Separation membrane module

Abstract

A separation membrane module (1) is provided with: a cylindrical case (20); a columnar reactor (10) housed in the housing (20) and extending in the longitudinal direction; and an annular first flange (30) surrounding the first end (10a) of the reactor (10). In the longitudinal direction, the first end surface (F2) of the reactor (10) is positioned further to the outside than the end surface (K1) of the first flange (30).

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. Prior art literature Patent Literature

[0003] Patent Document 1: International Publication No. 2018 / 180095 Patent Document 2: Japanese Patent Application Publication No. 2018-008940 Summary of the invention Technical problem to be solved by the invention

[0004] However, since a permeate-side space for recovering permeated components that have permeated the separation membrane needs to be provided between the membrane structure and the housing, a flange needs to be attached to the end of the membrane structure.

[0005] On the other hand, the length of the membrane structure may vary due to manufacturing variations of the membrane structure, so the length of the membrane structure may be larger than the designed value. In this case, if the length of the housing is also made longer to accommodate the membrane structure, it will be extremely complicated.

[0006] An object of the present invention is to provide a separation membrane module capable of housing a membrane structure regardless of the length dimension of the membrane structure. Technical solutions for solving technical problems

[0007] The separation membrane module of the first embodiment comprises: a cylindrical housing; a columnar membrane structure which is accommodated in the housing and extends in the longitudinal direction; and an annular first flange which surrounds a first end of the membrane structure. In the longitudinal direction, the first end face of the membrane structure is located outside the end face of the first flange.

[0008] In the separation membrane module of the second aspect according to the first aspect, the casing has a first opening centered on the axis of the membrane structure, and the outer peripheral surface of the membrane structure is located inside the inner peripheral surface of the first opening in a radial direction perpendicular to the longitudinal direction.

[0009] In the separation membrane module of the third aspect according to the first aspect or the second aspect, a part of the membrane structure is inserted into the first opening.

[0010] The separation membrane module of a fourth aspect according to any one of the first to third aspects further includes a first bonding material interposed between the membrane structure and the first flange. The first bonding material is separated from the casing.

[0011] In the separation membrane module of a fifth aspect according to any one of the first to fourth aspects, the first flange is made of a ceramic material.

[0012] The separation membrane module of the sixth aspect according to any one of the first to fifth aspects further comprises an annular second flange surrounding the second end of the membrane structure. The second end surface of the membrane structure is located outside the end surface of the second flange in the longitudinal direction.

[0013] In the separation membrane module of the seventh aspect according to the sixth aspect, the casing has a second opening centered on the axis of the membrane structure, and the outer peripheral surface of the membrane structure is located radially inside the inner peripheral surface of the second opening.

[0014] In the separation membrane module of the eighth aspect according to the sixth aspect or the seventh aspect, a part of the membrane structure is inserted into the second opening.

[0015] The separation membrane module of a ninth aspect according to any one of the sixth to eighth aspects further comprises a second bonding material interposed between the membrane structure and the second flange. The second bonding material is separated from the casing.

[0016] In the separation membrane module of a tenth aspect according to any one of the sixth to ninth aspects, the second flange is made of a ceramic material.

[0017] In the separation membrane module of an eleventh aspect according to any one of the first to tenth aspects, the membrane structure is a reactor.

[0018] In the separation membrane module of a twelfth aspect according to any one of the first to tenth aspects, the membrane structure is a separation filter. Effects of the Invention

