Separation membrane module

Abstract

A separation membrane module is provided with: a columnar reactor (10); an annular first flange (30) that surrounds a first end (10a) of the reactor (10); and a first intermediate section (50) that is disposed between a first end surface (F2) of the reactor (10) and a housing (20).

Description

Technical Field

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

[0002] Conventionally, a separation membrane module having a housing and a columnar membrane structure housed in the housing is known. Examples of the membrane structure include a separation filter configured to separate a given component from a mixed fluid using a separation membrane (for example, see Patent Document 1), a reactor configured to separate a product of a conversion reaction from a raw gas to a liquid fuel using a separation membrane (for example, see Patent Document 2), and the like.

[0003] Prior art literature Patent Literature Patent Document 1: International Publication No. 2018 / 180095 Patent Document 2: Japanese Patent Application Publication No. 2018-008940 Summary of the invention

[0004] Technical problem to be solved by the invention However, if the membrane structure is in direct contact with the housing, the membrane structure may be damaged, and therefore, it is preferable to adopt a structure in which the membrane structure is not in direct contact with the housing.

[0005] An object of the present invention is to provide a separation membrane module capable of suppressing damage to a membrane structure.

[0006] Technical solutions for solving technical problems The separation membrane module of the first aspect includes a cylindrical casing, a columnar membrane structure accommodated in the casing, an annular first flange surrounding a first end portion of the membrane structure, and a first intermediate portion disposed between a first end surface of the membrane structure and the casing.

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

[0008] In the separation membrane module of a third aspect according to the first or second aspect, the first intermediate portion and the first flange are integrated.

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

[0010] The separation membrane module of a fifth aspect according to any one of the first to fourth aspects includes: an annular second flange surrounding the second end portion of the membrane structure; and a second intermediate portion disposed between the second end surface of the membrane structure and the casing.

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

[0012] In the separation membrane module of a seventh aspect according to the fifth or sixth aspect, the second intermediate portion and the second flange are integrated.

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

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

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

[0016] Effects of the Invention According to the present invention, a separation membrane module capable of suppressing damage to a membrane structure can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a cross-sectional view of a separation membrane module according to an embodiment.

[0018] Figure 2 yes Figure 1 A partial enlarged view of .

[0019] Figure 3 yes Figure 1 A partial enlarged view of .

[0020] Figure 4 It is a cross-sectional view of a separation membrane module according to Modification Example 2.

[0021] Figure 5 yes Figure 4 AA cross-section diagram.

[0022] Figure 6 yes Figure 4 BB cross-section diagram.

[0023] Figure 7 It is a cross-sectional view of a separation membrane module according to Modification 4.

[0024] Figure 8 It is a cross-sectional view of a separation membrane module according to Modification 4.

[0025] Fig. 9 It is a cross-sectional view of a separation membrane module according to Modification 7.

[0026] Fig.10 It is a cross-sectional view of a separation membrane module according to Modification 7.

[0027] Fig.11 This is a cross-sectional view of a separation membrane module according to Modification 10.

[0028] Fig.12 This is a cross-sectional view of a separation membrane module according to Modification 10.

[0029] Fig.13 This is a cross-sectional view of a separation membrane module according to Modification 11.

[0030] Fig.14 This is a cross-sectional view of a separation membrane module according to Modification 11.

[0031] Fig.15 This is a cross-sectional view of a separation membrane module according to Modification 11.

[0032] Fig.16 It is a cross-sectional view of a separation membrane module according to Modification 12.

[0033] Fig.17 It is a cross-sectional view of a separation membrane module according to Modification 12.

[0034] Fig.18 This is a cross-sectional view of a separation membrane module according to Modification 13.

[0035] Fig.19 This is a cross-sectional view of a separation membrane module according to Modification 13.

[0036] Fig. 20 This is a cross-sectional view of a separation membrane module according to Modification 13. DETAILED DESCRIPTION

[0037] (Separation membrane module 1) The separation membrane module 1 according to the embodiment will be described. Figure 1 It is a cross-sectional view schematically showing the structure of the separation membrane module 1 .

[0038] like Figure 1 As shown, 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 joint 70, and a second joint 80. The reactor 10 is an example of the "membrane structure" according to the present invention.

[0039] [Reactor 10] The reactor 10 is housed in the 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 can be, for example, a cylindrical shape, an elliptical cylindrical shape, or a polygonal cylindrical shape.

[0040] Reactor 10 is a so-called membrane reactor for converting raw gas into liquid fuel. The raw gas contains at least hydrogen and carbon dioxide. The raw gas may contain carbon monoxide. The raw gas may be so-called synthesis gas (Syngas). Liquid fuel is a fuel that is in a liquid state at room temperature and pressure, or a fuel that can be liquefied under normal temperature and pressure. Examples of fuels that are in a liquid state at room temperature and pressure include methanol, ethanol, n H 2（m－2n） (m is an integer less than 90, n is an integer less than 30), and mixtures thereof. Examples of the fuel that can be liquefied under normal temperature and pressure include propane, butane, and mixtures thereof.

[0041] For example, the reaction formula (1) for synthesizing methanol by catalytic hydrogenation of a raw material gas containing hydrogen and carbon dioxide in the presence of a catalyst is as follows.

[0042] CO2+3H2 CH3OH+H2O(1) The above reaction is a balanced reaction, and the reactor 10 can shift the reaction equilibrium to the product side by separating the water vapor as the product of the conversion reaction. In order to improve the conversion efficiency and reaction rate, it is preferred to carry out the conversion reaction at high temperature and high pressure (for example, above 180°C and above 2MPa). The liquid fuel is in a gaseous state at the time of being synthesized, and the gaseous state is maintained unchanged at least before flowing out of the reactor 10. The reactor 10 preferably has heat resistance and pressure resistance suitable for the desired synthesis conditions of the liquid fuel.

