Crystalline material and membrane complex

Abstract

Crystalline material containing oxygen, aluminum and phosphorus, exhibiting the powder X-ray diffraction peaks shown in the table below. 2 θ (°) d (nm) Relative intensity 8,65±0,2 1,022 1-15 9,99±0,2 0,885 1-15 14,17±0,2 0,625 100 16,52±0,2 0,537 5-80 17,37±0,2 0,511 1-15 21,81±0,2 0,407 10-80 22,44±0,2 0,396 2-15 24,66±0,2 0,361 15-70 26,11±0,2 0,341 10-80 28,56±0,2 0,313 5-40 29,80±0,2 0,300 3-30 33,17±0,3 0,270 1-20 34,93±0,3 0,257 1-15 36,21±0,3 0,248 2-15 39,02±0,3 0,231 1-10 43,44±0,3 0,208 1-10

Description

Technical field

[0001] The present invention relates to a crystalline material and a membrane complex. Technical background

[0002] Various structures of zeolite are known, and one of these structures is a SAT type. For example, the process for preparing the powder of the SAT type is described in "The templated synthesis and structure determination by synchrotron microcrystal diffraction of the novel small pore magnesium aluminophosphate STA-2" by Graham W. Noble and two other colleagues, Journal of Chemical Society, Dalton Transactions 1997, pages 4485-4490 (Document 1), and "Molecular Modeling, Multinuclear NMR, and Diffraction Studies in the Templated Synthesis and Characterization of the Aluminophosphate Molecular Sieve STA-2" by Maria Castro and ten other colleagues, Journal of Physics and Chemistry C 2010, Volume 114, pages 12698-12710. Furthermore, US 2017 / 0 291 135 A1 (Document 3) describes a separation membrane structure and a method for reducing the nitrogen concentration.Furthermore, US 2017 / 0 296 980 A1 (Document 4) also describes a separating membrane structure.

[0003] Meanwhile, crystalline materials such as zeolite have been investigated and implemented in various applications, including specific gas separation and molecular adsorption. To expand the selection of crystalline materials with desired properties, there is therefore a constant need for crystalline materials with novel structures. Brief description of the invention

[0004] The present invention is intended for a crystalline material and it is an object of the present invention to provide a crystalline material with a new structure.

[0005] The crystalline material according to the present invention contains oxygen, aluminum and phosphorus and exhibits the powder X-ray diffraction peaks shown in Table 1 below. Table 1 2 θ (°) d (nm) Relative intensity 8,65±0,2 1,022 1-15 9,99±0,2 0,885 1-15 14,17±0,2 0,625 100 16,52±0,2 0,537 5-80 17,37±0,2 0,511 1-15 21,81 ±0,2 0,407 10-80 22,44±0,2 0,396 2-15 24,66±0,2 0,361 15-70 26,11±0,2 0,341 10-80 28,56±0,2 0,313 5-40 29,80±0,2 0,300 3-30 33,17±0,3 0,270 1-20 34,93±0,3 0,257 1-15 36,21±0,3 0,248 2-15 39,02±0,3 0,231 1-10 43,44±0,3 0,208 1-10

[0006] According to the present invention, it is possible to provide a crystalline material with a new structure.

[0007] Preferably, the crystalline material is a powder with a mean particle diameter of 0.01 to 10 µm.

[0008] Preferably, the crystalline material does not contain any structuring agent.

[0009] Preferably, the crystalline material further contains at least one of silicon, magnesium, zinc, titanium, cobalt, copper, iron and boron.

[0010] The present invention also applies to a membrane complex. The membrane complex according to the present invention comprises a support and a membrane made of the aforementioned crystalline material and arranged on the support.

[0011] These and other tasks, features, aspects and advantages of the present invention will become clearer from the following description of the present invention when considered in conjunction with the accompanying drawings. Brief description of the drawings Fig. Figure 1 is a flowchart showing a process for producing powder from a crystalline material; Fig. Figure 2 is a view showing a powder X-ray diffraction pattern of crystalline material; Fig. Figure 3 is a view showing a powder X-ray diffraction pattern of crystalline material; Fig. Figure 4 is a view showing a powder X-ray diffraction pattern of crystalline material; Fig. Figure 5 is a cross-sectional view showing a membrane complex; Fig. Figure 6 is a cross-sectional view showing a magnified portion of the membrane complex; Fig.Figure 7 is a flowchart showing a process for the production of the membrane complex; Fig. Figure 8 is a diagram showing a separating device; and Fig. Figure 9 is a flowchart showing a process for separating a mixed substance using the separation device. Description of the embodiments

[0012] A crystalline material according to the present invention (hereinafter referred to as "present crystalline material") contains oxygen (O), aluminium (Al) and phosphorus (P) and exhibits the powder X-ray diffraction peaks shown in Table 2. Table 2 2 θ (°) d (nm) Relative intensity 8,65±0,2 1,022 1-15 9,99±0,2 0,885 1-15 14,17±0,2 0,625 100 16,52±0,2 0,537 5-80 17,37±0,2 0,511 1-15 21,81 ±0,2 0,407 10-80 22,44±0,2 0,396 2-15 24,66±0,2 0,361 15-70 26,11±0,2 0,341 10-80 28,56±0,2 0,313 5-40 29,80±0,2 0,300 3-30 33,17±0,3 0,270 1-20 34,93±0,3 0,257 1-15 36,21±0,3 0,248 2-15 39,02±0,3 0,231 1-10 43,44±0,3 0,208 1-10