[0019] According to the present invention, it is possible to provide a separation membrane module capable of housing a membrane structure regardless of the length dimension of the membrane structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a cross-sectional view of a separation membrane module according to an embodiment. Figure 2 yes Figure 1 A partial enlarged view of . Figure 3 yes Figure 1 A partial enlarged view of . Figure 4It is a cross-sectional view of a separation membrane module according to Modification Example 2. Figure 5 yes Figure 4 AA cross-section diagram. Figure 6 yes Figure 4 BB cross-section diagram. Figure 7 It is a cross-sectional view of a separation membrane module according to Modification 5. Figure 8 It is a cross-sectional view of a separation membrane module according to Modification 7. Fig. 9 It is a cross-sectional view of a separation membrane module according to Modification 7. Fig.10 It is a cross-sectional view of a separation membrane module according to Modification Example 8. Fig.11 It is a cross-sectional view of a separation membrane module according to Modification Example 8. Fig.12 It is a cross-sectional view of a separation membrane module according to Modification Example 8. Fig.13 This is a cross-sectional view of a separation membrane module according to Modification Example 9. Fig.14 This is a cross-sectional view of a separation membrane module according to Modification Example 9. Fig.15 This is a cross-sectional view of a separation membrane module according to Modification 10. Fig.16 This is a cross-sectional view of a separation membrane module according to Modification 10. Fig.17 This is a cross-sectional view of a separation membrane module according to Modification 10. DETAILED DESCRIPTION

[0021] (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 . Figure 2 and Figure 3 They are Figure 1 A partial enlarged view of .

[0022] 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 bonding material 50, and a second bonding material 60. The reactor 10 is an example of the "membrane structure" according to the present invention.

[0023] [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.

[0024] 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 a so-called synthesis gas (Syngas). 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. Fuels that are in a liquid state at normal temperature and pressure include, for example, methanol, ethanol, a liquid fuel represented by CnH2(m-2n) (m is an integer less than 90, and n is an integer less than 30), and mixtures thereof. Fuels that can be liquefied under normal temperature and pressure include, for example, propane, butane, and mixtures thereof.

[0025] 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.

[0026] The above reaction is a balanced reaction, and the reactor 10 can move 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 maintains the gaseous state at least until it flows 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.

[0027] 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.

[0028] 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.

[0029] Here, the reactor 10 is composed of a porous support 11 , a separation membrane 12 , a catalyst 13 , and a catalyst stopper 14 .

[0030] 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., if the availability, clay stability and corrosion resistance are taken into consideration, alumina is preferred. As an inorganic binder for the ceramic material, at least one of titanium dioxide, mullite, sinterable alumina, silicon dioxide, glass powder, clay minerals and sinterable cordierite can be used. However, the ceramic material may not contain an inorganic binder.

[0031] 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 of the measurement object (randomly selected) measured by cross-sectional microstructure observation using a SEM (Scanning Electron Microscope).

[0032] 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.

[0033] 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 pass therethrough, thereby shifting the reaction equilibrium of the above-mentioned formula (1) to the product side by utilizing the equilibrium shift effect.

[0034] The separation membrane 12 preferably has a thermal conductivity 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)).

[0035] 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 more difficult 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").

[0036] As the separation membrane 12, an inorganic membrane can be used. The inorganic membrane has heat resistance, pressure resistance, and water vapor resistance, so it is preferred. As the inorganic membrane, for example, a zeolite membrane, a silicon dioxide membrane, an aluminum oxide membrane, or a composite membrane thereof can be cited. 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.

[0037] The catalyst 13 is arranged inside the separation membrane 12, that is, in the non-permeable side space S1. The catalyst 13 is preferably filled in the non-permeable 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 shown in the above formula (1).

[0038] The catalyst 13 can use a known catalyst suitable for the conversion reaction from the raw gas to the liquid fuel. 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 them with palladium, etc.).

[0039] 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 of 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 mounted on the housing 20, but it can also be mounted on the second end surface F3 of the reactor 10.

[0040] 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 .

[0041] 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.

[0042] [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 more, 2 MPa or more). 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.).

[0043] 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 .

[0044] 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.

[0045] 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 .

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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. As the purge gas, hydrogen and / or carbon dioxide can be used. 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 obliquely opposed when viewed in cross section, but the respective positions of the purge gas supply port T3 and the purge gas exhaust port T4 can be appropriately changed.

[0052] The first end plate 22 is an annular plate member. The first end plate 22 has a first opening 20a centered on the axis of the reactor 10. The shape of the first opening 20a is not particularly limited, and can be circular, polygonal, etc. The portion of the first end plate 22 surrounding the first opening 20a is expanded in diameter to be flange-shaped.

[0053] like Figure 1 and Figure 2 As shown, the first end plate 22 has an opposing surface J1 and an inner peripheral surface U1.