[0043] The reactor 10 involved in this embodiment is a so-called tubular type. Figure 1 As shown, 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 the side surface of the columnar reactor 10. The outer peripheral 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 at the first end surface F2. The raw gas flows into the interior 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 at the second end surface F3. The liquid fuel flows out to the outside of the reactor 10 from the second opening T2.

[0044] 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 length 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 length direction. The second end 10b includes the second end face F3 described above.

[0045] Here, the reactor 10 is composed of a porous support 11 , a separation membrane 12 , a catalyst 13 , and a catalyst stopper 14 .

[0046] The porous support 11 is formed into a cylindrical shape extending in the longitudinal direction. The porous support 11 is made of a porous material. As the porous material, ceramic materials, metal materials, resin materials, and composite members thereof can be used, and ceramic materials are particularly preferred. As the aggregate of the ceramic material, alumina (Al2O3), titanium dioxide (TiO2), mullite (Al2O3·SiO2), ceramic granules, cordierite (Mg2Al4Si5O 18 ), and composite materials containing two or more of them, etc., in view of the ease of acquisition, the stability of the green clay and the corrosion resistance, alumina is preferred. As the inorganic binding material of the ceramic material, at least one of titanium dioxide, mullite, sinterable alumina, silicon dioxide, glass powder, clay mineral and sinterable cordierite can be used. However, the ceramic material may not contain an inorganic binding material.

[0047] The average pore size of the porous support 11 can be set to be greater than 5 μm and less than 25 μm. The average pore size of the porous support 11 can be measured by mercury intrusion. The porosity of the porous support 11 can be set to be greater than 25% and less than 50%. The average particle size of the porous material can be set to be greater than 1 μm and less than 100 μm. The average particle size refers to the arithmetic mean of the maximum diameters of 30 particles (randomly selected) measured by cross-sectional microstructure observation using a SEM (Scanning Electron Microscope).

[0048] The separation membrane 12 is supported by the porous support 11. The separation membrane 12 is formed in a cylindrical shape extending in the longitudinal direction. The inner side of the separation membrane 12 is a non-permeable side space S1 to which the raw material gas is supplied. The non-permeable side space S1 is a space between the first opening T1 and the second opening T2. In the present embodiment, the separation membrane 12 is arranged on the inner surface of the porous support 11, but it can also be arranged on the outer surface of the porous support 11.

[0049] The separation membrane 12 allows water vapor, which is a product of the reforming reaction from the raw material gas to the liquid fuel, to permeate, thereby shifting the reaction equilibrium of the above-mentioned formula (1) to the product side by utilizing the equilibrium shift effect.

[0050] The separation membrane 12 preferably has a relative humidity of 100 nmol / (s·Pa·m 2 ) or more. The water vapor permeability coefficient can be determined by a known method (see Ind. Eng. Chem. Res., 40, 163-175 (2001)).

[0051] 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 pass through, and the harder it is for components other than water vapor (hydrogen, carbon dioxide, and liquid fuel, etc.) to pass through. The separation factor can be obtained by a known method (see Fig. 1 of "Separation and Purification Technology 239 (2020) 116533").

[0052] As the separation membrane 12, an inorganic membrane can be used. The inorganic membrane is preferred because it has heat resistance, pressure resistance, and water vapor resistance. Examples of the inorganic membrane include zeolite membranes, silica membranes, alumina membranes, or composite membranes thereof. In particular, an LTA-type zeolite membrane having a molar ratio (Si / Al) of silicon element (Si) to aluminum element (Al) of 1.0 or more and 3.0 or less is preferred because it has excellent water vapor permeability.

[0053] The catalyst 13 is arranged inside the separation membrane 12, that is, in the non-permeate side space S1. The catalyst 13 is preferably filled in the non-permeate side space S1, but may be arranged in a layer or island shape on the surface of the separation membrane 12. The catalyst 13 promotes the conversion reaction from the raw gas to the liquid fuel represented by the above formula (1).

[0054] A known catalyst suitable for the conversion reaction from the raw material gas to the liquid fuel can be used as the catalyst 13. Examples of the catalyst 13 include metal catalysts (copper, palladium, etc.), oxide catalysts (zinc oxide, zirconium oxide, gallium oxide, etc.), and composite catalysts thereof (copper-zinc oxide, copper-zinc oxide-alumina, copper-zinc oxide-chromium oxide-alumina, copper-cobalt-titanium dioxide, and catalysts obtained by modifying these with palladium, etc.).

[0055] The catalyst stopper 14 is configured to cover the second opening T2 formed on the second end surface F3. The catalyst stopper 14 prevents the catalyst 13 from leaking out from the second opening T2. The catalyst stopper 14 has a structure that does not hinder the outflow of liquid fuel while preventing the catalyst 13 from leaking out. As the catalyst stopper 14, for example, a mesh member, a perforated plate, etc. can be used. It should be noted that in the present embodiment, the catalyst stopper 14 is fixed by being sandwiched between the shell 20 and the second flange 40, but it can also be installed on the second end surface F3 of the reactor 10.

[0056] However, when the catalyst 13 is unlikely to leak out (for example, when the catalyst 13 is arranged in a layer or island shape on the surface of the separation membrane 12 ), the reactor 10 may not include the catalyst stopping portion 14 .

[0057] In the reactor 10 , the raw gas supplied to the non-permeate space S1 is converted into liquid fuel by the catalyst 13 , and water vapor as a product of the conversion reaction passes through the separation membrane 12 and the porous support 11 and is separated into the permeate space S2 described later.