[0013] Table 2 shows the diffraction angles 2θ of the powder X-ray diffraction peaks, values ​​obtained when CuKα radiation is used as the radiation source. Furthermore, if the peak at 2θ = 14.17 ± 0.2° is used as the reference peak and the intensity of the reference peak is set to 100, the relative intensity of each peak is displayed (the same applies to other tables). The height excluding the lower line in the powder X-ray diffraction pattern, i.e., the height excluding the background noise component, is used as the relative intensity of the peak. The lower line in the powder X-ray diffraction pattern is determined, for example, using the Sonneveld-Visser method or the spline interpolation method.

[0014] In the present embodiment, the crystalline material exhibiting the powder X-ray diffraction peaks shown in Table 2 is produced by subjecting the zeolite with the structure code “SAT” assigned by the International Zeolite Association to the treatment described below. The powder X-ray diffraction pattern shown in Table 2 differs from the powder X-ray diffraction pattern of the SAT-type zeolite (see, for example, (b) of Fig. 1 of the preceding document 1), and in the present crystalline material, for example, the relative intensity of the peak at 2θ = 8.65 ± 0.2° is smaller than that of the SAT-type zeolite. Therefore, the present crystalline material exhibits a novel structure that differs from that of the SAT-type zeolite. The crystalline material may exhibit a different peak than the powder X-ray diffraction peaks shown in Table 2. Such a peak may occur due to the inclusion of other substances or the like.

[0015] An example of a SAT-type zeolite used to produce the present crystalline material is an AIPO-type zeolite in which the atoms (T atoms) at the center of an oxygen tetrahedron (TO4) that forms the zeolite contain aluminum and phosphorus. Other suitable zeolites include SAPO-type zeolites in which the T atoms contain silicon (Si), aluminum, and phosphorus; MAPSO-type zeolites in which the T atoms contain magnesium (Mg), silicon, aluminum, and phosphorus; ZnAPSO-type zeolites in which the T atoms contain zinc (Zn), silicon, aluminum, and phosphorus; or similar materials. Some of the T atoms can be replaced by other elements such as titanium (Ti) and boron (B).

[0016] The crystalline material produced from SAT-type zeolite is a porous substance similar to SAT-type zeolite and is considered a zeolite. It also typically has a similar composition to SAT-type zeolite, containing oxygen, aluminum, and phosphorus. Furthermore, it may contain at least one of each of silicon, magnesium, zinc, titanium, cobalt, copper, iron, and boron. This allows for modification of the pore diameter and adsorption properties of the crystalline material.

[0017] The phosphorus / aluminium molar ratio (i.e., the value obtained by dividing the number of moles of phosphorus by the number of moles of aluminum; the same applies below) in the present crystalline material is preferably 0.5 to 4, more preferably 0.7 to 2. The phosphorus / aluminium ratio in the crystalline material can be adjusted, for example, by adjusting the mixing ratio of an aluminum source and a phosphorus source in the starting material solution described below (the same applies to the ratio of the other elements).

[0018] In the present crystalline material, it is preferred that the structure-directing agent (hereinafter referred to as "SDA") used at the time of the synthesis of the SAT-type zeolite is removed. That is, the preferred crystalline material contains no SDA. Consequently, pores are suitably present in the crystalline material. To confirm the presence or absence of SDA, for example, thermal desorption mass spectrometry (Temperature Programmed Desorption or Decomposition Mass Spectrometry - TPD-MS) can be used. If the value obtained by dividing the mass of CO2 gas when the crystalline material is heated in a helium atmosphere to 200 to 900 °C or higher by the mass of the crystalline material is, for example, 1000 ppm by weight or less, the crystalline material is considered to contain no SDA.In one example, the presence of an alkali metal alloy (AMA) is confirmed by analyzing the gas generated by heating the crystalline material at a heating rate of 10 °C / min with a simultaneous helium flow rate of 50 ml / min using a Shimadzu Corporation QP2010Plus gas chromatograph-mass spectrometer (GC / MS). Depending on the application of the crystalline material, it may contain an AMA. The crystalline material may also contain an alkali metal, such as sodium (Na) or potassium (K).

[0019] The mean pore diameter of the crystalline material present is 1 nm or less.

[0020] In one example, the crystalline material is produced as a powder. The mean particle diameter of the powdered crystalline material is, for example, 0.01 to 10 µm, preferably 0.05 to 5 µm, and more preferably 0.1 to 1 µm. The mean particle diameter of the powder is the median diameter (D). 50 ) in the particle diameter distribution obtained by the laser scattering method. As described later, the crystalline material can be produced as a membrane.