[0054] The facing surface J1 faces the end surface K1 of the first flange 30 described later. In the present embodiment, the facing surface J1 is separated from the end surface K1 of the first flange 30. The facing surface J1 may also abut against at least a portion of the end surface K1 of the first flange 30. The facing surface J1 abuts against the first end surface G2 of the tube body 21. An annular third recess H5 is formed on the facing surface J1.

[0055] The inner circumferential surface U1 is connected to the opposing surface J1. The inner circumferential surface U1 is cylindrical. The inner circumferential surface U1 is located at a position outside the outer circumferential surface F1 of the reactor 10 in the radial direction (direction perpendicular to the length direction). In the present embodiment, a portion of the reactor 10 (specifically, the end of the first end 10a) is inserted into the first opening 20a. Therefore, the inner circumferential surface U1 is opposite to a portion of the outer circumferential surface F1 of the reactor 10 in the radial direction.

[0056] It should be noted that the radially outer side refers to a side farther from the axis of the reactor 10 in the radial direction, and the radially inner side refers to a side closer to the axis of the reactor 10 in the radial direction.

[0057] 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.

[0058] The second end plate 23 is an annular plate member. The second end plate 23 has a second opening 20b centered on the axis of the reactor 10. The shape of the second opening 20b is not particularly limited, and can be circular, polygonal, etc. The portion of the second end plate 23 surrounding the second opening 20b is expanded in diameter to be flange-shaped.

[0059] like Figure 1 and Figure 3 As shown, the second end plate 23 has an opposing surface J2 and an inner peripheral surface U2.

[0060] The opposing surface J2 is opposed to the end surface K2 of the second flange 40 described later. In the present embodiment, the second opposing surface J2 is separated from the end surface K2 of the second flange 40. The opposing surface J2 may also abut against at least a portion of the end surface K2 of the second flange 40. The opposing surface J2 abuts against the second end surface G3 of the tube body 21. An annular fourth recess H6 is formed on the second abutting surface J2.

[0061] The inner circumferential surface U2 is connected to the opposing surface J2. The inner circumferential surface U2 is cylindrical. The inner circumferential surface U2 is located radially outside the outer circumferential surface F1 of the reactor 10. In the present embodiment, a portion of the reactor 10 (specifically, the end of the second end 10b) is inserted into the second opening 20b. Therefore, the inner circumferential surface U2 is radially opposite to a portion of the outer circumferential surface F1 of the reactor 10.

[0062] 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.

[0063] [First flange 30] The first flange 30 is mounted on the reactor 10. The first flange 30 is bonded to the reactor 10 by the first bonding material 50. 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.

[0064] like Figure 1 and Figure 2 As shown, the first flange 30 has an end surface K1 , an outer peripheral surface L1 , and an inner peripheral surface M1 .

[0065] The end face K1 is a face on the outside in the length direction of the first flange 30. In the length direction, the end face K1 is located at a position inside the first end face F2 of the reactor 10. In other words, in the length direction, the first end face F2 of the reactor 10 is located outside the end face K1 of the first flange 30. Therefore, the first flange 30 does not interfere with the reactor 10 in the length direction, so the position of the first flange 30 relative to the reactor 10 in the length direction can be freely set. Therefore, even if the length dimension of the reactor 10 is larger than the design value, the reactor 10 can be accommodated in the shell 20 regardless of the length dimension of the reactor 10. As a result, there is no need to prepare a plurality of shells 20 with different length dimensions, so the cost of the separation membrane module 1 can be reduced.

[0066] It should be noted that the outer side in the longitudinal direction refers to the side farther from the center of the reactor 10 in the longitudinal direction, and the inner side in the longitudinal direction refers to the side closer to the center of the reactor 10 in the longitudinal direction.

[0067] In addition, the end face K1 is opposite to the opposing face J1 of the first end plate 22. At least a portion of the end face K1 may also abut against the opposing face J1. In the present embodiment, the end face K1 is planar. The outer peripheral surface L1 is the radially outer surface 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 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 bonding material 50.

[0068] 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.

[0069] [Second flange 40] The second flange 40 is mounted on the reactor 10. The second flange 40 is bonded to the reactor 10 by the second bonding material 60. 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. Thus, a permeate side space S2 is formed between the reactor 10 and the cartridge body 21.

