Zeolite membrane composite, separation device, membrane reaction device, and method for producing zeolite membrane composite

Abstract

A zeolite membrane composite has a porous support and a zeolite membrane provided on the support and containing an ETL-type zeolite. In an X-ray diffraction pattern obtained by irradiating X-rays on the surface of the zeolite membrane, the intensity of a peak present near 2θ = 9.9° and the intensity of a peak present near 2θ = 19.8° are 0.8 times or more the intensity of a peak present near 2θ = 7.9°. Accordingly, a zeolite membrane composite having an ETL-type zeolite membrane with improved compactness can be easily provided.

Description

TECHNICAL FIELD

[0001] The present application relates to a zeolite membrane composite, a separation device, a membrane reaction device, and a method for manufacturing a zeolite membrane composite.

[0002] [REFERENCE TO RELATED APPLICATIONS]

[0003] This application claims the benefit of priority of Japanese Patent Application No. JP 2021-38089 filed on March 10, 2021, the entire disclosure of which is incorporated herein. BACKGROUND

[0004] As for zeolites, various structures of zeolites are known, and ETL-type zeolite is one of them. U.S. Patent No. 4581211 (Document 1), Abraham Araya et al., “Synthesis, properties, and catalytic behavior of zeolite EU-12” (ZEOLITES, 1992, Vol. 12, pp. 24-31) (Document 2), and Juna Bae et al., “EU-12: A Small-Pore, High-Silica Zeolite Containing Sinusoidal Eight-Ring Channels” (Angew. Chem. Int. Ed., 2016, Vol. 55, pp. 7369-7373) (Document 3) disclose a method for synthesizing a powder of ETL-type zeolite crystals (EU-12) by hydrothermal synthesis.

[0005] However, the inventors of the present application formed a zeolite membrane on a support using a raw material solution for EU-12 synthesis, and as a result, obtained an ETL-type zeolite membrane with low density, and could not obtain the desired separation performance. Therefore, a zeolite membrane composite of an ETL-type zeolite membrane with improved density was sought. SUMMARY

[0006] The present application relates to a zeolite membrane composite, the object of which is to provide a zeolite membrane composite of an ETL-type zeolite membrane with improved density.

[0007] The zeolite membrane composite according to the preferred one aspect of the present application has a porous support, and a zeolite membrane provided on the support and containing an ETL-type zeolite. In an X-ray diffraction pattern obtained by irradiating an X-ray to a surface of the zeolite membrane, the intensity of a peak present near 2θ = 9.9° and the intensity of a peak present near 2θ = 19.8° are 0.8 times or more of the intensity of a peak present near 2θ = 7.9°.

[0008] According to the present application, it is possible to provide a zeolite membrane composite of an ETL-type zeolite membrane having improved denseness.

[0009] Preferably, in the X-ray diffraction pattern, the intensity of the peak present near 2θ = 9.9° and the intensity of the peak present near 2θ = 19.8° are 1.0 times or more the intensity of the peak present near 2θ = 7.9°.

[0010] Preferably, the molar ratio of silicon / aluminum in the zeolite membrane is 3 or more.

[0011] Preferably, the permeation amount of CF4 gas in the zeolite membrane is 10 nmol / m 2 or less.

[0012] The present application also relates to a separation device. The separation device according to a preferred embodiment of the present application includes the above-described zeolite membrane composite and a supply portion that supplies a mixture containing a plurality of gases or liquids to the zeolite membrane composite. The zeolite membrane composite separates a highly permeable substance having high permeability from other substances by permeation of the highly permeable substance.

[0013] The present application also relates to a membrane reaction device. The membrane reaction device according to a preferred embodiment of the present application includes the above-described zeolite membrane composite, a catalyst for promoting a chemical reaction of a raw material substance, a reactor that houses the zeolite membrane composite and the catalyst, and a supply portion that supplies the raw material substance to the reactor. The zeolite membrane composite separates a highly permeable substance having high permeability from other substances by permeation of the highly permeable substance, which is a mixture containing a product substance generated by a chemical reaction of the raw material substance in the presence of the catalyst.

[0014] The present application also relates to a method for manufacturing a zeolite membrane composite. The method for manufacturing a zeolite membrane composite according to a preferred embodiment of the present application includes the following steps: a) attaching a seed crystal containing an ETL-type zeolite to a porous support; and b) immersing the support in a raw material solution to grow the ETL-type zeolite from the seed crystal by hydrothermal synthesis, thereby forming a zeolite membrane on the support. In the raw material solution, the molar ratio of silicon / aluminum is 10 to 100, the molar ratio of alkali metal / aluminum is 15 to 100, and the molar ratio of water / aluminum is 2000 to 10000.

[0015] The above-described objects and other objects, features, aspects, and advantages of the present application will become more apparent from the following detailed description of the application when taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 is a cross-sectional view of a zeolite membrane composite.

[0017] Figure 2 This is a magnified cross-sectional view of a portion of the zeolite membrane complex.

[0018] Figure 3 This is a diagram showing the X-ray diffraction pattern obtained from the surface of a zeolite film.

[0019] Figure 4 This is a SEM image representing the surface of the zeolite film.

[0020] Figure 5 This is a diagram showing the manufacturing process of zeolite membrane composites.

[0021] Figure 6 This is a diagram showing the separation device.

[0022] Figure 7 It is a diagram showing the separation process of a mixture. Detailed Implementation

[0023] Figure 1 This is a cross-sectional view of zeolite membrane composite 1. Figure 2 This is a cross-sectional view showing a portion of the zeolite membrane composite 1. The zeolite membrane composite 1 includes a porous support 11 and a zeolite membrane 12 disposed on the support 11. The zeolite membrane refers to a membrane in which zeolite is formed at least on the surface of the support 11, and does not contain a membrane in which zeolite particles are merely dispersed in an organic membrane. Figure 1 In the middle, the zeolite membrane 12 is drawn with thick lines. Figure 2 In the image, parallel oblique lines are marked on zeolite film 12. Additionally... Figure 2 In the text, the thickness of the zeolite film 12 is depicted as thicker than it actually is.

[0024] The support 11 is a porous component that is permeable to gas and liquid. Figure 1 In the example shown, the support 11 is: a columnar main body formed in one piece and connected in one piece, provided with supports respectively in the length direction (i.e. Figure 1 An integral support body with multiple through holes 111 extending in the left and right directions. Figure 1 In the example shown, the support 11 is generally cylindrical. The cross-section of each through hole 111 (i.e., compartment) perpendicular to the length direction is, for example, generally circular. Figure 1 In the diagram, the diameter of the through hole 111 is depicted as larger than it actually is, and the number of through holes 111 is depicted as fewer than it actually is. A zeolite film 12 is formed on the inner circumferential surface of the through hole 111, covering approximately the entire inner circumferential surface of the through hole 111.