[0021] Fig.Figure 1 is a flowchart illustrating the process for producing powder of a crystalline material with the powder X-ray diffraction peaks shown in Table 2. In this production example, SAT-type zeolite powder (crystals) is first synthesized and produced (step S11). The synthesis of the SAT-type zeolite powder involves preparing a starting material solution by dissolving, for example, an aluminum source, a phosphorus source, SDA, or similar substances in a solvent. The composition of the starting material solution is, for example, 1 Al₂O₃ : 1 P₂O₅ : 0.8 SDA : 200 H₂O. In addition to water, alcohol, such as ethanol, can be used as the solvent for the starting material solution. Examples of suitable aluminum sources include sodium aluminate, aluminum hydroxide, aluminum alkoxide, aluminum oxide sol, or similar substances. Examples of suitable phosphorus sources include phosphoric acid, phosphoric acid esters, aluminum phosphate, or similar substances.The SDA contained in the starting material solution is, for example, an organic substance. Hydroxylated 1,4-diazabicyclo[2.2.2]octane-C4-diquat or the like can be used as SDA.

[0022] Subsequently, a hydrothermal synthesis is carried out on the starting material solution. The temperature during the hydrothermal synthesis is, for example, 120 to 200 °C. The duration of the hydrothermal synthesis is, for example, 5 to 240 hours. After completion of the hydrothermal synthesis, the resulting crystals are washed with pure water. Then, by drying the washed crystals, SAT-type zeolite powder is produced. SAT-type zeolite powder can also be produced by other methods.

[0023] After the SAT-type zeolite powder is produced, it undergoes heat treatment under an oxidizing gas atmosphere to remove the SDA from the powder by combustion (step S12). Preferably, the SDA is almost completely removed. The heating temperature for SDA removal is, for example, 350 to 700 °C. The heating time is, for example, 10 to 200 hours. The oxidizing gas atmosphere is an oxygen-containing atmosphere, such as air.

[0024] The SAT-type zeolite powder is then mixed with hot water and heated (step S13). The temperature of the hot water is, for example, 100 to 300 °C, preferably 100 to 200 °C. The heating time is, for example, 10 to 100 hours, preferably 20 to 50 hours. After heating in the hot water is complete, the resulting crystals are washed with pure water. The crystalline material with the powder-X-ray diffraction peaks shown in Table 2 is then obtained by drying the washed crystals.

[0025] Next, examples of how to produce powder from the aforementioned crystalline material will be described. Example 1

[0026] Aluminum alkoxide (aluminum isopropoxide), 85% phosphoric acid, and hydroxylated 1,4-diazabicyclo[2.2.2]octane-C4 diquat as the aluminum source, phosphorus source, and SDA (structure-forming agent), respectively, were dissolved in pure water to prepare a starting material solution with a composition of 1 Al₂O₃ : 1 P₂O₅ : 0.8 SDA : 200 H₂O. This starting material solution was hydrothermally synthesized at 190 °C for 50 hours. The crystals obtained by hydrothermal synthesis were collected, thoroughly washed with pure water, and then completely dried at 100 °C. X-ray diffraction confirmed that the crystals obtained were SAT-type zeolites. The crystals were heat-treated for 20 hours at 500 °C to burn off the SDA, and for 15 hours in hot water at 150 °C.The crystals obtained were collected, thoroughly washed with pure water, and then completely dried at 100 °C. The result was a powder of a crystalline material.

[0027] Fig.Figure 2 shows a powder X-ray diffraction pattern of the crystalline material from Example 1. The X-ray diffraction pattern was measured by densely packing the sample powder in a sample holder of sufficient depth. An X-ray diffraction instrument manufactured by Rigaku Corporation (product name: MiniFlex600) was used for the powder X-ray diffraction measurement. The tube voltage was 40 kV, the tube current was 15 mA, the scan rate was 0.5° / min, and the scan step was 0.02°. The divergence gap was 1.25°, the scattering gap was 1.25°, the receiving gap was 0.3 mm, the incident solar gap was 5.0°, and the receiving solar gap was 5.0°. A monochromator was not used, and a nickel foil with a thickness of 0.015 mm was used as the CuKβ line filter. The relative intensity of each peak of the powder X-ray diffraction pattern from Fig.Example 2 is shown in Table 3. The relative intensity of each peak in Table 3 is contained within the range of relative intensity shown in Table 2, and the crystalline material of Example 1 exhibited the powder X-ray diffraction peaks shown in Table 2. Table 3 2 θ (°) d (nm) Relative intensity 8,65±0,2 1,022 9 9,99±0,2 0,885 7 14,17±0,2 0,625 100 16,52±0,2 0,537 13 17,37±0,2 0,511 5 21,81 ±0,2 0,407 17 22,44±0,2 0,396 7 24,66±0,2 0,361 34 26,11±0,2 0,341 22 28,56±0,2 0,313 15 29,80±0,2 0,300 9 33,17±0,3 0,270 2 34,93±0,3 0,257 5 36,21±0,3 0,248 9 39,02±0,3 0,231 4 43,44±0,3 0,208 5 1 Example 2