[0070] like Figure 1 and Figure 2 As shown, the second flange 40 has an end surface K2, an outer peripheral surface L2, and an inner peripheral surface M2.

[0071] The end face K2 is a face on the outside in the length direction of the second flange 40. In the length direction, the end face K2 is located at a position on the inside of the second end face F3 of the reactor 10. In other words, in the length direction, the second end face F3 of the reactor 10 is located at a position on the outside of the end face K2 of the second flange 40. Therefore, the second flange 40 does not interfere with the reactor 10 in the length direction, so the position of the first flange 30 relative to the reactor 10 in the length direction can be freely set. Therefore, even if the length dimension of the reactor 10 is larger than the design value, the reactor 10 can be accommodated in the shell 20 regardless of the length dimension of the reactor 10. As a result, there is no need to prepare a plurality of shells 20 with different length dimensions, so the cost of the separation membrane module 1 can be reduced.

[0072] In addition, the end face K2 is opposite to the second opposing face J2 of the second end plate 23. At least a portion of the end face K2 may also abut against the second opposing face J2. In the present embodiment, the end face K2 is planar. The outer peripheral surface L2 is the radially outer surface 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 disposed 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 bonding material 60.

[0073] 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.

[0074] [First bonding material 50] The first bonding material 50 is interposed between the first flange 30 and the reactor 10. The first bonding material 50 bonds the first flange 30 and the reactor 10. The first bonding material 50 is disposed in at least a portion of the gap between the first flange 30 and the reactor 10.

[0075] The first bonding material 50 is preferably separated from the housing 20 (specifically, the first end plate 22 ). This can prevent the first bonding material 50 from interfering with the housing 20 and being damaged.

[0076] It should be noted that the bonded body of the first flange 30 and the reactor 10 bonded via the first bonding material 50 is the “separation membrane module” according to the present invention.

[0077] As the first bonding material 50 , 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.

[0078] As the crystallized glass, for example, SiO2-B2O3 system, SiO2-CaO system, SiO2-Al2O3 system, SiO 2- Crystallized glass of MgO system, SiO-ZnO-BaO system, SiO2-B2O3-CaO system, or SiO2-MgO-CaO system, SiO2-Al2O3-B2O3 system, SiO2-MgO-Al2O3 system. It should be noted that in this specification, the so-called crystallized glass refers to a glass in which the ratio of "the volume occupied by the crystalline phase" to the total volume (degree of crystallinity) is more than 60% and the ratio of "the volume occupied by the amorphous phase and impurities" to the total volume is less than 40%.

[0079] [Second bonding material 60] The second bonding material 60 is interposed between the second flange 40 and the reactor 10. The second bonding material 60 bonds the second flange 40 and the reactor 10. The second bonding material 60 is disposed in at least a portion of the gap between the second flange 40 and the reactor 10.

[0080] The second bonding material 60 is preferably separated from the housing 20 (specifically, the second end plate 23 ). This can prevent the second bonding material 60 from interfering with the housing 20 and being damaged.

[0081] It should be noted that the bonded body of the second flange 40 and the reactor 10 bonded via the second bonding material 60 is the “separation membrane module” according to the present invention.

[0082] As the second bonding material 60 , 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 preferred.

[0083] [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 to the reactor 10 , and a step of housing the reactor assembly in the casing 20 .

[0084] The process of making a reactor assembly includes a first process of forming a molded body of a bonding material, a second process of installing a flange, and a third process of heating the molded body of the bonding material. In the first process, a molded body of the first bonding material 50 is formed at the first end 10a of the reactor 10, and a molded body of the second bonding material 60 is formed at the second end 10b of the reactor 10. In the second process, the first flange 30 is installed in a manner surrounding the molded body of the first bonding material 50, and the second flange 40 is installed in a manner surrounding the molded body of the second bonding material 60. In the third process, the molded bodies of the first bonding material 50 and the second bonding material 60 are heated to grow crystals or melt, and then cooled to room temperature, thereby forming the first bonding material 50 and the second bonding material 60. Thus, the reactor assembly is completed, and the first flange 30 and the second flange 4 are joined to the reactor 10 via the first bonding material 50 and the second bonding material 60.