[0058] [Housing 20] The shell 20 is formed in a cylindrical shape as a whole. The shell 20 accommodates the reactor 10. The shell 20 has a structure that can withstand the conversion reaction at high temperature and high pressure (for example, 180° C. or higher, 2 MPa or higher). When the raw gas and / or the purge gas contains hydrogen, the constituent material of the shell 20 is preferably resistant to hydrogen embrittlement. The shell 20 can be mainly composed of a metal material (stainless steel, etc.).

[0059] like Figure 1 As shown, the housing 20 is composed of a cylinder body 21 , a first end plate 22 and a second end plate 23 .

[0060] The cylinder body 21 is formed in a cylindrical shape extending in the longitudinal direction. Both ends of the cylinder body 21 are expanded in diameter to form a flange shape.

[0061] The tube body 21 has an inner peripheral surface G1 , a first end surface G2 , a second end surface G3 , a purge gas supply port T3 , and a purge gas discharge port T4 .

[0062] The inner peripheral surface G1 faces the outer peripheral surface F1 of the reactor 10 and is separated from the outer peripheral surface F1. The gap between the inner peripheral surface G1 and the outer peripheral surface F1 is a permeate side space S2 for recovering water vapor as a product of the reforming reaction.

[0063] An annular first recess H1 is formed at one end of the inner circumferential surface G1. An annular first elastic member 26a is disposed in the first recess H1. As the first elastic member 26a, for example, expanded graphite, a rubber O-ring, etc. can be used. The first elastic member 26a is in close contact with the first flange 30 described later. As a result, the cylinder body 21 and the first flange 30 are sealed.

[0064] An annular second recess H2 is formed at the other end of the inner circumferential surface G1. An annular second elastic member 26b is disposed in the second recess H2. As the second elastic member 26b, for example, expanded graphite, a rubber O-ring, etc. can be used. The second elastic member 26b is in close contact with the second flange 40 described later. As a result, the cylinder body 21 and the second flange 40 are sealed.

[0065] An annular first recess H3 is formed on the first end surface G2. A third elastic member 26c is disposed in the first recess H3. As the third elastic member 26c, for example, expanded graphite, a rubber O-ring, etc. can be used. The third elastic member 26c is in close contact with the first end plate 22. Thus, the cylinder body 21 and the first end plate 22 are sealed.

[0066] An annular second recess H4 is formed on the second end surface G3. A fourth elastic member 26d is disposed in the second recess H4. As the fourth elastic member 26d, for example, expanded graphite, a rubber O-ring, etc. can be used. The fourth elastic member 26d is in close contact with the second end plate 23. Thus, the cylinder body 21 and the second end plate 23 are sealed.

[0067] The purge gas supply port T3 and the purge gas exhaust port T4 are respectively connected to the permeate side space S2. The purge gas is supplied to the permeate side space S2 from the purge gas supply port T3. The purge gas absorbs water vapor in the permeate side space S2 and absorbs the reaction heat accompanying the conversion reaction. The purge gas is discharged from the purge gas exhaust port T4 together with the water vapor. Hydrogen and / or carbon dioxide can be used as the purge gas. In addition, as the purge gas, an inert gas (such as nitrogen), air, etc. can also be used. In the present embodiment, the purge gas supply port T3 and the purge gas exhaust port T4 are tilted opposite to each other when viewed in section, but the respective positions of the purge gas supply port T3 and the purge gas exhaust port T4 can be appropriately changed.

[0068] The first end plate 22 is an annular plate member. The first end plate 22 has an inlet 22a for the raw material gas to flow in. The raw material gas is supplied to the non-permeable side space S1 of the reactor 10 through the inlet 22a.

[0069] The central portion of the first end plate 22 is expanded into a flange shape. The first end plate 22 has a first opposing surface J1. The first opposing surface J1 is opposed to the first end surface F2 of the reactor 10 and the end surface K1 of the first flange 30 described later. In the present embodiment, the first opposing surface J1 is separated from the first end surface F2 of the reactor 10 and the end surface K1 of the first flange 30, respectively. The first opposing surface J1 abuts against the first end surface G2 of the barrel body 21.

[0070] The first end plate 22 is connected to the cylinder body 21 via a plurality of fixing members 27. The fixing members 27 are composed of, for example, bolts and nuts. The first end plate 22 is in close contact with the third elastic member 26c.

[0071] The second end plate 23 is an annular plate member. The second end plate 23 has an outflow port 23a through which the liquid fuel flows out. The liquid fuel is discharged from the non-permeable side space S1 of the reactor 10 to the outside through the outflow port 23a.

[0072] The central part of the second end plate 23 is expanded into a flange shape. The second end plate 23 has a second opposing surface J2. The second opposing surface J2 is opposed to the second end surface F3 of the reactor 10 and the end surface K2 of the second flange 40 described later. In the present embodiment, the second opposing surface J2 is separated from the second end surface F3 of the reactor 10 and the end surface K2 of the second flange 40, respectively. The second opposing surface J2 abuts against the second end surface G3 of the barrel body 21.

[0073] The second end plate 23 is connected to the cylinder body 21 via 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.

[0074] [First flange 30] The first flange 30 is mounted on the reactor 10. The first flange 30 is joined to the reactor 10 via the first joint 70. The first flange 30 functions as a spacer for forming a permeate side space S2 between the reactor 10 and the cartridge 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 embedded in one end of the cartridge body 21. The first flange 30 supports the first end 10a of the reactor 10 at a position separated from the cartridge body 21. Thus, a permeate side space S2 is formed between the reactor 10 and the cartridge body 21.