[0025] The length of support 11 (i.e. Figure 1The length of the support body 11 in the left-right direction (the length in the direction in which the through holes 111 are arranged in the support body 11) is, for example, 10 cm to 200 cm. The outer diameter of the support body 11 is, for example, 0.5 cm to 30 cm. The distance between the center axes of adjacent through holes 111 is, for example, 0.3 mm to 10 mm. The surface roughness (Ra) of the support body 11 is, for example, 0.1 μm to 5.0 μm, and preferably 0.2 μm to 2.0 μm. Note that the shape of the support body 11 can be, for example, honeycomb, flat plate, tube, cylinder, circular column, or polygonal column. In the case where the shape of the support body 11 is tube or cylinder, the thickness of the support body 11 is, for example, 0.1 mm to 10 mm.

[0026] The material of the support body 11 can be any material (for example, ceramic or metal) that has chemical stability in the process of forming the zeolite membrane 12 on the surface. In the present embodiment, the support body 11 is formed of a ceramic sintered body. As the ceramic sintered body selected as the material of the support body 11, for example, alumina, silica, mullite, zirconia, titania, yttria, silicon nitride, silicon carbide, or the like can be given. In the present embodiment, the support body 11 contains at least one of alumina, silica, and mullite.

[0027] The support body 11 can contain an inorganic bonding material. As the inorganic bonding material, at least one of titania, mullite, sinterable alumina, silica, glass frit, clay mineral, and sinterable cordierite can be given.

[0028] The average pore diameter of the support body 11 is, for example, 0.01 μm to 70 μm, and preferably 0.05 μm to 25 μm. The average pore diameter of the support body 11 in the vicinity of the surface on which the zeolite membrane 12 is to be formed is 0.01 μm to 1 μm, and preferably 0.05 μm to 0.5 μm. The average pore diameter can be measured, for example, with a mercury porosimeter, a pore size distribution measuring device, or a nano-size pore size distribution measuring device. The distribution of the pore diameter of the entire support body 11 including the surface and the inside is such that D5 is, for example, 0.01 μm to 50 μm, D50 is, for example, 0.05 μm to 70 μm, and D95 is, for example, 0.1 μm to 2000 μm. The porosity of the support body 11 in the vicinity of the surface on which the zeolite membrane 12 is to be formed is, for example, 20% to 60%.

[0029] The support 11 has, for example, a multilayer structure formed by stacking multiple layers with different average pore sizes in the thickness direction. The average pore size and sintered particle size of the surface layer, including the surface on which the zeolite film 12 is to be formed, are smaller than the average pore size and sintered particle size of the layers other than the surface layer. The average pore size of the surface layer of the support 11 is, for example, 0.01 μm to 1 μm, preferably 0.05 μm to 0.5 μm. When the support 11 has a multilayer structure, the material of each layer can be the material described above. The materials of the multiple layers forming the multilayer structure can be the same or different.

[0030] The zeolite membrane 12 is a porous membrane with micropores. The zeolite membrane 12 can be used as a separation membrane to separate a specific substance from a mixture containing multiple substances using molecular sieving. In the zeolite membrane 12, other substances are less likely to permeate compared to the specific substance. In other words, the permeation rate of the other substances through the zeolite membrane 12 is less than that of the specific substance.

[0031] The thickness of the zeolite membrane 12 is, for example, 0.05 μm to 30 μm. Preferably, the thickness of the zeolite membrane 12 is 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. If the zeolite membrane 12 is made thinner, the permeability of the highly permeable substances described later increases. The thickness of the zeolite membrane 12 is preferably 0.1 μm or more, more preferably 0.5 μm or more. If the zeolite membrane 12 is made thicker, the separation performance is improved. The surface roughness (Ra) of the zeolite membrane 12 is, for example, 5 μm or less, preferably 2 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less.

[0032] The particle size of the zeolite particles constituting the zeolite film 12 is, for example, 0.01 μm to 20 μm, preferably 0.05 μm to 10 μm, and more preferably 0.1 μm to 5 μm. The particle size of the zeolite particles is determined as follows: the surface of the zeolite film 12 is observed using a scanning electron microscope (SEM) at 3000x magnification, and the particle size (arithmetic mean of the minor and major axes) of any 20 zeolite particles is calculated. The particle size of the zeolite particles is then calculated by taking the arithmetic mean of the calculated particle sizes of the 20 zeolite particles.

[0033] The zeolite film 12 is composed of zeolites with an ETL-type structure. In other words, the zeolite film 12 contains zeolites with a structure code of "ETL" as specified by the International Zeolite Institute. The following description is obtained from the surface of the zeolite film 12. Figure 3 The X-ray diffraction pattern of the zeolite film is consistent with the X-ray diffraction pattern contemplated based on the structure of ETL-type zeolite, with peak positions matching. Typically, the zeolite film 12 is composed only of ETL-type zeolite; however, depending on the manufacturing method, the zeolite film 12 may contain a small amount (e.g., less than 1% by mass) of substances other than ETL-type zeolite.

[0034] The maximum number of members of the ring of the ETL-type zeolite is 8. Here, the arithmetic average of the short diameter and the long diameter of the 8-membered ring pore is set as the average pore diameter. The 8-membered ring pore refers to a fine pore in which the number of oxygen atoms that form a ring structure by bonding with a T atom described later is 8. The ETL-type zeolite has three kinds of 8-membered ring pores, and the pore diameters thereof are 0.27 nm x 0.50 nm, 0.28 nm x 0.46 nm, and 0.33 nm x 0.48 nm, and the average pore diameter is 0.39 nm. The average pore diameter of the zeolite membrane 12 is smaller than the average pore diameter of the support 11 in the vicinity of the surface where the zeolite membrane 12 is to be formed.

[0035] An example of the ETL-type zeolite that constitutes the zeolite membrane 12 is a silicoaluminate zeolite in which an atom (T atom) located at the center of an oxygen tetrahedron (TO4) that constitutes a zeolite contains silicon (Si) and aluminum (Al). A part of the T atom can be substituted with other elements (gallium, titanium, vanadium, iron, zinc, tin, and the like). Accordingly, it is possible to change the pore diameter and the adsorption properties.

