Membrane assemblies and separation membrane modules

Abstract

The membrane assembly includes a cylindrical reactor (10), a first annular flange (30) surrounding a first end (10a) of the reactor (10), a first intermediate portion (50) disposed between a first end face (F2) of the reactor (10) and the housing (20), and a first bonding material (70) interposed between each of the first flange (30) and the first intermediate portion (50) and the reactor (10).

Description

[Technical field]

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

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

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

[0004] Incidentally, since it is necessary to provide a permeate side space between the membrane structure and the housing for recovering the permeated components that have permeated the separation membrane, it is necessary to prepare a membrane assembly in which flanges are attached to the ends of the membrane structure using an adhesive material.

[0005] A certain seal length is necessary to ensure sealing between the flange and the membrane structure, but if the seal length in the longitudinal direction is increased, the internal stress on the bonding material increases, reducing the reliability of the seal.

[0006] An object of the present invention is to provide a membrane assembly and a separation membrane module that can improve the reliability of the seal provided by a bonding material between a flange and a membrane structure. [Means for solving the problem]

[0007] A membrane assembly according to a first aspect of the present invention is accommodated in a cylindrical housing, and includes a columnar membrane structure, a first annular flange surrounding a first end of the membrane structure, a first intermediate portion disposed between the first end face of the membrane structure and the housing, and a first bonding material interposed between the membrane structure and the first flange and between the membrane structure and the first intermediate portion.

[0008] A membrane assembly according to a second aspect of the present invention is related to the first aspect, wherein the first intermediate portion is integral with the first flange.

[0009] A membrane assembly according to a third aspect of the present invention is related to the first or second aspect and comprises a second annular flange surrounding a second end of the membrane structure, a second intermediate portion arranged between the second end face of the membrane structure and the housing, and a second bonding material interposed between each of the second flange and the second intermediate portion and the membrane structure.

[0010] A membrane assembly according to a fourth aspect of the present invention is related to the third aspect, wherein the second intermediate portion is integral with the second flange.

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

[0012] A membrane assembly according to a sixth aspect of the present invention relates to the first to fifth aspects, and the second flange is made of a ceramic material.

[0013] A membrane assembly according to a seventh aspect of the present invention relates to the first to sixth aspects, and the membrane structure is a reactor.

[0014] A membrane assembly according to an eighth aspect of the present invention relates to the first to sixth aspects, and the membrane structure is a separation filter.

[0015] A separation membrane module according to a ninth aspect of the present invention comprises the membrane assembly according to any one of the first to eighth aspects, and a cylindrical housing that houses the membrane assembly. Effect of the Invention

[0016] According to the present invention, it is possible to provide a separation membrane module capable of improving the reliability of the seal provided by the bonding material between the flange and 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. [Diagram 2] FIG. 2 is a partially enlarged view of FIG. [Diagram 3] FIG. 3 is a partially enlarged view of FIG. [Figure 4] FIG. 4 is a cross-sectional view of a reactor assembly according to an embodiment. [Diagram 5] FIG. 5 is a cross-sectional view of a reactor assembly according to a comparative example. [Figure 6] FIG. 6 is a cross-sectional view of a separation membrane module according to the second modification. [Figure 7] FIG. 7 is a cross-sectional view taken along line AA in FIG. [Figure 8] FIG. 8 is a cross-sectional view taken along line BB of FIG. [Figure 9] FIG. 9 is a cross-sectional view of a separation membrane module according to the fourth modification. [Figure 10] FIG. 10 is a cross-sectional view of a separation membrane module according to the fourth modification. [Figure 11] FIG. 11 is a cross-sectional view of a separation membrane module according to the sixth modification. [Figure 12] FIG. 12 is a cross-sectional view of a separation membrane module according to the sixth modification. [Figure 13] FIG. 13 is a cross-sectional view of a separation membrane module according to the seventh modification. [Figure 14] FIG. 14 is a cross-sectional view of a separation membrane module according to the seventh modification. [Figure 15]FIG. 15 is a cross-sectional view of a separation membrane module according to the seventh modification. [Figure 16] FIG. 16 is a cross-sectional view of a separation membrane module according to Modification 8. As shown in FIG. [Figure 17] FIG. 17 is a cross-sectional view of a separation membrane module according to Modification 8. As shown in FIG. [Figure 18] FIG. 18 is a cross-sectional view of a separation membrane module according to Modification 9. As shown in FIG. [Figure 19] FIG. 19 is a cross-sectional view of a separation membrane module according to Modification 9. As shown in FIG. [Figure 20] FIG. 20 is a cross-sectional view of a separation membrane module according to Modification 9. As shown in FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