[0028] The powder of a crystalline material was obtained in the same way as in Example 1, except that aluminum oxide sol was used as the aluminum source. Fig. Figure 3 shows a powder X-ray diffraction pattern of the crystalline material from Example 2. The relative intensity of each peak of the powder X-ray diffraction pattern from Fig.Example 3 is shown in Table 4. The relative intensity of each peak in Table 4 is contained within the range of relative intensity shown in Table 2, and the crystalline material of Example 2 exhibited the powder X-ray diffraction peaks shown in Table 2. Table 4 2 θ (°) d (nm) Relative intensity 8,65±0,2 1,022 9 9,99±0,2 0,885 9 14,17±0,2 0,625 100 16,52±0,2 0,537 37 17,37±0,2 0,511 6 21,81 ±0,2 0,407 18 22,44±0,2 0,396 11 24,66±0,2 0,361 38 26,11±0,2 0,341 32 28,56±0,2 0,313 16 29,80±0,2 0,300 13 33,17±0,3 0,270 3 34,93±0,3 0,257 3 36,21±0,3 0,248 11 39,02±0,3 0,231 6 43,44±0,3 0,208 6 Example 3

[0029] The powder of a crystalline material was obtained in the same way as in Example 1, except that magnesium acetate was added to the starting material solution. Fig. Figure 4 is a view showing a powder X-ray diffraction pattern of the crystalline material from Example 3. The relative intensity of each peak of the powder X-ray diffraction pattern from Fig.Example 4 is shown in Table 5. The relative intensity of each peak in Table 5 is contained within the range of relative intensity shown in Table 2, and the crystalline material of Example 3 exhibited the powder X-ray diffraction peaks shown in Table 2. Table 5 2 θ (°) d (nm) Relative intensity 8,65±0,2 1,022 8 9,99±0,2 0,885 10 14,17±0,2 0,625 100 16,52±0,2 0,537 49 17,37±0,2 0,511 8 21,81 ±0,2 0,407 49 22,44±0,2 0,396 14 24,66±0,2 0,361 43 26,11±0,2 0,341 40 28,56±0,2 0,313 18 29,80±0,2 0,300 16 33,17±0,3 0,270 4 34,93±0,3 0,257 12 36,21±0,3 0,248 12 39,02±0,3 0,231 6 43,44±0,3 0,208 6

[0030] Next, a membrane complex with a polycrystalline membrane made from the crystalline material present will be described. Fig. Figure 5 is a cross-sectional view showing a membrane complex 1. Fig.Figure 6 is a cross-sectional view showing an enlarged portion of the membrane complex 1. The membrane complex 1 comprises a porous support 11 and a polycrystalline membrane 12 arranged on the support 11. In the present preferred embodiment, the polycrystalline membrane is a membrane obtained by forming the aforementioned crystalline material on a surface of the support 11 in the form of a polycrystalline membrane. Fig. 5 The polycrystalline membrane 12 is represented by a thick line. Fig. Figure 6 shows the polycrystalline membrane 12 hatched. Furthermore, in Fig. 6 the thickness of the polycrystalline membrane 12 is shown to be larger than the actual thickness.

[0031] The support 11 is a porous element that can be permeated by gas and liquid. In the Fig.In the example shown in Figure 5, the support 11 is a monolithic support with an integrally and continuously shaped column-shaped main body, which is provided with a plurality of through holes 111 extending in a longitudinal direction (i.e., in Fig. 5 in an up-and-down direction). In the Fig. In the example shown in Figure 5, the support 11 has an essentially column-like shape. A cross-section perpendicular to the longitudinal direction of each of the through holes 111 (i.e., cells) is, for example, essentially circular. Fig. In 5, the diameter of each through-hole 111 is larger than the actual diameter, and the number of through-holes 111 is smaller than the actual number. The polycrystalline membrane 12 is arranged over an inner circumferential surface of each through-hole 111, covering substantially the entire inner circumferential surface of the through-hole 111.

[0032] The length of the support 11 (i.e. the length in the up-and-down direction of Fig. 5) is, for example, 10 cm to 200 cm. The outer diameter of the support 11 is, for example, 0.5 cm to 30 cm. The center-to-center distance between adjacent through-holes 111 is, for example, 0.3 mm to 10 mm. The surface roughness (Ra) of the support 11 is, for example, 0.1 µm to 5.0 µm and preferably 0.2 µm to 2.0 µm. Furthermore, the shape of the support 11 can be, for example, honeycomb-shaped, flat plate-shaped, tubular, cylindrical, columnar, polygonal prismatic, or the like. If the support 11 has a tubular or cylindrical shape, the thickness of the support 11 is, for example, 0.1 mm to 10 mm.

[0033] Various materials (e.g., ceramic or a metal) can be used as the material for the support 11 only if the materials ensure chemical stability during the process step of forming the polycrystalline membrane 12 on its surface. In the present preferred embodiment, the support 11 is formed from a ceramic sintered body. Examples of the ceramic sintered body selected as the material for the support 11 include aluminum oxide, silicon dioxide, mullite, zirconium dioxide, titanium dioxide, yttrium dioxide, silicon nitride, silicon carbide, and the like. In the present preferred embodiment, the support 11 contains at least one type of aluminum oxide, silicon dioxide, and mullite.