[0036] The molar ratio of silicon to aluminum (a value obtained by dividing the number of moles of silicon atoms by the number of moles of aluminum atoms. The same applies hereinafter.) in the zeolite membrane 12 is preferably 3 or more, more preferably 5 or more, and further preferably 10 or more. Accordingly, it is possible to improve the heat resistance and the acid resistance of the zeolite membrane 12. The upper limit of the molar ratio of silicon to aluminum is not particularly limited, and is, for example, 100,000. The molar ratio of silicon to aluminum can be measured by EDS (energy dispersive X-ray spectroscopy) analysis. The molar ratio of silicon to aluminum in the zeolite membrane 12 can be adjusted by adjusting the coordination ratio in the raw material solution described later (the same applies to the ratio of other elements). Of course, the ETL-type zeolite is not limited to the silicoaluminate type.

[0037] Typically, the zeolite membrane 12 contains an alkali metal. The molar ratio of the alkali metal to aluminum in the zeolite membrane 12 is preferably 0.01 to 1, and more preferably 0.1 to 1. Accordingly, the structure of the ETL-type zeolite becomes stable. In the case where the zeolite membrane 12 contains a plurality of alkali metals, the molar ratio of the alkali metal to aluminum is the molar ratio of the total of all the alkali metals contained in the zeolite membrane 12 with respect to aluminum. The alkali metal is, for example, rubidium (Rb) or sodium (Na). The zeolite membrane 12 can contain both rubidium and sodium. The zeolite membrane 12 can also contain other alkali metals such as potassium (K) and cesium (Cs). In addition, a part or all of the cations can be substituted with protons (H + ), ammonium ions (NH 4+ ), and the like by ion exchange or the like.

[0038] One example of the zeolite membrane 12 is manufactured using an organic substance called a structure-directing agent (hereinafter also referred to as "SDA"). In this case, it is preferable to remove the SDA almost or completely after forming the zeolite membrane 12. By doing so, the fine pores are properly ensured in the zeolite membrane 12. As the SDA, for example, tetramethylammonium hydroxide or the like can be used. The zeolite membrane 12 can also be manufactured without using the SDA.

[0039] The permeation amount of the CF4 gas in the zeolite membrane 12 is preferably 10 nmol / m 2 ·s·Pa or less, more preferably 5 nmol / m 2 ·s·Pa or less, further preferably 1 nmol / m 2 ·s·Pa or less. In this way, the CF4 gas hardly permeates through the zeolite membrane 12, and thus it can be said that the zeolite membrane 12 has high denseness. In the present embodiment, the permeation amount of the CF4 gas is measured in a state where the zeolite membrane 12 does not contain the SDA, but the CF4 gas cannot pass through the fine pores of the ETL-type zeolite in principle, and thus the zeolite membrane 12 can contain the SDA at the time of measuring the permeation amount of the CF4 gas.

[0040] Figure 3 is a drawing showing one example of an X-ray diffraction pattern obtained by irradiating the surface of the zeolite membrane 12 with X-rays. The X-ray diffraction pattern is a pattern obtained by irradiating the surface of the zeolite membrane 12 from which the SDA has been removed almost or completely as described later with Cu Kα rays as a ray source of an X-ray diffraction apparatus. Since the intensity of the peaks of the X-ray diffraction pattern is different, the zeolite membrane 12 before the SDA is removed cannot be used to obtain the X-ray diffraction pattern. As described above, the X-ray diffraction pattern obtained from the zeolite membrane 12 coincides with the peak positions of the X-ray diffraction pattern assumed from the structure of the ETL-type zeolite.

[0041] In the X-ray diffraction pattern of the zeolite membrane 12, the intensity of the peak present near 2θ = 9.9° and the intensity of the peak present near 2θ = 19.8° are 0.8 times or more the intensity of the peak present near 2θ = 7.9°. The peak near 2θ = 9.9° is a peak present in the range of 2θ = 9.9° ± 0.2° and derived from the (002) plane of the ETL-type zeolite. The peak near 2θ = 19.8° is a peak present in the range of 2θ = 19.8° ± 0.2° and derived from the (004) plane. The peak near 2θ = 7.9° is a peak present in the range of 2θ = 7.9° ± 0.2° and derived from the (021) plane.

[0042] In this way, in zeolite film 12, the peaks originating from the (002) plane of ETL-type zeolite and the peaks originating from the (004) plane have relatively high intensities, and zeolite film 12 becomes an oriented film in which the c-axis of its constituent particles is oriented in a direction approximately perpendicular to the film surface. In zeolite film 12, the zeolite particles have a consistent crystal orientation, therefore, the zeolite particles can easily bond with each other in a generally planar manner. Therefore, in zeolite film 12, like... Figure 4 As shown in the SEM image, gaps are less likely to form between adjacent zeolite particles, resulting in improved compactness. Consequently, zeolite membrane composite 1 achieves high separation performance.

[0043] In the X-ray diffraction pattern, the intensity of the peaks near 2θ = 9.9° and near 2θ = 19.8° is preferably at least 1.0 times, and more preferably at least 3.0 times, the intensity of the peak near 2θ = 7.9°. Accordingly, the compactness of the zeolite film 12 is further improved. Figure 3 In the example, the peak near 2θ = 19.8° has a greater intensity than the peak near 2θ = 9.9°, and is the largest among all peaks. There is no specific upper limit to the intensity ratio of these peaks; for example, the intensities of the peaks near 2θ = 9.9° and 2θ = 19.8° are less than 1000 times greater than the peak near 2θ = 7.9°. It should be noted that the peak intensity is taken from the height of the bottom line of the X-ray diffraction pattern, i.e., the background noise component. For example, the bottom line of the X-ray diffraction pattern can be determined using the Sonneveld-Visser method or spline interpolation.

[0044] Next, refer to Figure 5 An example of the manufacturing process for zeolite membrane composite 1 will be described. In manufacturing zeolite membrane composite 1, firstly, seed crystals for manufacturing zeolite membrane 12 are prepared (step S11). For example, ETL-type zeolite powder is generated by hydrothermal synthesis, and seed crystals are obtained from this zeolite powder. ETL-type zeolite powder can be generated using any or known manufacturing method (e.g., the methods described in References 1, 2, or 3 above). This zeolite powder can be used directly as seed crystals, or the powder can be processed by pulverization or the like to obtain seed crystals. As seed crystals, ETL-type zeolite containing SDA or ETL-type zeolite without SDA can be used. ETL-type zeolite without SDA is obtained as follows: typically, after synthesis using SDA, SDA is removed by calcination or the like, thereby obtaining ETL-type zeolite without SDA.