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

[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 oxides. At least one of carbon monoxide and carbon dioxide can be used as the carbon oxide. The raw material gas may be a so-called synthetic gas (Syngas). The liquid fuel is a fuel that is in a liquid state at normal temperature and pressure, or a fuel that can be liquefied under normal temperature and pressure. Examples of the fuel that is in a liquid state at normal temperature and pressure include methanol, ethanol, and C. n H 2(m-2n) (m is an integer less than 90, and n is an integer less than 30), and mixtures thereof. Examples of fuels that can be liquefied under 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. 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 water vapor, which is one of the products of the conversion reaction. In order to increase the conversion efficiency and reaction rate, it is preferable to carry out the conversion reaction under high temperature and pressure (e.g., 180°C or higher, 2 MPa or higher). The liquid fuel is in a gaseous state when synthesized, and is maintained in this state at least until it flows out of the reactor 10. The reactor 10 preferably has heat resistance and pressure resistance suitable for the synthesis conditions of the desired liquid fuel.

[0024] The reactor 10 according to the present embodiment is a so-called tubular type. As shown in FIG. 1, the reactor 10 has an outer peripheral surface F1, a first end surface F2, and a second end surface F3. The outer peripheral surface F1 is a side surface of the cylindrical reactor 10. The outer peripheral surface F1 is connected to the first end surface F2 and the second end surface F3. The first end surface F2 is one end surface of the cylindrical reactor 10. A first opening T1 is formed in the first end surface F2. The raw material gas flows into the inside of the reactor 10 from the first opening T1. The second end surface F3 is the other end surface of the cylindrical reactor 10. A second opening T2 is formed in the second end surface F3. The liquid fuel flows out of the reactor 10 from the second opening T2.

[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 preferable. As aggregates of the ceramic material, alumina (Al2O3), titania (TiO2), mullite (Al2O3·SiO2), cerium oxide, and cordierite (Mg2Al4Si5O 18 ), and composite materials containing two or more of these can be used, with alumina being preferred in consideration of availability, clay stability, and corrosion resistance. As the inorganic binder for the ceramic material, at least one of titania, mullite, sinterable alumina, silica, glass frit, clay minerals, and sinterable cordierite can be used. However, the ceramic material does not have to contain an inorganic binder.

[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 measurement target particles (randomly selected) measured by cross-sectional microstructural observation using a SEM (Scanning Electron Microscope).

[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 a non-permeation side space S1 to which a raw material gas is supplied. The non-permeation side space S1 is a space between a first opening T1 and a second opening T2. In this embodiment, the separation membrane 12 is disposed on the inner surface of the porous support 11, but may be disposed on the outer surface of the porous support 11.

[0030] The separation membrane 12 allows the permeation of water vapor, which is one of the products of the conversion reaction from the feed gas to liquid fuel, thereby making it possible to utilize the equilibrium shift effect to shift the reaction equilibrium of the above formula (1) to the product side.

[0031] The separation membrane 12 has a molecular weight of 100 nmol / (s·Pa·m 2 The water vapor permeability coefficient can be determined by a known method (see Ind. Eng. Chem. Res., 40, 163-175 (2001)).

[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 harder it is for components other than water vapor (such as hydrogen, carbon dioxide, and liquid fuel) to permeate. The separation factor can be determined by a known method (see FIG. 1 in "Separation and Purification Technology 239 (2020) 116533").

[0033] An inorganic membrane can be used as the separation membrane 12. Inorganic membranes are preferable because they have heat resistance, pressure resistance, and water vapor resistance. Examples of inorganic membranes include zeolite membranes, silica membranes, alumina membranes, and composite membranes of these. In particular, an LTA-type zeolite membrane in which the molar ratio (Si / Al) of silicon element (Si) to aluminum element (Al) is 1.0 or more and 3.0 or less is preferable because it has excellent water vapor permeability.