[0034] The carrier 11 may contain an inorganic binder. At least one of the following may be used as the inorganic binder: titanium dioxide, mullite, easily sinterable aluminum oxide, silica, glass frit, a clay mineral, and easily sinterable cordierite.

[0035] The mean pore diameter of the support 11 is, for example, 0.01 µm to 70 µm, preferably 0.05 µm to 25 µm. The mean pore diameter of the support 11 near the surface on which the polycrystalline membrane 12 is formed is 0.01 µm to 1 µm, and preferably 0.05 µm to 0.5 µm. Regarding the pore diameter distribution of the entire support 11, including its surface and its interior, D5 is, for example, 0.01 µm to 50 µm. 50 e.g. 0.05 µm to 70 µm and D 95 e.g. 0.1 µm to 2000 µm. The porosity of the support 11 near the surface on which the polycrystalline membrane 12 is formed is, for example, 25% to 50%.

[0036] The support 11, for example, has a multilayer structure in which several layers with different mean pore diameters are stacked in one thickness direction. The mean pore diameter and the sintered particle diameter in a surface layer that encloses the surface on which the polycrystalline membrane 12 is formed are smaller than those in layers other than the surface layer. The mean pore diameter in the surface layer of the support 11 is, for example, 0.01 µm to 1 µm and preferably 0.05 µm to 0.5 µm. If the support 11 has a multilayer structure, the materials for the respective layers can be those described above. The materials for the multiple layers that form the multilayer structure can be the same or different.

[0037] The polycrystalline membrane 12 is a porous membrane with small pores. The polycrystalline membrane 12 can be used as a separation membrane to separate a specific substance from a mixture of various substances by employing a molecular sieving function. Compared to the specific substance, it is more difficult for each of the other substances to permeate the polycrystalline membrane 12. In other words, the permeance of any other substance through the polycrystalline membrane 12 is lower than that of the specific substance.

[0038] The thickness of the polycrystalline membrane 12 is, for example, 0.05 µm to 30 µm, preferably 0.1 µm to 20 µm, and more preferably 0.5 µm to 10 µm. Increasing the thickness of the polycrystalline membrane 12 increases the separation efficiency. Decreasing the thickness of the polycrystalline membrane 12 increases the permeance. The surface roughness (Ra) of the polycrystalline membrane 12 is, for example, 5 µm or less, preferably 2 µm or less, more preferably 1 µm or less, and more preferably 0.5 µm or less.

[0039] The mean pore diameter of the polycrystalline membrane 12 made from the crystalline material is, for example, 1 nm or less, similar to the powder of the crystalline material. The mean pore diameter of the polycrystalline membrane 12 is preferably not less than 0.2 nm and not greater than 0.8 nm, more preferably not less than 0.3 nm and not greater than 0.5 nm, and further preferably not less than 0.3 nm and not greater than 0.4 nm. The mean pore diameter of the polycrystalline membrane 12 is smaller than that of the support 11 near the surface on which the polycrystalline membrane 12 is formed.

[0040] The permeation rate (permeance) of CO2 through the polycrystalline membrane 12 at 20 °C to 400 °C is, for example, 100 nmol / m². 2·s·Pa or more. Furthermore, the ratio (permeance ratio) of the permeance of CO2 through the polycrystalline membrane 12 to the permeance (leakage) of CH4 at 20 °C to 400 °C is, for example, 100 or more. The permeance and the permeance ratio are those in a case where the partial pressure difference of CO2 between the supply side and the permeation side of the polycrystalline membrane 12 is 1.5 MPa.

[0041] Fig. Figure 7 is a flowchart illustrating the process for the preparation of membrane complex 1. The preparation of membrane complex 1 begins with the production of seed crystals, which are used for the synthesis of polycrystalline membrane 12 (step S21). For example, SAT-type zeolite powder is produced by hydrothermal synthesis as described in step S11 of Fig.1. The zeolite is synthesized and the seed crystals are obtained from the zeolite powder. The zeolite powder itself can be used as seed crystals or processed by pulverization or the like to obtain the seed crystals.

[0042] The porous support 11 is then immersed in a solution in which the seed crystals are dispersed, and the seed crystals are thereby attached to the support 11 (step S22). Alternatively, the solution in which the seed crystals are dispersed is brought into contact with a section on the support 11 where the polycrystalline membrane 12 is to be formed, and the seed crystals are thereby attached to the support 11. This creates a support for attaching seed crystals. The seed crystals can be attached to the support 11 by any other method.

[0043] The support 11 with the seed crystals attached to it is immersed in a starting material solution. The starting material solution is prepared by dissolving an aluminum source, a phosphorus source, an SDA, and the like in a solvent in the same manner as in step S11. Then, the SAT-type zeolite is grown by hydrothermal synthesis using the seed crystals as nuclei to form the SAT-type zeolite membrane (the polycrystalline zeolite membrane) on the support 11 (step S23). The temperature during the hydrothermal synthesis is, for example, 120 to 200 °C. The time of the hydrothermal synthesis is, for example, 5 to 100 hours. During this time, the composition of the SAT-type zeolite membrane can be adjusted, for example, by changing the mixing ratio of the aluminum source and the phosphorus source in the starting material solution.After completion of the hydrothermal synthesis, the support 11 and the zeolite membrane are washed with pure water and then dried.