[0085] Next, the process of housing 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. Thus, the separation membrane module 1 in which the reactor assembly is housed in the shell 20 is completed.

[0086] Here, in the second step, as described above, the positions of the first flange 30 and the second flange 40 in the length direction relative to the reactor 10 can be freely set, so the first flange 30 and the second flange 40 can be installed at a position that does not interfere with the first end plate 22 and the second end plate 23. The interval between the end surface K1 of the first flange 30 and the end surface K2 of the second flange 40 in the length direction may be less than the interval between the facing surface J1 of the first end plate 22 and the facing surface J2 of the second end plate 23 in the length direction. As a result, in the fourth step, since the shell 20 does not interfere with the reactor 10 and the first flange 30 and the second flange 40, it is not necessary to prepare a plurality of shells 20 with different length dimensions.

[0087] (Variation 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.

[0088] [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.

[0089] 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.

[0090] [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.

[0091] 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.

[0092] 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.

[0093] 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 first permeation side space S21 and a second permeation side space S22. The stopper 90 suppresses the direct flow of the purge gas between the first permeation side space S21 and the second permeation side 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.

[0094] 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 .

[0095] 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.

[0096] 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.

[0097] 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 first permeation side space S21.

[0098] 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 second permeation side space S22.

[0099] 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 second permeable side 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 first permeable side space S21.

[0100] 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 intersecting the axis of the reactor 10 when viewed in cross section. As a result, the flow path length of the purge gas in the first permeable side space S21 can be equal to the flow path length of the purge gas in the second permeable side space S22, thereby suppressing the flow deviation of the purge gas. However, the positional relationship between the purge gas supply port T3 and the purge gas exhaust port T4 can be appropriately changed.

[0101] 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 in the outer peripheral surface F1. The purge gas flowing out from the two openings of the first slit 17 to the first permeable side space S21 passes through the first permeable side space S21 and is discharged to the outside from the purge gas outlet T4.

[0102] 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 θ1 of the first extension direction relative to the discharge direction is greater than or equal to 45 degrees and less than or equal to 135 degrees. Thus, the deviation of the gas flow from each opening of the first slit 17 to the purge gas outlet T4 can be suppressed, and thus the deviation of the purge gas in the first permeable side space S21 can be suppressed.

[0103] Figure 6 yes Figure 4 BB cross-section diagram. Figure 6 As shown, the second slit 18 passes through the reactor 100 in a straight line and opens on both sides of the reactor 100. The second slit 18 has two openings formed in the outer peripheral surface F1. The purge gas supplied from the purge gas supply port T3 to the second permeable side space S22 passes through the second permeable side space S22 and flows into the two openings of the second slit 18 respectively.

[0104] 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 second permeable side space S22. Specifically, the angle θ2 of the second extension direction relative to the supply direction is preferably 45 degrees or more and 135 degrees or less. Thus, the deviation of the gas flow from the purge gas supply port T3 to each opening of the second slit 18 can be suppressed, and thus the deviation of the purge gas in the second permeable side space S22 can be suppressed.

[0105] [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.

[0106] [Variation 4] 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.

[0107] In addition, when the separation membrane 12 allows the liquid fuel to pass through, the reaction without by-production of water vapor (for example, )When liquid fuel is generated, the reaction equilibrium can also be shifted to the product side.

[0108] [Variation 5] In the above embodiment, a portion of the reactor 10 is inserted into the first opening 20a, but Figure 7 As shown, if the length of the reactor 10 is short, the reactor 10 may not be inserted into the first opening 20a.

[0109] Likewise, in the above embodiment, a portion of the reactor 10 is inserted into the second opening 20b, but Figure 7 As shown, if the length of the reactor 10 is short, the reactor 10 may not be inserted into the second opening 20b.

[0110] [Variation 6] 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.

[0111] For example, Figure 8 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 20c may be provided to block a portion of the gap between the reactor 10 and the housing 20. Figure 8 In the embodiment, three rectifying plates 20c are provided, but the number of rectifying plates 20c may be one, two, or four or more. The position of the rectifying plates 20c may be appropriately set.