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

[0035] Any known catalyst suitable for a conversion reaction from a raw material gas to a liquid fuel can be used as the catalyst 13. Examples of the catalyst 13 include metal catalysts (copper, palladium, etc.), oxide catalysts (zinc oxide, zirconia, gallium oxide, etc.), and catalysts made by combining these (copper-zinc oxide, copper-zinc oxide-alumina, copper-zinc oxide-chromium oxide-alumina, copper-cobalt-titania, and catalysts made by modifying these with palladium, etc.).

[0036] The catalyst stopper 14 is attached to the second end face F3. The catalyst stopper 14 is disposed so as to cover the second opening T2 formed in the second end face F3. The catalyst stopper 14 stops the catalyst 13 from leaking out from the second opening T2. The catalyst stopper 14 has a configuration that stops the catalyst 13 from leaking out while not impeding the outflow of liquid fuel. For example, a mesh member, a perforated plate, or the like can be used as the catalyst stopper 14.

[0037] However, in cases where leakage of the catalyst 13 is unlikely to occur (for example, when the catalyst 13 is arranged in a layer or island form on the surface of the separation membrane 12), the reactor 10 does not need to have the catalyst stopper 14.

[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 water vapor, which is one of the products of the conversion reaction, passes through the separation membrane 12 and the porous support 11 and is separated into the permeation side space S2 described later.

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

[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 .

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

[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 exhaust port T4.

[0043] The inner circumferential surface G1 faces the outer circumferential surface F1 of the reactor 10, and is spaced apart from the outer circumferential surface F1. The gap between the inner circumferential surface G1 and the outer circumferential surface F1 is a permeation side space S2 for recovering water vapor, which is one of the products of the conversion reaction.

[0044] An annular first notch H1 is formed at one end of the inner circumferential surface G1. An annular first elastic member 26a is disposed in the first notch H1. For example, an O-ring made of expanded graphite or rubber can be used as the first elastic member 26a. The first elastic member 26a is pressed by the first pressing member 24 inserted into the first notch H1 and comes into close contact with the first flange 30 described below. This seals the gap between the tube main body 21 and the first flange 30. The first pressing member 24 is fixed to the first end surface G2 of the tube main body 21 by a bolt or the like. In this embodiment, the first pressing member 24 has an L-shaped cross section.

[0045] At the other end of the inner circumferential surface G1, an annular second notch H2 is formed. An annular second elastic member 26b is disposed in the second notch H2. For example, an O-ring made of expanded graphite or rubber can be used as the second elastic member 26b. The second elastic member 26b is pressed by the second pressing member 25 inserted into the second notch H2 and comes into close contact with the second flange 40 described below. This seals the gap between the tube main body 21 and the second flange 40. The second pressing member 25 is fixed to the second end surface G3 of the tube main body 21 by a bolt or the like. In this embodiment, the second pressing member 25 has an L-shaped cross section.

[0046] The first end face G2 has a first recess H3 formed therein. The third elastic member 26c is disposed in the first recess H3. For example, an O-ring made of expanded graphite or rubber can be used as the third elastic member 26c. The third elastic member 26c is in close contact with the first end plate 22.

[0047] A ring-shaped second recess H4 is formed in the second end face G3. A fourth elastic member 26d is disposed in the second recess H4. For example, an O-ring made of expanded graphite or rubber can be used as the fourth elastic member 26d. The fourth elastic member 26d is in close contact with the second end plate 23.

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

[0049] The first end plate 22 is an annular plate member. The central portion of the first end plate 22 is expanded in diameter in a flange shape. The first end plate 22 has a first opposing surface J1. The first opposing surface J1 faces the first end surface F2 of the reactor 10 and the end surface K1 of the first flange 30 described later. However, the first opposing surface J1 does not have to face the first end surface F2 of the reactor 10. The first opposing surface J1 abuts against the first end surface G2 of the tube main body 21. The first opposing surface J1 is formed with an annular third recess H5. The third recess H5 accommodates a portion of the first pressing member 24 that protrudes from the first end surface G2.