[0044] Subsequently, the support 11 and the zeolite membrane are subjected to heat treatment under an oxidizing gas atmosphere, as in step S12, to remove the SDA from the zeolite membrane by combustion (step S24). This process perforates micropores in the zeolite membrane. Preferably, the SDA is almost completely removed. The heating temperature for removing the SDA is, for example, in the range of 350 to 700 °C. The heating time is, for example, 10 to 200 hours.

[0045] The support 11 and the zeolite membrane are then immersed in hot water and heated (step S25). The temperature of the hot water is, for example, 100 to 300 °C, preferably 100 to 200 °C. The heating time is, for example, 10 to 100 hours, preferably 20 to 50 hours. After heating in the hot water is complete, the support 11 and the polycrystalline membrane are washed with pure water and then dried, for example, at 100 °C. The result is the membrane complex 1, comprising the support 11 and the polycrystalline membrane 12. The polycrystalline membrane 12 is produced from the crystalline material exhibiting the powder X-ray diffraction peaks shown in Table 2.

[0046] Next, with reference to the Fig. 8 and Fig. 9 the separation of a mixed substance using membrane complex 1 is described. Fig. Figure 8 is a diagram showing a separating device 2. Fig.Figure 9 is a flowchart showing a process for separating a mixed substance using the separation device 2.

[0047] In the separation device 2, a mixed substance containing several types of fluids (i.e., gases or liquids) is fed to the membrane complex 1, and a substance with high permeability in the mixed substance is caused to permeate the membrane complex 1, thereby being separated from the mixed substance. The separation in the separation device 2 can be carried out, for example, to extract a substance with high permeability from a mixed substance or to concentrate a substance with low permeability.

[0048] The mixed substance (i.e., the mixed fluid) can be a mixed gas containing several types of gases, a mixed liquid containing several types of liquids, or a gas-liquid biphase fluid containing both a gas and a liquid.

[0049] The mixed substance contains at least one of, for example, hydrogen (H2), helium (He), nitrogen (N2), oxygen (O2), water (H2O), water vapor (H2O), carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxide, ammonia (NH3), sulfur oxide, hydrogen sulfide (H2S), sulfur fluoride, mercury (Hg), arsine (AsH3), hydrogen cyanide (HCN), carbonyl sulfide (COS), C1 to C8 hydrocarbons, organic acid, alcohol, mercaptans, esters, ethers, ketones and aldehydes.

[0050] Nitrogen oxide is a compound of nitrogen and oxygen. The nitrogen oxide described above is, for example, NO₂. Xdesignated gas such as nitrogen oxide (NO), nitrogen dioxide (NO2), nitrous oxide (also known as nitrous monoxide) (N2O), nitrous trioxide (N2O3), nitrous tetroxide (N2O4), nitrous pentoxide (N2O5) or the like.

[0051] Sulfur oxide is a compound of sulfur and oxygen. The sulfur oxide described above is, for example, SO₂. X designated gas such as sulfur dioxide (SO2), sulfur trioxide (SO3) or the like.

[0052] Sulfur fluoride is a compound of fluorine and sulfur. Examples of the sulfur fluoride described above include disulfur difluoride (SFSF, S=SF2), sulfur difluoride (SF2), sulfur tetrafluoride (SF4), sulfur hexafluoride (SF6), and disulfur decafluoride (SF2F). 10 ) or the like.

[0053] C1 to C8 hydrocarbons are hydrocarbons with no fewer than 1 and no more than 8 carbon atoms. C3 to C8 hydrocarbons can be straight-chain, side-chain, or ring-shaped compounds. Furthermore, C3 to C8 hydrocarbons can be either saturated (i.e., containing no double or triple bonds in a single molecule) or unsaturated (i.e., containing one double and / or one triple bond in a single molecule). Examples of C1 to C4 hydrocarbons are methane (CH4), ethane (C2H6), ethylene (C2H4), propane (C3H8), propylene (C3H6), normal butane (CH3(CH2)2CH3), isobutane (CH(CH3)3), 1-butene (CH2=CHCH2CH3), 2-butene (CH3CH=CHCH3) or isobutene (CH2=C(CH3)2).

[0054] The organic acid described above is a carboxylic acid, sulfonic acid, or the like. Examples of carboxylic acids include formic acid (CH₂O₂), acetic acid (C₂H₄O₂), oxalic acid (C₂H₂O₄), acrylic acid (C₃H₄O₂), benzoic acid (C₆H₅COOH), and the like. Examples of sulfonic acids include ethanesulfonic acid (C₂H₆O₃S) and the like. The organic acid can be either a chain compound or a ring compound.

[0055] The alcohol described above is, for example, methanol (CH3OH), ethanol (C2H5OH), isopropanol (2-propanol) (CH3CH(OH)CH3), ethylene glycol (CH2(OH)CH2(OH)), butanol (C4H9OH) or the like.