[0045] Next, the porous support 11 is immersed in the dispersion liquid in which the seeds are dispersed, and the seeds are attached to the support 11 (step S12). Alternatively, the portion of the support 11 on which the zeolite membrane 12 is to be formed is brought into contact with the dispersion liquid in which the seeds are dispersed, and thereby the seeds are attached to the support 11. In this case, in order for the mass of the seeds attached per unit area of the portion of the support 11 on which the zeolite membrane 12 is to be formed to reach a prescribed value or more, for example, the concentration of the seeds in the dispersion liquid is adjusted or the like. The seeds can also be attached to the support 11 by other methods.

[0046] The support 11 to which the seeds are attached is immersed in a raw material solution. The raw material solution is prepared by dissolving or dispersing, for example, a silicon source, an aluminum source, an alkali metal source, an SDA, or the like in water as a solvent. The silicon source is, for example, colloidal silica, fumed silica, sodium silicate, a silicon alkoxide, water glass, or the like. The aluminum source is, for example, aluminum hydroxide, sodium aluminate, an aluminum alkoxide, or the like. The alkali metal source includes, for example, a rubidium source or a sodium source, and can include both a rubidium source and a sodium source. In addition, the alkali metal source can include a compound containing an alkali metal other than rubidium and sodium. The rubidium source is, for example, rubidium hydroxide, rubidium chloride, or the like. The sodium source is, for example, sodium hydroxide, sodium chloride, or the like. The SDA is, for example, tetramethylammonium hydroxide, choline chloride, or the like.

[0047] In the raw material solution, the molar ratio of silicon / aluminum is 10 to 100, preferably 10 to 75, and more preferably 15 to 50. The molar ratio of alkali metal / aluminum (the molar ratio of the total of all the alkali metals contained in the raw material solution with respect to aluminum) is 15 to 100, preferably 15 to 80, and more preferably 20 to 70. The molar ratio of water / aluminum is 2000 to 10000, preferably 2500 to 10000, and more preferably 3000 to 8000. The molar ratio of SDA / aluminum is, for example, 2 to 100, preferably 3 to 70, and more preferably 3 to 50. The raw material solution can not contain an SDA. Other raw materials can be mixed in the raw material solution, and a solvent other than water can be used for the solvent of the raw material solution.

[0048] After the support 11 is immersed in the raw material solution, hydrothermal synthesis is performed, and an ETL-type zeolite is grown using the seeds on the support 11 as nuclei, and thereby an ETL-type zeolite membrane 12 is formed on the support 11 (step S13). The temperature at the time of the hydrothermal synthesis is preferably 110 to 230°C. The hydrothermal synthesis time is preferably 5 to 100 hours. The shorter the hydrothermal synthesis time, the more the manufacturing cost of the zeolite membrane composite 1 can be reduced.

[0049] After the hydrothermal synthesis is completed, the support 11 and the zeolite membrane 12 are washed with pure water. The washed support 11 and the zeolite membrane 12 are dried at, for example, 1000C. After the support 11 and the zeolite membrane 12 are dried, the zeolite membrane 12 is subjected to a heat treatment in an oxidizing gas atmosphere, whereby the SDA in the zeolite membrane 12 is combusted and removed (step S14). By this, the fine pores in the zeolite membrane 12 are penetrated. It is preferable that the SDA be almost or completely removed. The heat treatment temperature in the SDA removal is, for example, 400 to 10000C. The heat treatment time is, for example, 1 to 100 hours. The oxidizing gas atmosphere is an atmosphere containing oxygen, for example, the atmosphere. By the above treatment, a dense zeolite membrane 12 is formed, and the above-described zeolite membrane composite 1 having a high separation performance is obtained.

[0050] The zeolite membrane 12 can be ion-exchanged as needed. As the ion to be exchanged, there can be mentioned: a proton, an ammonium ion, Na + , K + , Li + , and the like alkali metal ions; Ca 2+ , Mg 2+ , Sr 2+ , Ba 2+ , and the like alkaline earth metal ions; Fe 2+ , Fe 3+ , Cu 2+ , Zn 2+ , Ag + , and the like transition metal ions.

[0051] Next, the separation of a mixed substance using the zeolite membrane composite 1 will be described with reference to Figure 6 and Figure 7 . Figure 6 is a view showing a separation apparatus 2. Figure 7 is a view showing a separation flow of a mixed substance using the separation apparatus 2.

[0052] In the separation apparatus 2, a mixed substance containing a plurality of fluids (i.e., gas or liquid) is supplied to the zeolite membrane composite 1, and a substance having a high permeability in the mixed substance (hereinafter also referred to as "highly permeable substance") is caused to permeate the zeolite membrane composite 1, whereby it is separated from the mixed substance. For example, the separation in the separation apparatus 2 can be performed for the purpose of extracting the highly permeable substance from the mixed substance, or can be performed for the purpose of concentrating a substance having a low permeability (hereinafter also referred to as "lowly permeable substance").

[0053] The mixed substance (i.e., mixed fluid) can be a mixed gas containing a plurality of gases, can be a mixed liquid containing a plurality of liquids, or can be a gas-liquid two-phase fluid containing both gas and liquid.

[0054] The mixed substance contains, for example, one or more of hydrogen (H2), helium (He), nitrogen (N2), oxygen (O2), water (H2O), carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxides, ammonia (NH3), sulfur oxides, hydrogen sulfide (H2S), sulfur fluoride, mercury (Hg), arsine (AsH3), hydrogen cyanide (HCN), carbonyl sulfide (COS), C1 to C8 hydrocarbons, organic acids, alcohols, mercaptans, esters, ethers, ketones, and aldehydes. The above-mentioned high-permeable substance is, for example, one or more of H2, He, N2, O2, CO2, NH3, and H2O, and is preferably H2O.