[0075] 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 a face on the outside of the first flange 30 in the longitudinal direction. The end face K1 is opposite to the first opposing surface J1 of the first end plate 22. At least a portion of the end face K1 may also abut against the first opposing surface J1. In the present embodiment, the end face K1 is planar. The outer peripheral surface L1 is a face on the radially outer side of the first flange 30. The outer peripheral surface L1 is opposite to the inner peripheral surface G1 of the barrel body 21 and is in close contact with the first elastic member 26a. The outer peripheral surface L1 may also abut against the inner peripheral surface G1. The inner peripheral surface M1 is arranged on the opposite side of the outer peripheral surface L1. The inner peripheral surface M1 is opposite to the outer peripheral surface F1 of the reactor 10 via the first coupling member 70. The inner peripheral surface M1 may also abut against the first intermediate portion 50 described later.

[0076] The first flange 30 is made of a dense ceramic material. As the ceramic material, for example, aluminum oxide, zirconium oxide, silicon carbide, aluminum nitride, cordierite, and a composite material containing two or more of them can be used. The first flange 30 needs to have airtightness and liquid-tightness. Therefore, the porosity of the first flange 30 is preferably 10.0% or less, and more preferably 5.0% or less.

[0077] [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 joint 80. The second flange 40 is arranged 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 cartridge 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 embedded in the other end of the cartridge body 21. The second flange 40 supports the second end 10b of the reactor 10 at a position separated from the cartridge body 21.

[0078] 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 a face on the outside of the second flange 40 in the longitudinal direction. The end face K2 is opposite to the second opposing surface J2 of the second end plate 23. At least a portion of the end face K2 may also abut against the second opposing surface J2. In the present embodiment, the end face K2 is planar. The outer peripheral surface L2 is a face on the radially outer side of the second flange 40. The outer peripheral surface L2 is opposite to the inner peripheral surface G1 of the barrel body 21 and is in close contact with the second elastic member 26b. The outer peripheral surface L2 may also abut against the inner peripheral surface G1. The inner peripheral surface M2 is arranged on the opposite side of the outer peripheral surface L2. The inner peripheral surface M2 is opposite to the outer peripheral surface F1 of the reactor 10 via the second joint 80. The inner peripheral surface M2 may also abut against the second intermediate portion 60 described later.

[0079] The second flange 40 is made of a dense ceramic material. As the ceramic material, for example, aluminum oxide, zirconium oxide, silicon carbide, aluminum nitride, cordierite, and a composite material containing two or more of them can be used. The second flange 40 needs to have airtightness and liquid-tightness. Therefore, the porosity of the second flange 40 is preferably 10.0% or less, and more preferably 5.0% or less.

[0080] [First intermediate portion 50] The first intermediate portion 50 is an annular thin plate member. The first intermediate portion 50 is disposed between the reactor 10 and the shell 20. Specifically, the first intermediate portion 50 is disposed between the first end face F2 of the reactor 10 and the first opposing face J1 of the first end plate 22. In this way, by interposing the first intermediate portion 50 between the reactor 10 and the shell 20, direct contact between the reactor 10 and the first end plate 22 can be suppressed. Therefore, damage (nicks, cracks, etc.) on the reactor 10 can be suppressed.

[0081] like Figure 1 As shown, the first intermediate portion 50 is preferably joined to the reactor 10 by a first jointer 70. Thus, the first intermediate portion 50 and the reactor 10 can be substantially integrated, and thus damage to the reactor 10 can be further suppressed.

[0082] The first intermediate portion 50 can be made of a ceramic material, a resin material, or a metal material. As the ceramic material, the ceramic material constituting the first flange 30 described above can be used. The first intermediate portion 50 is preferably harder than the porous support 11 of the reactor 10. Thus, the reactor 10 can be further protected by the first intermediate portion 50, so that damage to the reactor 10 can be further suppressed.

[0083] Here, Figure 2 yes Figure 1 A partial enlarged view of Figure 2 As shown, the first intermediate portion 50 has an opposing surface P1 , a contact surface Q1 , a joining surface R1 , and an inner peripheral surface U1 .

[0084] The opposing surface P1 is opposed to the shell 20. The opposing surface P1 may also abut against the opposing surface J1 of the first end plate 22. In the present embodiment, the opposing surface P1 and the end surface K1 of the first flange 30 are in the same plane, but a step may be formed between the opposing surface P1 and the end surface K1. The abutting surface Q1 abuts against the inner peripheral surface M1 of the first flange 30. The joining surface R1 is joined to the first joining member 70. In the present embodiment, the inner peripheral surface U1 and the inner peripheral surface U2 of the first end plate 22 are in the same plane, but it may not be in the same plane with the inner peripheral surface U2. In the present embodiment, the opposing surface P1, the abutting surface Q1 and the joining surface R1 are each planar, but at least one of them may be bent or folded as a whole or partially.

[0085] [Second intermediate portion 60] The second intermediate portion 60 is an annular thin plate member. The second intermediate portion 60 is disposed between the reactor 10 and the shell 20. Specifically, the second intermediate portion 60 is disposed between the second end face F3 of the reactor 10 and the second opposing face J2 of the second end plate 23. In this way, by interposing the second intermediate portion 60 between the reactor 10 and the second end plate 23, direct contact between the reactor 10 and the shell 20 can be suppressed. Therefore, damage (notches, cracks, etc.) on the reactor 10 can be suppressed.

[0086] like Figure 1 As shown, the second intermediate portion 60 is preferably joined to the reactor 10 by a second jointer 80. Thus, the second intermediate portion 60 and the reactor 10 can be substantially integrated, and thus damage to the reactor 10 can be further suppressed.

[0087] The second intermediate portion 60 can be made of a ceramic material, a resin material, or a metal material. As the ceramic material, the ceramic material constituting the second flange 40 described above can be used. The second intermediate portion 60 is preferably harder than the porous support 11 of the reactor 10. Thus, the reactor 10 can be further protected by the second intermediate portion 60, so that damage to the reactor 10 can be further suppressed.