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

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

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

[0053] [First flange 30] The first flange 30 is attached to the reactor 10. The first flange 30 is joined to the reactor 10 by a first joining material 70. The first flange 30 functions as a spacer for forming a permeate side space S2 between the reactor 10 and the tube body 21. The first flange 30 is formed in an annular shape. The first flange 30 surrounds the first end 10a of the reactor 10. The first flange 30 is fitted into one end of the tube body 21. The first flange 30 supports the first end 10a of the reactor 10 at a position away from the tube body 21. As a result, a permeate side space S2 is formed between the reactor 10 and the tube body 21.

[0054] The first flange 30 has an end face K1, an outer peripheral surface L1, and an inner peripheral 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 flat. The outer peripheral surface L1 is the radially outer surface of the first flange 30. The outer peripheral surface L1 faces the inner peripheral surface G1 of the tube main body 21 and is in close contact with the first elastic member 26a. The outer peripheral surface L1 may abut against the inner peripheral surface G1. The inner peripheral surface M1 is provided on the opposite side of the outer peripheral surface L1.

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

[0056] [Second flange 40] The second flange 40 is attached to the reactor 10. The second flange 40 is joined 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 tube 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 tube body 21. The second flange 40 supports the second end 10b of the reactor 10 at a position away from the tube body 21.

[0057] The second flange 40 has an end face K2, an outer peripheral surface L2, and an inner peripheral 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 flat. The outer peripheral surface L2 is the radially outer surface of the second flange 40. The outer peripheral surface L2 faces the inner peripheral surface G1 of the tube main body 21 and is in close contact with the second elastic member 26b. The outer peripheral surface L2 may abut against the inner peripheral surface G1. The inner peripheral surface M2 is provided on the opposite side of the outer peripheral surface L2.

[0058] The second flange 40 is made of a dense ceramic material. Examples of the ceramic material that can be used include alumina, zirconia, silicon carbide, aluminum nitride, cordierite, and composite materials containing two or more of these. The second flange 40 needs to be airtight and liquidtight. Therefore, the porosity of the second flange 40 is preferably 10.0% or less, and more preferably 5.0% or less.

[0059] [First intermediate section 50] The first intermediate portion 50 is an annular thin plate member. The first intermediate portion 50 is bonded to the reactor 10 by a first bonding material 70.

[0060] The first intermediate portion 50 is disposed between the reactor 10 and the housing 20. Specifically, the first intermediate portion 50 is disposed between the first end surface F2 of the reactor 10 and the first opposing surface J1 of the first end plate 22.

[0061] 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, a contact surface Q1, and a joining surface R1.

[0062] The opposing surface P1 faces the housing 20. The opposing surface P1 may be in contact with 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 the first flange 30. The abutting surface Q1 abuts the inner peripheral surface M1 of the first flange 30. The joining surface R1 is joined to the first joining material 70. 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 curved or bent entirely or partially.

[0063] [Second intermediate portion 60] The second intermediate portion 60 is an annular thin plate member. The second intermediate portion 60 is bonded to the reactor 10 by a second bonding material 80.

[0064] The second intermediate portion 60 is disposed between the reactor 10 and the housing 20. Specifically, the second intermediate portion 60 is disposed between the second end surface F3 of the reactor 10 and the second opposing surface J2 of the second end plate 23.

[0065] 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, a contact surface Q2, and a joining surface R2.

[0066] The opposing surface P2 faces the housing 20. The opposing surface P2 may be in contact with 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 peripheral surface M2 of the second flange 40. The joining surface R2 is joined to the second joining material 80. 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 curved or bent entirely or partially.

[0067] [First bonding material 70] The first bonding materials 70 are interposed between the first flange 30 and the reactor 10, and between the first intermediate portion 50 and the reactor 10. The first bonding materials 70 bond the first flange 30 to the reactor 10 and bond the first intermediate portion 50 to the reactor 10. The first bonding materials 70 are disposed in at least a portion of the gap between the first flange 30 and the reactor 10 and at least a portion 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.

[0068] The assembly of the first flange 30 and the reactor 10 joined by the first bonding material 70 is the "membrane assembly" according to the present invention.

[0069] The first bonding material 70 may be made of crystallized glass, amorphous glass, brazing material, ceramics, or the like, with crystallized glass being particularly preferable in terms of heat resistance and pressure resistance.