[0055] The nitrogen oxides are compounds of nitrogen and oxygen. The above-mentioned nitrogen oxides are, for example, nitric oxide (NO), nitrogen dioxide (NO2), nitrous oxide (also called nitrous oxide) (N2O), dinitrogen trioxide (N2O3), dinitrogen tetroxide (N2O4), dinitrogen pentoxide (N2O5), and the like, which are called NOx gases. X

[0056] The sulfur oxides are compounds of sulfur and oxygen. The above-mentioned sulfur oxides are, for example, sulfur dioxide (SO2), sulfur trioxide (SO3), and the like, which are called SOx gases. X

[0057] The sulfur fluoride is a compound of fluorine and sulfur. The above-mentioned sulfur fluoride is, for example, disulfur difluoride (F-S-S-F, S=S F2), sulfur difluoride (SF2), sulfur tetrafluoride (SF4), sulfur hexafluoride (SF6), or disulfur decafluoride (S2F10), and the like. 10

[0058] The C1 to C8 hydrocarbons are hydrocarbons in which the number of carbons is one or more and eight or less. The C3 to C8 hydrocarbons can be any one of a straight chain compound, a branched chain compound, and a cyclic compound. In addition, the C2 to C8 hydrocarbons can be any one of a saturated hydrocarbon (i.e., a hydrocarbon in which no double bond and no triple bond exist in the molecule) and an unsaturated hydrocarbon (i.e., a hydrocarbon in which a double bond and / or a triple bond exists in the molecule). The C1 to C4 hydrocarbons are, for example, methane (CH4), ethane (C2H6), ethylene (C2H4), propane (C3H8), propylene (C3H6), n-butane (CH3(CH2)2CH3), isobutane (CH(CH3)3), 1-butene (CH2=CHCH2CH3), 2-butene (CH3CH=CHCH3), or isobutylene (CH2=C(CH3)2).

[0059] ​​​The organic acid described above is a carboxylic acid or a sulfonic acid, or the like. The carboxylic acid is, for example, formic acid (CH2O2), acetic acid (C2H4O2), oxalic acid (C2H2O4), acrylic acid (C3H4O2), or benzoic acid (C6H5COOH), or the like. The sulfonic acid is, for example, ethanesulfonic acid (C2H6O3S), or the like. The organic acid can be a chain compound or a cyclic compound.

[0060] The alcohol described above is, for example, methanol (CH3OH), ethanol (C2H5OH), isopropyl alcohol (2-propanol) (CH3CH(OH)CH3), ethylene glycol (CH2(OH)CH2(OH)), or butanol (C4H9OH), or the like.

[0061] The thiol is an organic compound having a hydrogenated sulfur (SH) at the terminal end, and is also referred to as Thiol or Thioalcohol. The thiol described above is, for example, methyl mercaptan (CH3SH), ethyl mercaptan (C2H5SH), or 1-propanethiol (C3H7SH), or the like.

[0062] The ester described above is, for example, a formate or an acetate, or the like.

[0063] The ether described above is, for example, dimethyl ether ((CH3)2O), methyl ethyl ether (C2H5OCH3), or diethyl ether ((C2H5)2O), or the like.

[0064] The ketone described above is, for example, acetone ((CH3)2CO), methyl ethyl ketone (C2H5COCH3), or diethyl ketone ((C2H5)2CO), or the like.

[0065] The aldehyde described above is, for example, acetaldehyde (CH3CHO), propionaldehyde (C2H5CHO), or butyraldehyde (C3H7CHO), or the like.

[0066] In the following description, a mixture of a plurality of liquids, which is separated by the separation device 2, is exemplified as a mixed liquid.

[0067] The separation device 2 includes the zeolite membrane composite 1, a sealing portion 21, a housing 22, two sealing members 23, a supply portion 26, a first recovery portion 27, and a second recovery portion 28. The zeolite membrane composite 1, the sealing portion 21, and the sealing members 23 are housed in the housing 22. The supply portion 26, the first recovery portion 27, and the second recovery portion 28 are disposed outside the housing 22 and are connected to the housing 22.

[0068] The sealing portion 21 is installed in the length direction of the support 11, that is, the direction in which the support 11 extends, and is provided with a plurality of holes 211. Figure 6The sealing portion 21 is a component that seals the two ends of the support body 11 in the left-right direction and covers the two end faces of the support body 11 in the longitudinal direction and the outer peripheral surfaces near the two end faces. The sealing portion 21 prevents liquid from flowing in and out through the two end faces of the support body 11. The sealing portion 21 is a plate-shaped component made of, for example, glass or resin. The material and shape of the sealing portion 21 can be appropriately changed. It should be noted that since the sealing portion 21 has multiple openings that overlap with the multiple through holes 111 of the support body 11, the two ends of each through hole 111 in the longitudinal direction of the support body 11 are not covered by the sealing portion 21. Therefore, liquids and the like can flow in and out of the through holes 111 through these two ends.

[0069] The shape of the outer shell 22 is not particularly limited; for example, it may be a generally cylindrical cylindrical component. The outer shell 22 is formed of, for example, stainless steel or carbon steel. The length direction of the outer shell 22 is approximately parallel to the length direction of the zeolite membrane composite 1. At one end of the length direction of the outer shell 22 (i.e....) Figure 6 A supply port 221 is provided at the left end of the housing 22, and a first discharge port 222 is provided at the other end. A second discharge port 223 is provided on the side of the housing 22. A supply unit 26 is connected to the supply port 221. A first recovery unit 27 is connected to the first discharge port 222. A second recovery unit 28 is connected to the second discharge port 223. The internal space of the housing 22 is a sealed space isolated from the space surrounding the housing 22.

[0070] Two sealing components 23 are arranged circumferentially between the outer peripheral surface of the zeolite membrane composite 1 and the inner peripheral surface of the outer shell 22 near both ends along the length of the zeolite membrane composite 1. Each sealing component 23 is a generally annular component formed of a liquid-impermeable material. The sealing component 23 is, for example, an O-ring formed of a flexible resin. The sealing components 23 are in close contact with the outer peripheral surface of the zeolite membrane composite 1 and the inner peripheral surface of the outer shell 22 throughout the entire circumference. Figure 6 In the example shown, the sealing component 23 is in close contact with the outer peripheral surface of the sealing part 21, and indirectly in close contact with the outer peripheral surface of the zeolite membrane composite 1 through the sealing part 21. The sealing component 23 is sealed between the outer peripheral surface of the zeolite membrane composite 1 and between the sealing component 23 and the inner peripheral surface of the outer shell 22, making it almost impossible or completely impossible for liquid to pass through.

[0071] The supply unit 26 supplies the mixture to the internal space of the outer casing 22 via the supply port 221. The supply unit 26 includes, for example, a pump that pressurizes the mixture toward the outer casing 22. The pump includes a temperature regulating unit and a pressure regulating unit that regulate the temperature and pressure of the mixture supplied to the outer casing 22, respectively. The first recovery unit 27 includes, for example, a storage container for storing liquid discharged from the outer casing 22 or a pump for transferring and conveying the liquid. The second recovery unit 28 includes, for example, a vacuum pump for depressurizing the space outside the outer periphery of the zeolite membrane composite 1 inside the outer casing 22 (i.e., the space sandwiched between two sealing members 23), and a liquid nitrogen trap for cooling and liquefying the vaporized gas that passes through the zeolite membrane composite 1.