[0088] Here, Figure 3 yes Figure 1 A partial enlarged view of Figure 3 As shown, the second intermediate portion 60 has an opposing surface P2, a contact surface Q2, a joining surface R2, and an inner peripheral surface U3.

[0089] The opposing surface P2 is opposed to the shell 20. The opposing surface P2 may also abut against the opposing surface J2 of the second end plate 23. In the present embodiment, the opposing surface P2 and the end surface K2 of the second flange 40 are in the same plane, 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 member 80. In the present embodiment, the inner peripheral surface U3 is in the same plane as the inner peripheral surface U4 of the second end plate 23, but it may not be in the same plane as the inner peripheral surface U4. In the present embodiment, the opposing surface P2, the abutting surface Q2, and the joining surface R2 are each planar, but at least one of them may be bent or folded as a whole or partially.

[0090] [First joining member 70] The first joint 70 is respectively interposed between the first flange 30 and the reactor 10, and between the first middle portion 50 and the reactor 10. The first joint 70 joins the first flange 30 to the reactor 10, and joins the first middle portion 50 to the reactor 10. The first joint 70 is disposed 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 middle portion 50 and the reactor 10. Figure 2 As shown, the cross section of the first coupling member 70 is L-shaped.

[0091] It should be noted that the joint body of the first flange 30 and the reactor 10 joined by the first joint member 70 is the “separation membrane module” according to the present invention.

[0092] As the first bonding material 70 , crystallized glass, amorphous glass, brazing material, ceramics, or the like can be used. In consideration of heat resistance and pressure resistance, crystallized glass is particularly preferable.

[0093] As crystallized glass, for example, SiO2-B2O3 system, SiO2-CaO system, SiO2-Al2O3 system, SiO2-MgO system, SiO-ZnO-BaO system, SiO2-B2O3-CaO system, or SiO2-MgO-CaO system, SiO2-Al2O3-B2O3 system, SiO2-MgO-Al2O3 system crystallized glass can be used. It should be noted that in this specification, so-called crystallized glass refers to a glass in which the ratio (degree of crystallinity) of "volume occupied by crystalline phase" relative to total volume is more than 60%, and the ratio of "volume occupied by amorphous phase and impurities" relative to total volume is less than 40%.

[0094] [Second joining member 80] The second joint 80 is respectively interposed between the second flange 40 and the reactor 10, and between the second middle portion 60 and the reactor 10. The second joint 80 joins the second flange 40 to the reactor 10, and joins the second middle portion 60 to the reactor 10. The second joint 80 is disposed at least a portion of the gap between the second flange 40 and the reactor 10, and at least a portion of the gap between the second middle portion 60 and the reactor 10. Figure 3 As shown, the cross section of the second coupling member 80 is L-shaped.

[0095] It should be noted that the joint body of the second flange 40 and the reactor 10 joined by the second joint member 80 is the “separation membrane module” according to the present invention.

[0096] As the second bonding material 80 , crystallized glass, amorphous glass, brazing material, ceramics, or the like can be used. In consideration of heat resistance and pressure resistance, crystallized glass is particularly preferable.

[0097] [Assembly of Separation Membrane Module 1] The assembly process of the separation membrane module 1 includes a step of manufacturing a reactor assembly by joining the first flange 30 and the second flange 40 and the first intermediate portion 50 and the second intermediate portion 60 to the reactor 10 , and a step of housing the reactor assembly in the casing 20 .

[0098] The process of making the reactor assembly includes a first process of forming a molded body of a bonding material, a second process of installing a flange and an intermediate portion, and a third process of heating the molded body of the bonding material. In the first process, a molded body of the first bonding member 70 is formed at the first end 10a of the reactor 10, and a molded body of the second bonding member 80 is formed at the second end 10b of the reactor 10. In the second process, the first flange 30 and the first intermediate portion 50 are installed in a manner surrounding the molded body of the first bonding member 70, and the second flange 40 and the second intermediate portion 60 are installed in a manner surrounding the molded body of the second bonding member 80. In the third process, the molded bodies of the first bonding member 70 and the second bonding member 80 are heated to grow crystals or melt, and then cooled to room temperature, thereby forming the first bonding member 70 and the second bonding member 80. Through the above processes, the reactor assembly is completed, and the first flange 30 and the second flange 40, and the first intermediate portion 50 and the second intermediate portion 60 are connected to the reactor 10 via the first bonding member 70 and the second bonding member 80.

[0099] Next, the process of accommodating the reactor assembly includes a fourth process of inserting the reactor assembly, a fifth process of installing the elastic member, and a sixth process of connecting the end plate. In the fourth process, after the reactor assembly is inserted into the barrel body 21, the two ends of the reactor assembly are aligned. In the fifth process, the first to fourth elastic members 26a to 26d are embedded in the first to fourth recesses H1 to H4 of the barrel body 21. In the sixth process, the first end plate 22 is connected to the barrel body 21 by the fixing member 27, and the second end plate 23 is connected to the barrel body 21 by the fixing member 28. Through the above processes, the separation membrane module 1 in which the reactor assembly is accommodated in the shell 20 is completed.

[0100] Since the first intermediate portion 50 is interposed between the reactor 10 and the first end plate 22, it is possible to suppress the first end plate 22 from directly contacting the reactor 10 in the sixth step. Therefore, it is possible to suppress damage to the reactor 10. Similarly, since the second intermediate portion 60 is interposed between the reactor 10 and the second end plate 23, it is possible to suppress the second end plate 23 from directly contacting the reactor 10 in the sixth step. Therefore, it is possible to suppress damage to the reactor 10.

[0101] (Modification of the embodiment) As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, Various changes can be made within the range which does not deviate from the summary of this invention.