[0070] As the crystallized glass, for example, SiO2-B2O3-based, SiO2-CaO-based, SiO2-Al2O3-based, SiO2-MgO-based, SiO2-ZnO-BaO-based, SiO2-B2O3-CaO-based, or SiO2-MgO-CaO-based, SiO2-Al2O3-B2O3-based, SiO2-MgO-Al2O3-based crystallized glass can be used. In this specification, crystallized glass means glass in which the ratio of the "volume occupied by the crystalline phase" to the total volume (degree of crystallinity) is 60% or more, and the ratio of the "volume occupied by the amorphous phase and impurities" to the total volume is less than 40%.

[0071] [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 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.

[0072] The assembly of the second flange 40 and the reactor 10 joined by the second bonding material 80 is the "membrane assembly" according to the present invention.

[0073] As the second bonding material 80, crystallized glass, amorphous glass, brazing material, ceramics, or the like can be used, and in consideration of heat resistance and pressure resistance, crystallized glass is particularly preferable.

[0074] [Assembly of separation membrane module 1] The process of assembling the separation membrane module 1 includes a step of preparing a reactor assembly in which the first and second flanges 30, 40 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.

[0075] The process of producing the reactor assembly includes a first step of forming a molded body of the bonding material, a second step of attaching the flange and the intermediate portion, and a third step of heating the molded body of the bonding material. In the first step, a molded body of the first bonding material 70 is formed at the first end portion 10a of the reactor 10, and a molded body of the second bonding material 80 is formed at the second end portion 10b of the reactor 10. In the second step, the first flange 30 and the first intermediate portion 50 are attached so as to surround the molded body of the first bonding material 70, and the second flange 40 and the second intermediate portion 60 are attached so as to surround the molded body of the second bonding material 80. In the third step, the molded bodies of the first and second bonding materials 70 and 80 are heated to cause crystal growth or melting, and then cooled to room temperature to form the first and second bonding materials 70 and 80. As a result of the above, the 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 via the first and second bonding materials 70, 80 is completed.

[0076] Next, the process of accommodating the reactor assembly includes a fourth step of inserting the reactor assembly, a fifth step of attaching the elastic members, and a sixth step of connecting the end plates. In the fourth step, the reactor assembly is inserted into the cylindrical body 21, and then both ends of the reactor assembly are aligned. In the fifth step, the first and second elastic members 26a and 26b fitted into the first and second notches H1 and H2 of the cylindrical body 21 are pressed by the first and second pressing members 24 and 25, and the third and fourth elastic members 26c and 26d are fitted into the first and second recesses H3 and H4 of the cylindrical body 21. In the sixth step, the first end plate 22 is connected to the cylindrical body 21 by the fixing member 27, and the second end plate 23 is connected to the cylindrical body 21 by the fixing member 28. With the above steps, the separation membrane module 1 in which the reactor assembly is accommodated in the housing 20 is completed.

[0077] Here, when the molded body of the first bonding material 70 is heated in the third step, no internal stress is generated in the first flange 30, the first bonding material 70, and the reactor 10. When the temperature is subsequently lowered to room temperature, internal stress may remain in the first bonding material 70. The internal stress is a concept including stress generated within the first bonding material 70 and stress generated at the interfaces between the first flange 30 and the reactor 10 and the first bonding material 70 (particularly, the interface between the reactor 10 and the first bonding material 70).

[0078] In this embodiment, as described above, the separation membrane module 1 includes the first intermediate portion 50 disposed between the reactor 10 and the housing 20, and the first bonding material 70 interposed between the first flange 30 and the first intermediate portion 50, and the reactor 10. Therefore, as shown in FIG. 4, the first bonding material 70 is subjected to an internal stress f1 inclined with respect to the longitudinal direction. This internal stress f1 is a composite stress of an internal stress f2 applied in the radial direction and an internal stress f3 applied in the longitudinal direction. The total seal length of the first bonding material 70 is the sum of the seal length v1 along the longitudinal direction and the seal length v2 along the radial direction. The total seal length of the first bonding material 70 is a seal length required to ensure the sealability between the first flange 30 and the reactor 10.

[0079] On the other hand, assuming that the separation membrane module 1 does not include the first intermediate section 50, in order to ensure the same sealing performance as the first bonding material 70 in Fig. 4, a total sealing length of the first bonding material 70 needs to be a sealing length v0 equal to the sum of sealing length v1 and sealing length v2, as shown in Fig. 5. In this case, an internal stress f0 larger than the internal stress f1 shown in Fig. 4 is applied to the first bonding material 70.