[0072] During the separation of the mixture, the zeolite membrane composite 1 is prepared by preparing the separation device 2 described above. Figure 7 (Step S21) Next, using the supply unit 26, a mixture containing multiple liquids with different permeabilities to the zeolite membrane 12 is supplied to the interior space of the housing 22. For example, the main components of the mixture are water (H2O) and ethanol (C2H5OH). The mixture may contain liquids other than water and ethanol. The pressure (i.e., the introduction pressure) of the mixture supplied from the supply unit 26 to the interior space of the housing 22 is, for example, 0.1 MPa to 2 MPa, and the temperature of the mixture is, for example, 10°C to 200°C.

[0073] The mixture supplied from the supply section 26 to the outer casing 22 is introduced into each through hole 111 of the support 11 from the left end of the zeolite membrane composite 1 in the figure, as shown by arrow 251. The highly permeable liquid in the mixture, i.e., the highly permeable substance, vaporizes and passes through the zeolite membrane 12 provided on the inner peripheral surface of each through hole 111 and the support 11, and is discharged from the outer peripheral surface of the support 11. Thus, the highly permeable substance (e.g., water) is separated from the less permeable liquid in the mixture, i.e., the low-permeability substance (e.g., ethanol) (step S22).

[0074] The gas (hereinafter referred to as "permeable material") discharged from the outer peripheral surface of the support 11 is introduced into the second recovery section 28 through the second outlet 223 as shown by arrow 253, where it is cooled and recovered in liquid form. The pressure (i.e., permeation pressure) of the gas recovered by the second recovery section 28 through the second outlet 223 is, for example, about 50 Torr (about 6.67 kPa). In addition to the high-permeability material described above, the permeable material may also contain a low-permeability material that permeates from the zeolite membrane 12.

[0075] Further, liquid other than the substance that has permeated the zeolite membrane 12 and the support 11 (hereinafter referred to as "non-permeated substance") is caused to pass through each through-hole 111 of the support 11 from the left side to the right side in the figure, and is recovered by the first recovery section 27 via the first discharge port 222 as indicated by an arrow 252. The pressure of the liquid recovered by the first recovery section 27 via the first discharge port 222 is, for example, substantially the same as the introduction pressure. The non-permeated substance includes, in addition to the low-permeability substance described above, a high-permeability substance that does not permeate the zeolite membrane 12. The non-permeated substance recovered by the first recovery section 27 can be, for example, circulated to the supply section 26 and supplied again into the housing 22.

[0076] Figure 6 The separation device 2 illustrated can be used as, for example, a membrane reaction device. In this case, the housing 22 functions as a reactor. Inside the housing 22, a catalyst for promoting a chemical reaction of a raw material substance supplied from the supply section 26 is housed. The catalyst is disposed, for example, between the supply port 221 and the first discharge port 222. Preferably, the catalyst is disposed in the vicinity of the zeolite membrane 12 of the zeolite membrane composite 1. The catalyst is used in an appropriate material and shape according to the kind of the raw material substance and the kind of the chemical reaction to be caused in the raw material substance. The raw material substance includes one or two or more kinds of substances. The membrane reaction device can further be provided with a heating device for heating the reactor (i.e., the housing 22) and the raw material substance, so as to promote the chemical reaction of the raw material substance.

[0077] In the separation device 2 used as a membrane reaction device, a mixture including a product substance generated by causing a raw material substance to undergo a chemical reaction in the presence of a catalyst is supplied to the zeolite membrane 12 as described above, and a high-permeability substance in the mixture permeates the zeolite membrane 12, whereby the high-permeability substance is separated from other substances having a permeability smaller than that of the high-permeability substance. For example, the mixture can be a fluid including the product substance and an unreacted raw material substance. Further, the mixture can include two or more kinds of product substances. The high-permeability substance can be a product substance generated from the raw material substance, or a substance other than the product substance. Preferably, the high-permeability substance includes one or more kinds of product substances.

[0078] In the case where the high-permeability substance is a product substance generated from the raw material substance, the product substance is separated from other substances by the zeolite membrane 12, whereby the yield of the product substance can be improved. In the case where the mixture includes two or more kinds of product substances, the two or more kinds of product substances can all be high-permeability substances, or a part of the two or more kinds of product substances can be high-permeability substances.

[0079] Next, an embodiment of the zeolite membrane composite will be described.

[0080] <Example>

[0081] (Preparation of seed crystal)

[0082] As an aluminum source, a silicon source, an alkali metal source, and a structure directing agent (SDA), aluminum hydroxide, 30% colloidal silica, rubidium hydroxide, and tetramethylammonium hydroxide were dissolved in pure water to prepare a raw material solution having a composition of 1 Al203: 30 Si02: 5 Rb20: 5 SDA: 1500 H20 in terms of molar ratio. The raw material solution was subjected to hydrothermal synthesis at 180°C for 100 hours. The crystal obtained by the hydrothermal synthesis was recovered, washed thoroughly with pure water, and then completely dried at 100°C. As a result of X-ray diffraction measurement, the crystal obtained was an ETL crystal. The crystal was put in pure water at 10 to 20 mass%, and then pulverized by a ball mill to prepare a seed crystal.

[0083] (Preparation of ETL membrane)

[0084] The entire porous alumina support was contacted with a solution in which the aforementioned seed crystal was dispersed, and the seed crystal was coated in the cells. Thereafter, as an aluminum source, a silicon source, an alkali metal source, and a structure directing agent (SDA), aluminum hydroxide, 30% colloidal silica, rubidium hydroxide, and sodium hydroxide, and tetramethylammonium hydroxide were dissolved in pure water to prepare a raw material solution having a composition of 1 Al203: 30 Si02: 15 Rb20: 6 Na20: 10 SDA: 3000 H20 in terms of molar ratio. The alumina support on which the seed crystal was coated was immersed in the raw material solution, and subjected to hydrothermal synthesis at 180°C for 15 hours. After the hydrothermal synthesis, the ETL-type zeolite membrane (hereinafter referred to as "ETL membrane") formed on the support was washed thoroughly with pure water, and then completely dried at 100°C. After the drying, the N2 permeation amount of the ETL membrane was measured, and the result was 0.05 nmol / m 2 ·s·Pa or less. Accordingly, it was confirmed that the ETL membrane had a density to the extent that was practical. Next, the ETL membrane was subjected to heat treatment at 500°C for 20 hours, whereby the SDA was combusted and removed, and the pores in the ETL membrane were penetrated. The CF4 gas permeation amount of the ETL membrane obtained was measured, and the result was 10 nmol / m 2 ·s·Pa or less. In addition, the molar ratio of silicon to aluminum of the ETL membrane obtained was 3 or more as a result of EDS analysis.