[0102] [Modification 1] In the above embodiment, the case where the reactor 10 is used as the membrane structure is described, but a separation filter can also be used as the membrane structure. The separation filter has the same structure as the reactor 10 except that a separation membrane that allows a desired component contained in the mixed fluid to pass is used instead of the separation membrane 12 that allows water vapor to pass through and that the catalyst 13 is not provided. In addition, in the present invention, even if a separation filter is used as a membrane structure, it is assumed that it is used under high temperature and high pressure conditions.

[0103] It should be noted that when a separation filter is used as a membrane structure, no reaction heat is generated and the need for temperature control is low. Therefore, the components that have passed through the separation membrane can be discharged from the purge gas outlet T4 by reducing the pressure on the purge gas outlet T4 side compared to the purge gas supply port T3 side.

[0104] [Modification 2] In the above embodiment, the reactor 10 as an example of a membrane structure is a tube type, but it may also be a monolithic type. In addition, when a separation filter is used as a membrane structure, the separation filter may be a tube type or a monolithic type. The so-called monolithic type refers to a shape having a plurality of small chambers penetrating in the length direction, which is a concept including a honeycomb type.

[0105] Figure 4 is a cross-sectional view schematically showing the structure of a separation membrane module 1a having a monolithic reactor 100. Figure 4 , only the reactor 100 is shown in a side view.

[0106] 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. In the reactor 100, the catalyst stopper 14 is also an arbitrary structure.

[0107] The stopper 90 is formed in an annular shape. The stopper 90 is disposed between the reactor 100 and the shell 20. The stopper 90 divides the gap between the reactor 100 and the shell 20 into a purge gas discharge space S21 and a purge gas supply space S22. The stopper 90 suppresses the purge gas from flowing directly between the purge gas discharge space S21 and the purge gas supply space S22. The stopper 90 may not seal the space between the reactor 100 and the shell 20 as long as it can suppress the direct flow of the purge gas. The stopper 90 may be made of, for example, expanded graphite, rubber, resin, metal, or the like.

[0108] The reactor 100 includes a plurality of first flow paths 15 , a plurality of second flow paths 16 , a first slit 17 , and a second slit 18 .

[0109] The first flow path 15 penetrates the reactor 100 in the longitudinal direction. The first flow path 15 opens at the first end face F2 and the second end face F3. The separation membrane 12 is formed on the inner surface of the first flow path 15. The inner side of the separation membrane 12 is the non-permeable side space S1. The catalyst 13 is arranged in the non-permeable side space S1.

[0110] The second flow path 16 is formed inside the reactor 100. The second flow path 16 extends in the longitudinal direction. The second flow path 16 is closed at the first end surface F2 and the second end surface F3.

[0111] The first slit 17 is formed at the first end 100a of the reactor 100. The first slit 17 penetrates through each second flow path 16 in the radial direction and opens at the outer peripheral surface F1. Therefore, the first slit 17 communicates with each second flow path 16 and the purge gas discharge space S21.

[0112] The second slit 18 is formed at the second end 100b of the reactor 100. The second slit 18 penetrates through each second flow path 16 in the radial direction and opens at the outer peripheral surface F1. Therefore, the second slit 18 communicates with each second flow path 16 and the purge gas supply space S22.

[0113] When the raw gas is supplied to the first flow path 15, the raw gas is converted into liquid fuel under the action of the catalyst 13, and water vapor as a product of the conversion reaction flows into the second flow path 16 through the separation membrane 12. The water vapor flowing into the second flow path 16 enters the purge gas flowing into the second flow path 16 from the purge gas supply port T3 via the purge gas supply space S22 and the second slit 18, and is then discharged to the outside from the purge gas discharge port T4 via the first slit 17 and the purge gas discharge space S21.

[0114] It should be noted that in this modification, the purge gas supply port T3 and the purge gas exhaust port T4 are arranged on a straight line that intersects the axis of the reactor 10 when viewed in cross section. As a result, the flow path length of the purge gas in the purge gas exhaust space S21 can be equal to the flow path length of the purge gas in the purge gas supply space S22, so the flow deviation of the purge gas can be suppressed. However, the positional relationship between the purge gas supply port T3 and the purge gas exhaust port T4 can be appropriately changed.

[0115] Figure 5 yes Figure 4 AA cross-section diagram. Figure 5 As shown, the first slit 17 passes through 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 peripheral surface F1. The purge gas flowing out from the two openings of the first slit 17 to the purge gas discharge space S21 passes through the purge gas discharge space S21 and is discharged to the outside from the purge gas discharge port T4.

[0116] Here, the first extension direction of the first slit 17 extending inside the reactor 100 is preferably inclined or orthogonal to the discharge direction of the purge gas discharged from the purge gas outlet T4 to the outside. Specifically, the angle of the first extension direction to the discharge direction is θ 1 is 45 degrees or more and 135 degrees or less. This can suppress the deviation of the gas flow from each opening of the first slit 17 to the purge gas discharge port T4, and thus can suppress the deviation of the purge gas in the purge gas discharge space S21.

[0117] Figure 6 yes Figure 4 BB cross-section diagram. Figure 6 As shown, the second slit 18 passes through 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 peripheral surface F1. The purge gas supplied from the purge gas supply port T3 to the purge gas supply space S22 passes through the purge gas supply space S22 and flows into the two openings of the second slit 18 respectively.

[0118] Here, the second extension direction of the second slit 18 extending inside the reactor 100 is preferably inclined or orthogonal to the supply direction of the purge gas supplied from the purge gas supply port T3 to the purge gas supply space S22. Specifically, the angle of the second extension direction relative to the supply direction is θ 2 is preferably 45 degrees or more and 135 degrees or less. This can suppress the deviation of the gas flow from the purge gas supply port T3 to each opening of the second slit 18, and thus can suppress the deviation of the purge gas in the purge gas supply space S22.