[0056] Mercaptans are organic compounds with hydrogenated sulfur (SH) at the terminal end and are substances also known as thiols or thioalcohols. Examples of mercaptans described above include methyl mercaptan (CH3SH), ethyl mercaptan (C2H5SH), 1-propanethiol (C3H7SH), and similar compounds.

[0057] The ester described above is, for example, formic acid ester, acetic acid ester, or the like.

[0058] The ether described above is, for example, dimethyl ether ((CH3)2O), methyl ethyl ether (C2H5OCH3), diethyl ether ((C2H5)2O) or the like.

[0059] The ketone described above is, for example, acetone ((CH3)2CO), methyl ethyl ketone (C2H5COCH3), diethyl ketone ((C2Hs)2CO) or the like.

[0060] The aldehyde described above is, for example, acetaldehyde (CH3CHO), propionaldehyde (C2H5CHO), butanal (butylaldehyde) (C3H7CHO) or the like.

[0061] The following description assumes that the mixed substance separated by the separation device 2 is a mixed gas containing a variety of gas types.

[0062] The separating device 2 comprises the membrane complex 1, sealing parts 21, a housing 22, two sealing elements 23, a supply part 26, a first collecting part 27, and a second collecting part 28. The membrane complex 1, the sealing parts 21, and the sealing elements 23 are housed in the housing 22. The supply part 26, the first collecting part 27, and the second collecting part 28 are arranged outside the housing 22 and connected to the housing 22.

[0063] The sealing parts 21 are elements that are attached to the two end sections of the support 11 in the longitudinal direction (i.e., left-right direction). Fig.8) are attached and serve to cover and seal the two end faces of the support 11 in the longitudinal direction and the outer circumferential surface near the two end faces. The sealing elements 21 prevent the inflow and outflow of gases through the two end faces of the support 11. The sealing elements 21 are, for example, plate-shaped elements made of glass or resin. The material and shape of each sealing element 21 can be modified accordingly. Furthermore, the sealing elements 21 have a plurality of openings that overlap the through-holes 111 of the support 11, so that the two ends of each through-hole 111 of the support 11 in the longitudinal direction are not covered by the sealing elements 21. This allows the inflow and outflow of gases or the like from these two ends into the through-holes 111.

[0064] The housing 22 is a tubular element with an essentially circular cylindrical shape. The housing 22 is made, for example, of stainless steel or carbon steel. The longitudinal direction of the housing 22 is essentially parallel to the longitudinal direction of the membrane complex 1. A supply port 221 is arranged at an end section on one side in the longitudinal direction of the housing 22 (i.e., an end section on the left side in Fig. 8), and a first outlet port 222 is located at another end section on the opposite side. A second outlet port 223 is located on a circumferential surface of the housing 22. The supply section 26 is connected to the supply port 221. The first collector section 27 is connected to the first outlet port 222. The second collector section 28 is connected to the second outlet port 223. An interior of the housing 22 is a sealed space that is isolated from the space surrounding the housing 22.

[0065] The two sealing elements 23 are arranged longitudinally around the entire circumference between an outer circumferential surface of the membrane complex 1 and an inner circumferential surface of the housing 22, near the two end sections of the membrane complex 1. Each of the sealing elements 23 is an essentially ring-shaped element made of a gas-impermeable material. The sealing element 23 is, for example, an O-ring made of a flexible resin. The sealing elements 23 come into close contact with the outer circumferential surface of the membrane complex 1 and the inner circumferential surface of the housing 22 around their entire circumference. Fig.In the example shown in Figure 8, the sealing elements 23 lie close to the outer circumferential surface of the sealing parts 21 and come into indirect contact with the outer circumferential surface of the membrane complex 1 via the sealing parts 21. The sections between the sealing elements 23 and the outer circumferential surface of the membrane complex 1, as well as between the sealing elements 23 and the inner circumferential surface of the housing 22, are sealed, thus largely or completely preventing gas passage through these sections.

[0066] The supply unit 26 feeds the mixed gas into the interior of the housing 22 via the supply port 221. The supply unit 26 is, for example, a blower or a pump for pumping the mixed gas towards the housing 22. The blower or pump includes a pressure control unit for regulating the pressure of the mixed gas supplied to the housing 22. The first collecting unit 27 and the second collecting unit 28 are each, for example, a reservoir for storing the gas discharged from the housing 22, or a blower or a pump for transporting the gas.

[0067] In the separation of the mixed gas, the separation device 2 described above is manufactured to produce the membrane complex 1 (step S31). Subsequently, a mixed gas containing a variety of gases with different permeabilities for the polycrystalline membrane 12 is introduced into the interior of the housing 22 via the supply section 26. The main component of the mixed gas is, for example, CO2 and CH4. The mixed gas can contain any gas other than CO2 and CH4. The pressure (i.e., inlet pressure) of the mixed gas to be supplied from the supply section 26 into the interior of the housing 22 is, for example, 0.1 MPa to 20.0 MPa. The temperature for separating the mixed gas is, for example, 10 °C to 150 °C.