[0085] (Evaluation of ETL membrane)

[0086] By circulating a 50 mass% ethanol aqueous solution heated to 50°C using a circulation pump, the ETL membrane was evaluated for the separation of ethanol and water. The separation container in which the ETL membrane was installed was connected to a gas flow meter, and the permeation amount of ethanol was measured. The result was 0.5 g / m Figure 6The water-selective ETL film was produced using the raw material solution prepared in the same manner as in Example 1, except that the molar ratio of silicon / aluminum in the mixture ratio of the raw materials was changed to 10 to 100, the molar ratio of alkali metal / aluminum was changed to 15 to 100, and the molar ratio of water / aluminum was changed to 2000 to 10000. The water-selective ETL film was produced in the same manner as in Example 1, except that the pressure in the supply-side space of the separation device 2) was supplied with an ethanol aqueous solution, and the through-side space was depressurized using a vacuum pump under the condition that the pressure controller was controlled to 50 Torr, and the vapor that had passed through the ETL film and the support was recovered using a liquid nitrogen trap. The amount and the concentration of the liquid recovered by the liquid nitrogen trap were measured, and the water selectivity and the water permeation flux of the ETL film were calculated. The water selectivity of the ETL film was calculated by dividing the water concentration (mass %) in the recovered liquid by the ethanol concentration (mass %) in the recovered liquid. The water permeation flux was calculated from the amount of water in the recovered liquid. The water selectivity of the ETL film was 50, and the water permeation flux was 0.3 kg / m 2 • h. In this way, the obtained ETL film was a film that exhibited water selectivity.

[0087] In the X-ray diffraction pattern obtained by irradiating X-rays on the film surface of the ETL film, the intensity of the peak present near 2θ = 9.9° and the intensity of the peak present near 2θ = 19.8° were 1.0 times or more the intensity of the peak present near 2θ = 7.9°. Note that, in the X-ray diffraction measurement, an X-ray diffractometer (device name: MiniFlex600) manufactured by Rigaku Corporation was used, and the tube voltage was set to 40 kV, the tube current was set to 15 mA, the scan speed was set to 0.5° / min, and the scan step was set to 0.02°. In addition, the divergence slit was set to 1.25°, the scattering slit was set to 1.25°, the light-receiving slit was set to 0.3 mm, the incident soller slit was set to 5.0°, and the light-receiving soller slit was set to 5.0°. A 0.015 mm-thick nickel foil was used as a Cu Kβ-ray filter without using a monochromator.

[0088] Further, in the case where the production of the ETL film was performed using a raw material solution prepared in such a manner that the molar ratio of silicon / aluminum in the mixture ratio of the raw materials was 10 to 100, the molar ratio of alkali metal / aluminum was 15 to 100, and the molar ratio of water / aluminum was 2000 to 10000, in the X-ray diffraction pattern obtained by irradiating X-rays on the film surface of the ETL film, the intensity of the peak present near 2θ = 9.9° and the intensity of the peak present near 2θ = 19.8° were 0.8 times or more the intensity of the peak present near 2θ = 7.9°. The obtained ETL film was a film that exhibited water selectivity and had high density. In particular, it was confirmed that the density of the ETL film in which the intensity of the peak present near 2θ = 9.9° and the intensity of the peak present near 2θ = 19.8° were 1.0 times or more the intensity of the peak present near 2θ = 7.9° was higher than the density of the ETL film in which the intensity of the peak present near 2θ = 9.9° and the intensity of the peak present near 2θ = 19.8° were 0.8 times or more and less than 1.0 times the intensity of the peak present near 2θ = 7.9°.

[0089] <Comparative Example>

[0090] (Production of the seed crystal)

[0091] A seed crystal was produced in the same manner as in the example.

[0092] (Production of ETL film)

[0093] The entire shape of the porous alumina support was contacted with the solution in which the aforementioned seed crystal was dispersed, and the seed crystal was coated in the compartment. A raw material solution having the same composition as the raw material solution used to produce the seed crystal was prepared, and the alumina support coated with the seed crystal was immersed in the raw material solution, and hydrothermal synthesis was performed at 180°C for 15 hours. After the hydrothermal synthesis, the ETL film was sufficiently washed with pure water, and then, was completely dried at 100°C. After the drying, the N2permeation amount of the ETL film was measured, and the result was 1 nmol / m 2 ·s·Pa or more. Accordingly, it was confirmed that the ETL film did not have compactness. Next, the ETL film was subjected to heat treatment at 500°C for 20 hours, whereby the SDA was combusted and removed, and the pores in the ETL film were penetrated. The permeation amount of CF4gas was measured for the obtained ETL film, and the result was greater than 50 nmol / m 2 ·s·Pa.

[0094] (Evaluation of ETL film)

[0095] An aqueous 50 mass% ethanol solution heated to 50°C was circulated by using a circulation pump, and the aqueous ethanol solution was supplied to the supply side space of the separation container in which the ETL film was installed, and the permeation side space was depressurized by using a vacuum pump in a state where the pressure was controlled to 50 Torr, and as a result, the aqueous ethanol solution directly permeated through the ETL film and the support. In this way, the obtained ETL film was a film in which compactness was poor and water selectivity was not exhibited.

[0096] In an X-ray diffraction pattern obtained by irradiating X-rays to the film surface of the ETL film, the intensity of a peak present near 2θ = 9.9° and the intensity of a peak present near 2θ = 19.8° were less than 0.8 times the intensity of a peak present near 2θ = 7.9°.

[0097] As described above, the zeolite membrane composite 1 has: a porous support 11; and a zeolite membrane 12 provided on the support 11 and containing an ETL-type zeolite. In an X-ray diffraction pattern obtained by irradiating X-rays to the surface of the zeolite membrane 12, the intensity of a peak present near 2θ = 9.9° and the intensity of a peak present near 2θ = 19.8° are 0.8 times or more the intensity of a peak present near 2θ = 7.9°. In this way, the zeolite membrane 12 becomes an oriented film in which the c-axes of the constituent particles are oriented in a direction substantially perpendicular to the film surface, and accordingly, the compactness of the zeolite membrane 12 is improved. As a result, it is possible to easily provide a zeolite membrane composite 1 having an ETL-type zeolite film in which the compactness is improved.