[0119] [Variation 3] In the above-mentioned 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 can inhibit the generation of cracks starting from the contact point with the catalyst 13 in the separation membrane 12 when the catalyst becomes high temperature due to the heat of reaction by physically isolating the catalyst 13 from the separation membrane 12. The buffer layer can be composed of a ceramic material or an organic polymer material. As a ceramic material, silicon dioxide, aluminum oxide, chromium oxide, etc. can be used. As an organic polymer material, PTFE, PVA, PEG, etc. can be used.

[0120] [Variation 4] In the above embodiment, the first flange 30 and the first middle portion 50 are separate bodies. Figure 7 As shown, the first flange 30 may be integrated with the first intermediate portion 50. When the first flange 30 and the first intermediate portion 50 are integrated, the workability in the assembly process of the separation membrane module 1 can be improved.

[0121] Similarly, in the above embodiment, the second flange 40 and the second middle portion 60 are separate bodies, but Figure 7 As shown, the second flange 40 may also be integral with the second intermediate portion 60 .

[0122] In addition, if Figure 8 As shown, when the one-piece membrane structure described in the above modification 2 is used, the first flange 30 can be integrated with the first middle portion 50 , and the second flange 40 can be integrated with the second middle portion 60 .

[0123] [Variation 5] In the above embodiment, the first intermediate portion 50 is disposed in the entire gap between the reactor 10 and the first end plate 22, but may be disposed only in a portion of the gap. In this case, as the first intermediate portion 50, a C-shaped thin plate member, a plurality of thin plate members separated and disposed in the circumferential direction, etc. may be used.

[0124] Likewise, in the above-described embodiment, the second intermediate portion 60 is disposed in the entire gap between the reactor 10 and the second end plate 23 , but may be disposed only in a portion of the gap.

[0125] [Variation 6] In the above embodiment, the first joint 70 is interposed between the first flange 30 and the reactor 10 and between the first middle portion 50 and the reactor 10, but may not be interposed between the first middle portion 50 and the reactor 10. In this case, the first middle portion 50 may be in direct contact with the reactor 10.

[0126] Similarly, in the above embodiment, the second joint 80 is interposed between the second flange 40 and the reactor 10, and between the second middle portion 60 and the reactor 10, but may not be interposed between the second middle portion 60 and the reactor 10. In this case, the second middle portion 60 may be in direct contact with the reactor 10.

[0127] [Variation 7] In the above embodiment, if Figure 2 As shown in FIG. 5 , the inner circumferential surface U1 of the first intermediate portion 50 and the inner circumferential surface U2 of the first end plate 22 are in the same plane, but the present invention is not limited thereto. Fig. 9 As shown, the inner circumferential surface U1 of the first intermediate portion 50 may also be located radially inward of the inner circumferential surface U2 of the first end plate 22. Fig.10 As shown, the inner peripheral surface U1 of the first intermediate portion 50 may be located radially outward from the inner peripheral surface U2 of the first end plate 22 .

[0128] Similarly, in the above embodiment, if Figure 3 As shown, the inner circumferential surface U3 of the second intermediate portion 60 and the inner circumferential surface U4 of the second end plate 23 are in the same plane, but the present invention is not limited thereto. Although not shown, the inner circumferential surface U3 of the second intermediate portion 60 may be located radially inward of the inner circumferential surface U4 of the second end plate 23, or radially outward of the inner circumferential surface U4 of the second end plate 23.

[0129] [Variation 8] In the above embodiment, the separation membrane 12 allows water vapor, which is a product of the conversion reaction from the raw gas to the liquid fuel, to pass through, but the present invention is not limited thereto. The separation membrane 12 may also allow the liquid fuel itself, which is a product of the conversion reaction from the raw gas to the liquid fuel, to pass through. In this case, the reaction equilibrium of the above formula (1) can also be shifted to the product side.

[0130] In addition, when the separation membrane 12 allows liquid fuel to permeate, the reaction without by-product water vapor (for example, H2+CO When CH3OH) is used to generate liquid fuel, the reaction equilibrium can also be shifted to the product side.

[0131] [Variation 9] In the separation membrane module 1 according to the above embodiment (see Figure 1 ), the purge gas supply port T3 and the purge gas exhaust port T4 are obliquely opposed to each other in a side view, and the purge gas flows from the purge gas supply port T3 toward the purge gas exhaust port T4, but the present invention is not limited to this.

[0132] For example, Fig.11 As shown, the purge gas supply port T3 and the purge gas exhaust port T4 may be arranged on the same side of the reactor 10 in a side view, and a rectifying plate 20a may be provided to block a portion of the gap between the reactor 10 and the housing 20. Fig.11 In the embodiment, three rectifying plates 20a are provided, but the number of rectifying plates 20a may be one, two, or four or more. The position of the rectifying plates 20a may be appropriately set.

[0133] In addition, if Fig.12 As shown, the housing 20 may not have the purge gas supply port T3, and the purge gas may not 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 purge gas discharge port T4. The position of the purge gas discharge port T4 can be appropriately set.

[0134] It should be explained that Fig.11 and Fig.12 The structure can also be applied to the case where a separation filter is used as the membrane structure instead of the reactor 10.

[0135] [Variation 10] In the separation membrane module 1 according to the above embodiment (see Figure 1 ), only one reactor 10 is housed in the shell 20, but the present invention is not limited to this.

[0136] For example, Fig.13 As shown, a plurality of reactors 10 may be housed in the housing 20 .