[0068] The mixed gas supplied from the supply section 26 into the housing 22 is introduced from the left end of the membrane complex 1 in the drawing into the interior of each through-hole 111 of the support 11, as indicated by arrow 251. High-permeability gas (e.g., CO2, hereinafter referred to as the "high-permeability substance") in the mixed gas permeates the polycrystalline membrane 12, which is arranged on the inner circumferential surface of each through-hole 111 and of the support 11, and is drawn out of the outer circumferential surface of the support 11. The high-permeability substance is thereby separated from the low-permeability gas (e.g., CH4, hereinafter referred to as the "low-permeability substance") in the mixed gas (step S32).The gas (hereinafter referred to as the “permeate substance”) that is discharged from the outer circumferential surface of the support 11 is collected by the second collecting section 28 through the second outlet port 223, as indicated by an arrow 253. The pressure (i.e., the permeation pressure) of the gas collected by the second collecting section 28 through the second outlet port 223 is, for example, about 1 atmosphere pressure (0.101 MPa).

[0069] Furthermore, a different gas (hereinafter referred to as the "non-permeate substance") flows in the mixed gas, other than the gas that has permeated the polycrystalline membrane 12 and the support 11, through each through-hole 111 of the support 11 from left to right in the drawing and is collected by the first collecting section 27 through the first outlet port 222, as indicated by arrow 252. The pressure of the gas to be collected by the first collecting section 27 through the first outlet port 222 is, for example, essentially the same as the inlet pressure. The non-permeate substance can comprise either a highly permeable substance that has not permeated the polycrystalline membrane 12 or the low-permeable substance described above.

[0070] Various modifications can be made to the crystalline material and membrane complex 1 described above.

[0071] The crystalline material with the powder X-ray diffraction peaks shown in Table 2 can be produced from substances other than SAT-type zeolite.

[0072] In addition to the support 11 and the polycrystalline membrane 12, the membrane complex 1 can contain a functional layer or a protective layer laminated onto the polycrystalline membrane 12. Such a functional or protective layer can be an inorganic membrane such as a zeolite membrane, a silicon dioxide membrane, a carbon membrane, or the like, or an organic membrane such as a polyimide membrane, a silicone membrane, or the like. Furthermore, a substance capable of readily and specifically adsorbing molecules such as CO2 or the like can be added to the functional layer or the protective layer laminated onto the polycrystalline membrane 12.

[0073] As a membrane of the membrane complex 1, in addition to the polycrystalline membrane 12, which consists of the crystalline material present, a membrane produced by dispersing particles of the crystalline material present in a membrane, such as an organic membrane, or a membrane produced by mixing particles of the crystalline material present with an organic substance, an inorganic substance, or the like, and forming the mixture into a membrane-like shape, can be used. As described above, the membrane arranged on the support 11 must contain only the crystalline material present.

[0074] In the separation device 2 with the membrane complex 1, any substance other than the substances shown by way of example in the preceding description can be separated from the mixed substance.

[0075] The configurations in the preferred embodiment described above and the variations may only be combined if they do not contradict each other.

[0076] While the invention has been shown and described in detail, the foregoing description is explanatory in all aspects and not limiting. It is therefore understood that numerous modifications and variations can be developed without deviating from the scope of the invention. Industrial applicability

[0077] The crystalline material of the present invention can be used for various other applications besides the membrane complex. The membrane complex can, for example, be used as a gas separation membrane and can be further used in various fields, such as as a separation membrane for any substance other than gas, as an adsorption membrane for various substances, or the like. Reference symbol list 1 Membrane complex 2. Separating device 11 carriers 12 polycrystalline membrane 21 Sealing part 22 cases 23 Sealing element 26 Supply section 27 first collection part 28 second collection 111 Through hole 221 Supply connection 222 first outlet port 223 second outlet port 251, 252, 253 Arrow S11 Step S11 S12 Step S12 S13 Step S13 S21 Step S21 S22 Step S22 S23 Step S23 S24 Step S24 S25 Step S25 S31 Step S31 S32 Step S32

Claims

[1] Crystalline material containing oxygen, aluminium and phosphorus, with the powder X-ray diffraction peaks shown in the table below. 2 θ (°) d (nm) Relative intensity 8,65±0,2 1,022 1-15 9,99±0,2 0,885 1-15 14,17±0,2 0,625 100 16,52±0,2 0,537 5-80 17,37±0,2 0,511 1-15 21,81±0,2 0,407 10-80 22,44±0,2 0,396 2-15 24,66±0,2 0,361 15-70 26,11±0,2 0,341 10-80 28,56±0,2 0,313 5-40 29,80±0,2 0,300 3-30 33,17±0,3 0,270 1-20 34,93±0,3 0,257 1-15 36,21±0,3 0,248 2-15 39,02±0,3 0,231 1-10 43,44±0,3 0,208 1-10 [2] Crystalline material according to claim 1, wherein the material is a powder with a mean particle diameter of 0.01 to 10 µm. [3] Crystalline material according to claim 1 or 2, containing no structuring agent. [4] Crystalline material according to any one of claims 1 to 3, further comprising at least one of silicon, magnesium, zinc, titanium, cobalt, copper, iron and boron. [5] Membrane complex comprising: a carrier; and a membrane consisting of the crystalline material according to one of claims 1 to 4 and arranged on the support.

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