a C-shaped thin plate member or a plurality of thin plate members spaced apart in the circumferential direction.

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

[0106] [Modification 6] In the above embodiment, the first joining member 70 is interposed between the first flange 30 and the first intermediate portion 50 and the reactor 10, but it is not necessary for the first intermediate portion 50 to be interposed between the reactor 10 and the first intermediate portion 50. 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 joining member 80 is interposed between the second flange 40 and the second intermediate portion 60 and the reactor 10, but it 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] [Difference 7] In the above embodiment, as shown in Figure 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, but it is not limited to this. As shown in Figure 9, the inner circumferential surface U1 of the first intermediate portion 50 may be located radially inward from the inner circumferential surface U2 of the first end plate 22. Alternatively, as shown in Figure 10, the inner circumferential surface U1 of the first intermediate portion 50 may be located radially outward from the inner circumferential surface U2 of the first end plate 22.

[0109] Similarly, in the above embodiment, as shown in Figure 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, but it 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 radially outward from the inner circumferential surface U4 of the second end plate 23.

[0110] [Differentiation 8] In the above embodiment, the separation membrane 12 is designed to allow water vapor, a product of the conversion reaction from the raw gas to the liquid fuel, to pass through, but it is not limited to this. The separation membrane 12 may also allow the liquid fuel itself, a product of the conversion reaction from the raw gas to the liquid fuel, to pass through. In this case as well, the reaction equilibrium of formula (1) can be shifted to the product side.

[0111] Furthermore, when the separation membrane 12 allows liquid fuel to permeate, the reaction equilibrium can be shifted to the product side even when liquid fuel is produced by a reaction that does not produce water vapor as a by-product (for example, H2 + CO ⇔ CH3OH).

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

[0113] For example, as shown in Figure 11, the sweep gas supply port T3 and the sweep gas discharge port T4 may be located on the same side of the reactor 10 in a side view, or a rectifier plate 20a may be provided to close a portion of the gap between the reactor 10 and the housing 20. In Figure 11, three rectifier plates 20a are provided, but the number of rectifier plates 20a may be one, two, or four or more. The position of the rectifier plates 20a can be set as appropriate.

[0114] Furthermore, as shown in Figure 12, the housing 20 does not have a sweep gas supply port T3, and sweep gas does not need to be supplied into the housing 20. In this case, the products separated by the separation membrane 12 of the reactor 10 flow out of the housing 20 through the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set as appropriate.

[0115] Furthermore, the configurations shown in Figures 11 and 12 are also applicable when a separation filter is used as the membrane structure instead of the reactor 10.

[0116] [Example 10] In the separation membrane module 1 according to the above embodiment (see Figure 1), only one reactor 10 is housed in the housing 20, but this is not the only configuration.

[0117] For example, as shown in Figure 13, multiple reactors 10 may be housed within the housing 20.

[0118] Furthermore, as shown in Figure 14, a rectifier plate 20a may be provided to seal a portion of the gap between each reactor 10 and the housing 20. In Figure 14, three rectifier plates 20a are provided, but the number of rectifier plates 20a may be one, two, or four or more. The position of the rectifier plates 20a can be set as appropriate. Also, as shown in Figure 14, the sweep gas supply port T3 and the sweep gas discharge port T4 may be located on the same side of the reactor 10 in a side view.

[0119] Furthermore, as shown in Figure 15, the housing 20 does not have a sweep gas supply port T3, and sweep gas does not need to be supplied into the housing 20. In this case, the products separated by the separation membrane 12 of the reactor 10 flow out of the housing 20 through the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set as appropriate.

[0120] Furthermore, the configurations shown in Figures 13 to 15 are also applicable when a separation filter is used as the membrane structure instead of the reactor 10.

[0121] [Example 11] In the separation membrane module 1a (see Figure 4) according to the above modified example 2, the sweep gas supply port T3 and the sweep gas outlet T4 are positioned diagonally opposite each other in a side view, but the invention is not limited to this configuration.