[0080] In this way, if the total seal length of the first bonding material 70 is the same, the internal stress applied to the first bonding material 70 can be reduced when the intermediate portion 50 is provided compared to when the intermediate portion 50 is not provided. Therefore, the reliability of the seal provided by the first bonding material 70 between the first flange 30 and the reactor 10 can be improved.

[0081] The first bonding material 70 is subjected to internal stress not only in the third step described above. For example, the first bonding material 70 is subjected to internal stress when a raw material gas is supplied at high pressure. Therefore, even when no internal stress remains in the first bonding material 70, the effect of improving the reliability of the seal by the first bonding material 70 can be obtained.

[0082] The above-mentioned effects can be obtained in the relationship between the second flange 40, the second bonding material 80, and the reactor 10 in the same manner.

[0083] (Modification of the embodiment) Although the embodiment of the present invention has been described above, the present invention is not limited to the above embodiment, and various modifications are possible without departing from the gist of the invention.

[0084] [Variation 1] In the above embodiment, the reactor 10 is used as the membrane structure, but a separation filter can be used as the membrane structure. The separation filter has the same configuration as the reactor 10, except that a separation membrane that allows the permeation of a desired component contained in a mixed fluid is used instead of the separation membrane 12 that allows the permeation of water vapor, and that the separation filter does not include a catalyst 13. In addition, in the present invention, even if a separation filter is used as the membrane structure, it is assumed that it will be used under high temperature and high pressure conditions.

[0085] 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 components that have permeated the separation membrane may be discharged from the sweep gas outlet T4 by reducing the pressure on the sweep gas outlet T4 side more than on the sweep gas supply port T3 side.

[0086] [Variation 2] In the above embodiment, the reactor 10, which is an example of a membrane structure, is a tubular type, but it may be a monolith type. In addition, 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 a plurality of cells penetrating in the longitudinal direction, and is a concept including a honeycomb type.

[0087] Fig. 6 is a cross-sectional view that illustrates a schematic configuration of a separation membrane module 1a that includes a monolithic reactor 100. However, in Fig. 6, only the reactor 100 is illustrated in side view.

[0088] 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 includes a reactor 100 instead of the reactor 10. Note that the catalyst stopper 14 is also an optional configuration in the reactor 100.

[0089] 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 first permeate side space S21 and a second permeate side space S22. The flow stopper 90 suppresses the sweep gas from directly flowing between the first permeate side space S21 and the second permeate side space S22. The flow stopper 90 only needs to be able to directly suppress the flow of the sweep gas, and does not need to seal between the reactor 100 and the housing 20. The flow stopper 90 can be made of, for example, expanded graphite, rubber, resin, metal, or the like.

[0090] 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 .

[0091] The first flow path 15 penetrates the reactor 100 in the longitudinal direction. The first flow path 15 opens to the first and second end faces F2, F3. The above-mentioned separation membrane 12 is formed on the inner surface of the first flow path 15. The inside of the separation membrane 12 is the non-permeation side space S1. The above-mentioned catalyst 13 is disposed in the non-permeation side space S1.

[0092] The second flow passage 16 is formed inside the reactor 100. The second flow passage 16 extends along the longitudinal direction. The second flow passage 16 is closed at the first and second end faces F2, F3.

[0093] The first slits 17 are formed in the first end 100a of the reactor 100. The first slits 17 radially penetrate each of the second flow paths 16 and open to the outer circumferential surface F1. Therefore, the first slits 17 communicate with each of the second flow paths 16 and the first permeate side space S21.

[0094] The second slits 18 are formed in the second end 100b of the reactor 100. The second slits 18 radially penetrate each second flow path 16 and open to the outer circumferential surface F1. Therefore, the second slits 18 communicate with each second flow path 16 and the second permeate side space S22.