[0112] In addition, if Fig. 9 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.

[0113] It should be explained that Figure 8 and Fig. 9 The structure can also be applied to the case where a separation filter is used as the membrane structure instead of the reactor 10.

[0114] [Variation 7] 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 thereto.

[0115] For example, Fig.10 As shown, a plurality of reactors 10 may be housed in the housing 20 .

[0116] In addition, if Fig.11 As shown, a rectifying plate 20c may be provided to block a portion of the gap between each reactor 10 and the housing 20. Fig.11 In the embodiment, three rectifier plates 20c are provided, but the number of rectifier plates 20c may be one, two or more than four. The position of the rectifier plates 20c may be appropriately set. 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.

[0117] In addition, if Fig.12As 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.

[0118] It should be explained that Figure 10 to Figure 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.

[0119] [Variation 8] 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.

[0120] For example, Fig.13 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 20d may be provided to block a portion of the gap between the reactor 100 and the housing 20. Fig.13 In the embodiment, a rectifying plate 20d is provided on each side of the stopper 90. The rectifying plate 20d 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 20d 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 20d can be appropriately set. In addition, a portion of the purge gas may also pass through the inside of the stopper 90.

[0121] In addition, if Fig.14 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.

[0122] It should be explained that Fig.13 and Fig.14 The structure can also be applied to the case where a separation filter is used as the membrane structure instead of the reactor 100.

[0123] [Variation 9] 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 thereto.

[0124] For example, Fig.15 As shown, a plurality of reactors 100 may be housed in the housing 20 .

[0125] In addition, if Fig.16 As shown, a rectifying plate 20d may be provided, and the rectifying plate 20b blocks a portion of the gap between the reactor 100 and the housing 20. Fig.16 In the figure, a rectifying plate 20d is provided on each side of the stop portion 90. The rectifying plate 20d 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 20d 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 20d 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.16 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.

[0126] 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.

[0127] It should be explained that Figure 15 to Figure 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. Description of Reference Numerals

[0128] 1Separation membrane module 10 Reactors 10a First end 10b Second end F1 outer surface F2 first end face F3 second end face 20 Shell 20a First opening U1 inner surface 20b Second opening U2 inner surface 21 barrel body 22 First end plate 23 Second end plate 30 First flange K1 end face 40 Second flange K2 end face 50 first bonding material 60 second bonding material.

Claims

1. A separation membrane module, comprising: A cylindrical shell; a columnar membrane structure, which is accommodated in the housing and extends in a length direction; and an annular first flange surrounding the first end of the membrane structure, In the longitudinal direction, the first end surface of the membrane structure is located outside the end surface of the first flange.

2. The separation membrane module according to claim 1, wherein: The housing has a first opening centered on the axis of the membrane structure. The outer peripheral surface of the membrane structure is located inside the inner peripheral surface of the first opening in a radial direction perpendicular to the longitudinal direction.

3. The separation membrane module according to claim 2, wherein: A portion of the membrane structure is inserted into the first opening.

4. The separation membrane module according to claim 1, wherein: The separation membrane module further includes a first bonding material interposed between the membrane structure and the first flange. The first bonding material is separated from the housing.

5. The separation membrane module according to claim 1, wherein: The first flange is made of ceramic material.

6. The separation membrane module according to any one of claims 1 to 5, wherein The separation membrane module further includes an annular second flange surrounding the second end of the membrane structure. The second end surface of the membrane structure is located outside the end surface of the second flange in the longitudinal direction.

7. The separation membrane module according to claim 6, wherein: The housing has a second opening centered on the axis of the membrane structure. In the radial direction, the outer peripheral surface of the membrane structure is located inside the inner peripheral surface of the second opening.

8. The separation membrane module according to claim 7, wherein: A portion of the membrane structure is inserted into the second opening.

9. The separation membrane module according to claim 6, wherein: The separation membrane module further includes a second bonding material interposed between the membrane structure and the second flange. The second bonding material is separated from the housing.

10. The separation membrane module according to claim 6, wherein: The second flange is made of a ceramic material.

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

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

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