[0122] For example, as shown in Figure 16, the sweep gas supply port T3 and the sweep gas outlet T4 may be located on the same side of the reactor 100 in a side view, or a flow straightening plate 20b may be provided to block a portion of the gap between the reactor 100 and the housing 20. In Figure 16, one flow straightening plate 20b is provided on each side of the flow-stopping section 90. The flow 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 flow straightening plate 20b on the sweep gas outlet T4 side divides the space on the sweep gas outlet 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 position of the flow straightening plates 20b can be set as appropriate. Furthermore, some of the swept gas may pass through the inside of the flow-stopping section 90.

[0123] Furthermore, as shown in Figure 17, the housing 20 does not have a sweep gas supply port T3, and sweep gas does not need to be supplied into the housing 20. In this case, the products separated by the separation membrane 12 of the reactor 100 flow out of the housing 20 through the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set as appropriate.

[0124] Furthermore, the configurations shown in Figures 16 and 17 are also applicable when a separation filter is used as the membrane structure instead of the reactor 100.

[0125] [Example 12] In the separation membrane module 1a (see Figure 4) relating to the above modified example 2, only one reactor 100 is housed in the housing 20, but this is not the only option.

[0126] For example, as shown in Figure 18, multiple reactors 100 may be housed within the housing 20.

[0127] Furthermore, as shown in Figure 19, a flow straightening plate 20b may be provided to block a portion of the gap between the reactor 100 and the housing 20. In Figure 19, one flow straightening plate 20b is provided on each side of the flow-stopping section 90. The flow 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 flow straightening plate 20b on the sweep gas outlet T4 side divides the space on the sweep gas outlet 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 position of the flow straightening plates 20b can be set as appropriate. Also, a portion of the sweep gas may pass through the inside of the flow-stopping section 90. As shown in Figure 19, the sweep gas supply port T3 and the sweep gas discharge port T4 may be located on the same side of the reactor 100 in a side view.

[0128] Furthermore, as shown in Figure 20, the housing 20 does not have a sweep gas supply port T3, and sweep gas does not need to be supplied into the housing 20. In this case, the products separated by the separation membrane 12 of the reactor 100 flow out of the housing 20 through the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set as appropriate.

[0129] Furthermore, the configurations shown in Figures 18 to 20 are also applicable when a separation filter is used as the membrane structure instead of the reactor 100. [Explanation of Symbols]

[0130] 1 Separation membrane module 10 Reactors 10a 1st end 10b 2nd end F1 outer surface F2 1st end face F3 2nd end face 20 Housing 21. Main body of the cylinder 22. First end plate 23. Second end plate 30 First Flange 40 Second flange 50 First Intermediate Section 60 Second Intermediate Section 70 1st bonding material 80 Second bonding material

Claims

1. A cylindrical housing, A columnar membrane structure housed in the aforementioned housing, An annular first flange surrounding the first end of the membrane structure, A first intermediate portion is disposed between the first end face of the membrane structure and the housing, A first joining material is interposed between the first flange and the first intermediate portion and the membrane structure, and joins the first flange and the first intermediate portion to the membrane structure, Equipped with, The first bonding material is composed of crystallized glass, amorphous glass, brazing material, or ceramics. Separation membrane module.

2. The first intermediate portion is integrated 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. An annular second flange surrounding the second end of the aforementioned membrane structure, A second intermediate portion is disposed between the second end face of the membrane structure and the housing, The separation membrane module according to claim 1, further comprising the following:

5. The present invention further comprises a second joining member interposed between the second flange and the second intermediate portion and the membrane structure, which joins the second flange and the second intermediate portion to the membrane structure, The second bonding material is composed of crystallized glass, amorphous glass, brazing material, or ceramics. The separation membrane module according to claim 4.

6. The aforementioned second intermediate portion is integrated with the aforementioned 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 aforementioned membrane structure is a reactor. The separation membrane module according to claim 1.

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

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