[0098] Preferably, the intensity of the peak present near 2θ = 9.9° and the intensity of the peak present near 2θ = 19.8° in the X-ray diffraction pattern are 1.0 times or more the intensity of the peak present near 2θ = 7.9°. By this, the compactness of the zeolite membrane 12 can be further improved.

[0099] Preferably, the molar ratio of silicon / aluminum in the zeolite membrane 12 is 3 or more. By this, the heat resistance and the acid resistance of the zeolite membrane 12 can be improved. The permeation amount of CF4 gas in the zeolite membrane 12 is preferably 10 nmol / m 2 ·s·Pa or less.

[0100] The manufacturing method of the above-described zeolite membrane composite 1 includes the following steps: attaching a seed crystal of an ETL-type zeolite to a porous support 11; and immersing the support 11 in a raw material solution, growing the ETL-type zeolite from the seed crystal by hydrothermal synthesis, and forming a zeolite membrane 12 on the support 11. In the raw material solution, the molar ratio of silicon / aluminum is 10 to 100, the molar ratio of alkali metal / aluminum is 15 to 100, and the molar ratio of water / aluminum is 2000 to 10000. By this, the zeolite membrane composite 1 having an ETL-type zeolite membrane with improved compactness can be easily provided.

[0101] As described above, the separation device 2 is provided with: the above-described zeolite membrane composite 1; and a supply portion 26 that supplies a mixture containing a plurality of gases or liquids to the zeolite membrane composite 1. The zeolite membrane composite 1 separates a high-permeability substance having high permeability in the mixture from other substances. By this, the high-permeability substance can be efficiently separated from other substances.

[0102] As described above, the membrane reaction device is provided with: the above-described zeolite membrane composite 1; a catalyst for promoting a chemical reaction of a raw material substance; a reactor (the housing 22 in the above-described example) that houses the zeolite membrane composite 1 and the catalyst; and a supply portion 26 that supplies the raw material substance to the reactor. The zeolite membrane composite 1 separates a high-permeability substance having high permeability in a mixture of product substances generated by causing the raw material substance to chemically react in the presence of the catalyst from other substances. By this, as in the above-described case, the high-permeability substance can be efficiently separated from other substances.

[0103] Various modifications can be made to the above-described zeolite membrane composite 1, separation device 2, membrane reaction device, and manufacturing method of the zeolite membrane composite 1.

[0104] The molar ratio of silicon / aluminum in the zeolite membrane 12 can be less than 3. The permeation amount of CF4 gas in the zeolite membrane 12 can be more than 10 nmol / m2 ·s·Pa.

[0105] In the support 11 with through holes, the zeolite membrane 12 can be disposed on the inner circumferential surface or the outer circumferential surface, or it can be disposed on both the inner circumferential surface and the outer circumferential surface at the same time.

[0106] The zeolite membrane composite 1 can be manufactured using methods other than those described above.

[0107] In addition to the support 11 and the zeolite membrane 12, the zeolite membrane composite 1 may further include functional membranes and protective membranes laminated on the zeolite membrane 12. These functional and protective membranes can be inorganic membranes such as zeolite membranes, silica membranes, or carbon membranes, or organic membranes such as polyimide membranes or silicone membranes. Furthermore, substances that readily adsorb water can be added to the functional and protective membranes laminated on the zeolite membrane 12.

[0108] In the separation device 2 and separation method, in addition to the pervaporation method exemplified above, the mixture can also be separated by steam permeation, reverse osmosis, gas permeation, etc. The same applies to membrane reactors.

[0109] In the separation apparatus 2 and separation method, substances other than those exemplified in the above description can be separated from the mixture. The same applies to the membrane reactor.

[0110] The components in the above-described embodiments and their variations can be appropriately combined as long as they do not contradict each other.

[0111] Although the invention has been described in detail, the above description is exemplary and not limiting. Therefore, it can be said that various modifications and solutions can be adopted without departing from the scope of the invention.

[0112] Industrial availability

[0113] The zeolite membrane composite of the present invention can be used as, for example, a dehydration membrane, and further, it can be used in various fields utilizing zeolite as a separation membrane for various substances other than water or an adsorption membrane for various substances.

[0114] Explanation of reference numerals in the attached figures

[0115] 1. Zeolite membrane complex

[0116] 11 Support

[0117] 12 Zeolite membrane

[0118] Steps S11~S14, S21, S22

Claims

1. A zeolite membrane composite, wherein, Possessing: a porous support; and a zeolite membrane provided on the support and containing an ETL-type zeolite, in an X-ray diffraction pattern obtained by irradiating an X-ray to a surface of the zeolite membrane, an intensity of a peak present near 2θ = 9.9° and an intensity of a peak present near 2θ = 19.8° are 0.8 times or more of an intensity of a peak present near 2θ = 7.9°.

2. The zeolite membrane composite according to claim 1, characterized in that, in the X-ray diffraction pattern, the intensity of the peak present near 2θ = 9.9° and the intensity of the peak present near 2θ = 19.8° are 1.0 times or more of the intensity of the peak present near 2θ = 7.9°.

3. The zeolite membrane composite according to claim 1 or 2, characterized in that, a molar ratio of silicon / aluminum in the zeolite membrane is 3 or more.

4. The zeolite membrane composite according to claim 1 or 2, characterized in that, The zeolite membrane has a CF4 gas permeance of 10 nmol / m 2 ·s·Pa or less.

5. The zeolite membrane composite according to claim 1 or 2, characterized in that, the zeolite membrane contains rubidium.

6. The zeolite membrane composite according to claim 1 or 2, characterized in that, a molar ratio of alkali metal / aluminum in the zeolite membrane is 0.01 to 1.

7. A separating device, wherein, Possessing: the zeolite membrane composite according to any one of claims 1 to 6; and a supply portion that supplies a mixed substance containing a plurality of gases or liquids to the zeolite membrane composite, the zeolite membrane composite is separated from other substances by permeation of a high-permeability substance having high permeability among the mixed substance.

8. A membrane reaction device, wherein, Possessing: the zeolite membrane composite according to any one of claims 1 to 6; a catalyst for promoting a chemical reaction of a raw material substance; a reactor that accommodates the zeolite membrane composite and the catalyst; and a supply portion that supplies the raw material substance to the reactor, the zeolite membrane composite is separated from other substances by permeation of a high-permeability substance having high permeability among a mixed substance containing a product substance generated by causing the raw material substance to chemically react in the presence of the catalyst.

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