[0095] When the raw material gas is supplied to the first flow passage 15, the raw material gas is converted into liquid fuel by the action of the catalyst 13, and water vapor, which is one of the products of the conversion reaction, passes through the separation membrane 12 and flows into the second flow passage 16. The water vapor that has flowed into the second flow passage 16 is taken in by the sweep gas that flows into the second flow passage 16 from the sweep gas supply port T3 through the second permeate side space S22 and the second slit 18, and then is discharged to the outside from the sweep gas discharge port T4 through the first slit 17 and the first permeate side space S21.

[0096] Here, Fig. 7 is a cross-sectional view taken along line AA in Fig. 6. As shown in Fig. 7, the first slit 17 penetrates the inside of the reactor 100 in a straight line and opens to both sides of the reactor 100. The first slit 17 has two openings formed in the outer circumferential surface F1. The sweep gas flowing out from each of the two openings of the first slit 17 into the first permeate side space S21 passes through the first permeate side space S21 and is discharged to the outside from the sweep gas outlet T4.

[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 first permeation side space S21.

[0098] Fig. 8 is a cross-sectional view taken along line BB in Fig. 6. As shown in Fig. 8, the second slit 18 penetrates the inside of the reactor 100 in a straight line and opens to both sides of the reactor 100. The second slit 18 has two openings formed in the outer circumferential surface F1. The sweep gas supplied from the sweep gas supply port T3 to the second permeate side space S22 passes through the second permeate side space S22 and flows into each of the two openings of the second slit 18.

[0099] Here, the second extension direction in which the second slit 18 extends inside the reactor 100 is preferably inclined or perpendicular to the supply direction of the sweep gas supplied from the sweep gas supply port T3 to the second permeate side space S22. Specifically, the angle θ2 of the second extension direction with respect to the supply direction is preferably 45 degrees or more and 135 degrees or less. This makes it possible to suppress bias in the gas flow from the sweep gas supply port T3 to each opening of the second slit 18, thereby suppressing bias in the sweep gas flow in the second permeate side space S22.

[0100] [Variation 3] In the above embodiment, the separation membrane 12 is in contact with the catalyst 13, but a buffer layer may be interposed between the separation membrane 12 and the catalyst 13. The buffer layer physically isolates the catalyst 13 from the separation membrane 12, thereby preventing cracks from occurring in the separation membrane 12 originating from the contact point with the catalyst 13 when the catalyst becomes hot due to reaction heat. The buffer layer may be made of a ceramic material or an organic polymer material. Examples of the ceramic material that may be used include silica, alumina, and chromia. Examples of the organic polymer material that may be used include PTFE, PVA, and PEG.

[0101] [Variation 4] In the above embodiment, the first flange 30 is separate from the first intermediate portion 50, but as shown in Fig. 9, the first flange 30 may be integral with the first intermediate portion 50. When the first flange 30 is integral with the first intermediate portion 50, the handling property in 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 FIG. 9, the second flange 40 may be integral with the second intermediate portion 60.

[0103] Also, as shown in Figure 10, even when using the monolith-type membrane structure described in the above-mentioned 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 separation membrane 12 is permeable to water vapor, which is one of the products of the conversion reaction from the raw material gas to liquid fuel, but this is not limited to this. The separation membrane 12 may also be permeable to the liquid fuel itself, which is produced by the conversion reaction from the raw material gas to liquid fuel. In this case as well, the reaction equilibrium of the above formula (1) can be shifted to the product side.

[0105] In addition, when the separation membrane 12 allows liquid fuel to permeate, even when the liquid fuel is produced by a reaction that does not produce water vapor (for example, 2H2+CO⇔CH3OH), the reaction equilibrium can be shifted to the product side.

[0106] [Variation 6] In the separation membrane module 1 according to the above embodiment (see FIG. 1), the sweep gas supply port T3 and the sweep gas exhaust port T4 are diagonally opposed to each other in a side view, and the sweep gas flows from the sweep gas supply port T3 to the sweep gas exhaust port T4, but this is not limited to this.

[0107] For example, as shown in Fig. 11, the sweep gas supply port T3 and the sweep gas exhaust port T4 may be disposed on the same side of the reactor 10 in a side view, and a straightening plate 20a may be provided to close a part of the gap between the reactor 10 and the housing 20. In Fig. 11, three straightening plates 20a are provided, but the number of the straightening plates 20a may be one, two, or four or more. The position of the straightening plate 20a can be set appropriately.

[0108] 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 from the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set appropriately.

[0109] 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.