[0137] In addition, if Fig.14 As shown, a rectifying plate 20a may be provided to block a portion of the gap between each reactor 10 and the housing 20. Fig.14 In the embodiment, three rectifier plates 20a are provided, but the number of rectifier plates 20a may be one, two or more than four. The position of the rectifier plates 20a can be appropriately set. Fig.14 As shown, the purge gas supply port T3 and the purge gas exhaust port T4 may be arranged on the same side of the reactor 10 in a side view.

[0138] In addition, if Fig.15 As shown, the housing 20 may not have the purge gas supply port T3, and the purge gas may not 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 purge gas discharge port T4. The position of the purge gas discharge port T4 can be appropriately set.

[0139] It should be explained that Figure 13 to Figure 15 The structure can also be applied to the case where a separation filter is used as the membrane structure instead of the reactor 10.

[0140] [Variation 11] In the separation membrane module 1a according to the above-mentioned modification 2 (see Figure 4 ), the purge gas supply port T3 and the purge gas exhaust port T4 are obliquely opposed to each other in a side view, but the present invention is not limited to this.

[0141] For example, Fig.16 As shown, the purge gas supply port T3 and the purge gas exhaust port T4 may be arranged on the same side of the reactor 100 in a side view, and a rectifying plate 20b may be provided to block a portion of the gap between the reactor 100 and the housing 20. Fig.16 In the embodiment, a rectifying plate 20b is provided on each side of the stopper 90. The rectifying plate 20b on the purge gas supply port T3 side divides the space on the purge gas supply port T3 side into: a gap where the purge gas mainly flows into the second slit 18 of the reactor 100; and a gap where the purge gas flows in from the side of the reactor 100. The rectifying plate 20b on the purge gas discharge port T4 side divides the space on the purge gas discharge port T4 side into: a gap where the purge gas mainly flows out from the first slit 17 of the reactor 100; and a gap where the purge gas flows out from the side of the reactor 100. However, the number and position of the rectifying plates 20b can be appropriately set. In addition, a portion of the purge gas may also pass through the inside of the stopper 90.

[0142] In addition, if Fig.17 As shown, the housing 20 may not have the purge gas supply port T3, and the purge gas may not 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 purge gas discharge port T4. The position of the purge gas discharge port T4 can be appropriately set.

[0143] It should be explained that Fig.16 and Fig.17 The structure can also be applied to the case where a separation filter is used as the membrane structure instead of the reactor 100.

[0144] [Variation 12] In the separation membrane module 1a according to the above-mentioned modification 2 (see Figure 4 ), only one reactor 100 is housed in the shell 20, but the present invention is not limited to this.

[0145] For example, Fig.18 As shown, a plurality of reactors 100 may be housed in the housing 20 .

[0146] In addition, if Fig.19 As shown, a rectifying plate 20b may be provided to block a portion of the gap between the reactor 100 and the housing 20. Fig.19 In the figure, a rectifying plate 20b is provided on each side of the stop portion 90. The rectifying plate 20b on the side of the purge gas supply port T3 divides the space on the side of the purge gas supply port T3 into: a gap where the purge gas mainly flows into the second slit 18 of the reactor 100; and a gap where the purge gas flows in from the side of the reactor 100. The rectifying plate 20b on the side of the purge gas discharge port T4 divides the space on the side of the purge gas discharge port T4 into: a gap where the purge gas mainly flows out from the first slit 17 of the reactor 100; and a gap where the purge gas flows out from the side of the reactor 100. However, the number and position of the rectifying plates 20b can be appropriately set. In addition, a portion of the purge gas may also pass through the interior of the stop portion 90. It should be noted that, Fig.19 As shown, the purge gas supply port T3 and the purge gas exhaust port T4 may be disposed on the same side of the reactor 100 in a side view.

[0147] In addition, if Fig. 20 As shown, the housing 20 may not have the purge gas supply port T3, and the purge gas may not 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 purge gas discharge port T4. The position of the purge gas discharge port T4 can be appropriately set.

[0148] It should be explained that Figures 18 to 20 The structure can also be applied to the case where a separation filter is used as the membrane structure instead of the reactor 100.

[0149] Description of Reference Numerals 1Separation membrane module 10 Reactors 10a First end 10b Second end F1 outer surface F2 first end face F3 second end face 20 Shell 21 barrel body 22 First end plate 23 Second end plate 30 First flange 40 Second flange 50 first middle part 60 Second middle section 70 first joint member 80 second engaging member.

Claims

1. A separation membrane module, comprising: A cylindrical shell; A columnar membrane structure housed in the housing; an annular first flange surrounding the first end of the membrane structure; and The first intermediate portion is disposed between the first end surface of the membrane structure and the housing.

2. The separation membrane module according to claim 1, wherein: The separation membrane module further includes a first fastener interposed between the first flange and the membrane structure and between the first intermediate portion and the membrane structure.

3. The separation membrane module according to claim 1, wherein: The first intermediate portion is integral with the first flange.

4. The separation membrane module according to claim 1, wherein: The first intermediate portion and the first flange are respectively made of ceramic material.

5. The separation membrane module according to claim 1, wherein: The separation membrane module also has: an annular second flange surrounding the second end of the membrane structure; and The second intermediate portion is disposed between the second end surface of the membrane structure and the housing.

6. The separation membrane module according to claim 5, wherein: The separation membrane module further includes a second fastener interposed between the second flange and the membrane structure and between the second intermediate portion and the membrane structure.

7. The separation membrane module according to claim 5, wherein: The second intermediate portion is integral with the second flange.

8. The separation membrane module according to claim 5, wherein: The second intermediate portion and the second flange are respectively made of ceramic material.

9. The separation membrane module according to claim 1, wherein: The membrane structure is a reactor.

10. The separation membrane module according to claim 1, wherein: The membrane structure is a separation filter.

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