[0110] [Variation 7] In the separation membrane module 1 according to the above embodiment (see FIG. 1), only one reactor 10 is accommodated in the housing 20, but this is not limiting.

[0111] For example, as shown in FIG. 13, a plurality of reactors 10 may be housed within a housing 20.

[0112] Also, as shown in Fig. 14, a straightening plate 20a may be provided to close a part of the gap between the reactor 10 and the housing 20. In Fig. 14, three straightening plates 20a are provided, but the number of the straightening plates 20a may be one, two, or four or more. The position of the straightening plate 20a can be set appropriately. Note that, as shown in Fig. 14, the sweep gas supply port T3 and the sweep gas exhaust port T4 may be disposed on the same side of the reactor 10 in a side view.

[0113] 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 from the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set appropriately.

[0114] 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.

[0115] [Variation 8] In the separation membrane module 1a according to the above-described modified example 2 (see FIG. 6), the sweep gas supply port T3 and the sweep gas exhaust port T4 are arranged diagonally opposite each other in a side view, but this is not limiting.

[0116] For example, as shown in FIG. 16, the sweep gas supply port T3 and the sweep gas exhaust port T4 may be disposed on the same side of the reactor 100 in a side view, or a straightening plate 20b may be provided to block a part of the gap between the reactor 100 and the housing 20. In FIG. 16, one straightening plate 20b is provided on each side of the flow stopper 90. The straightening plate 20b on the sweep gas supply port T3 side divides the space on the sweep gas supply port T3 side into a space where the sweep gas mainly flows into the second slit 18 of the reactor 100 and a space where the sweep gas flows in from the side of the reactor 100. The straightening plate 20b on the sweep gas exhaust port T4 side divides the space on the sweep gas exhaust port T4 side into a space where the sweep gas mainly flows out from the first slit 17 of the reactor 100 and a space where the sweep gas flows out from the side of the reactor 100. However, the number and positions of the straightening plates 20b can be set appropriately. Also, a portion of the sweep gas may pass through the interior of the flow stopper 90 .

[0117] 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 from the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set appropriately.

[0118] 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.

[0119] [Variation 9] In the separation membrane module 1a according to the above-mentioned modified example 2 (see FIG. 6), only one reactor 100 is accommodated in the housing 20, but this is not limiting.

[0120] For example, as shown in FIG. 18, a plurality of reactors 100 may be housed within the housing 20.

[0121] 19, a straightening plate 20b may be provided to block a part 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 appropriately. Also, a part 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.

[0122] 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 from the sweep gas outlet T4. The position of the sweep gas outlet T4 can be set appropriately.

[0123] 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. [Explanation of symbols]

[0124] 1. Separation membrane module 10 Reactor 10a 1st end 10b 2nd end 20. Housing G1 Inner surface J1 First opposing surface J2 2nd facing surface 21 Cylinder body 22 First end plate 23 Second end plate 30 No. 1 Furuno K1 end face L1 Outer surface M1 inner surface 40 No. 2 Furuno K2 end face L2 outer surface M2 inner surface 50 1st middle section P1 facing surface Q1 When meeting R1 joint surface 60 2nd middle part P2 facing surface Q2 When meeting R2 joint surface 70 1st bonding material 80 Second bonding material

Claims

1. A membrane assembly contained in a cylindrical housing, A columnar membrane structure; a first annular flange surrounding a first end of the membrane structure; a first intermediate portion disposed between a first end surface 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 membrane assembly comprising:

2. the first intermediate portion is integral with the first flange; The membrane assembly of claim 1 .

3. 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; a second bonding material interposed between the second flange and the membrane structure, and between the second intermediate portion and the membrane structure; The membrane assembly according to claim 1 or 2, comprising:

4. the second intermediate portion is integral with the second flange; The membrane assembly of claim 3.

5. The first flange is made of a ceramic material. The membrane assembly of claim 1 .

6. The second flange is made of a ceramic material. The membrane assembly of claim 3.

7. The membrane structure is a reactor. A membrane assembly according to claim 1 or 2.

8. The membrane structure is a separation filter. A membrane assembly according to claim 1 or 2.

9. A membrane assembly according to claim 1; a cylindrical housing that contains the membrane assembly; A separation membrane module comprising:

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