Gas separation membrane, method for manufacturing the same, module using a gas separation membrane, and gas separation method

Abstract

To provide an organic and inorganic hybrid membrane which has a high gas permeability coefficient and a high separation factor, which has gas separation performance exceeding Robeson Upper Bound, and which is excellent in workability.SOLUTION: An organic and inorganic hybrid membrane includes a resin having a glass transformation temperature of 15°C or lower and a CO2 permeability coefficient of 200 Barrer or more at 35°C, and an inorganic filler having gas selectivity. The content of the inorganic filler having the gas selectivity is 35 mass% or more. The inorganic filler having the gas selectivity includes zeolite.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] This invention relates to an organic-inorganic hybrid membrane, a module using an organic-inorganic hybrid membrane, a method for separating gases, and a method for manufacturing an organic-inorganic hybrid membrane. [Background technology]

[0002] There are several methods for separating and purifying gases, including membrane separation, adsorption separation, absorption separation, and cryogenic separation. Membrane separation is a method that uses pressure as a driving force to separate gases based on the difference in gas velocity as they permeate the membrane. In gas separation, there is almost no phase change during the separation process, so it consumes less energy compared to other gas separation and purification methods. In recent times, with global climate change demanding a reduction in greenhouse gas emissions, membrane separation, which consumes less energy, is attracting attention as an alternative to conventional separation methods and as a means of separating and recovering greenhouse gases.

[0003] For gas separation, there are various types of membranes, including polymer membranes, which have been proposed since the 1970s; zeolite membranes fabricated on ceramic supports; and organic-inorganic hybrid membranes called Mixed Matrix Membranes (MMMs), which are polymer membranes with inorganic fillers. While polymer films have excellent processability, they have the disadvantage that there is a trade-off relationship between the gas permeability coefficient and the separation coefficient, and the Present Upper Bound (hereinafter referred to as Robeson Upper Bound) is generally the upper limit of their performance (Non-Patent Literature 1).

[0004] Some inorganic films, such as zeolite films, exhibit gas permeability and separation coefficients far exceeding the Robeson Upper Bound (Patent Document 1). However, because these inorganic films are fabricated on ceramic supports, they have the disadvantage of being difficult to process and tending to be expensive.

[0005] As described above, organic-inorganic hybrid membranes (MMMs), which are formed by incorporating inorganic fillers such as zeolites with gas separation capabilities into a matrix resin, are attracting attention as a membrane that overcomes the drawbacks of both polymer membranes and inorganic membranes and combines their advantages (Non-Patent Literature 2). However, even among organic-inorganic hybrid membranes, there have been very few reports of membranes that possess both high permeability and separation coefficients exceeding the Robeson Upper Bound (Non-Patent Literature 2).

[0006] In organic-inorganic hybrid membranes, it is thought that the more inorganic fillers, which have higher separation and permeability performance than the matrix resin, are mixed in, the closer the gas separation performance will be to that of the inorganic fillers alone. However, in reality, it has been reported that when the proportion of inorganic fillers such as zeolites exceeds a certain level, voids form between the matrix resin and the inorganic fillers, and gases pass through these voids, rendering the separation performance of the inorganic fillers useless, resulting in a decrease in performance (Non-Patent Literature 2). Many attempts have been made to modify the inorganic fillers to suppress the formation of voids between the inorganic fillers and the matrix resin and to improve their affinity with the matrix resin, but the effect has been limited.

[0007] On the other hand, stress applied to the interface during film formation is cited as a cause of voids between the matrix resin and inorganic filler in organic-inorganic hybrid films (Non-Patent Literature 3). Therefore, it is thought that using a flexible rubber-based matrix resin at film formation and operating temperatures can alleviate interfacial stress during film formation, thereby suppressing the generation of voids. However, there are few reports on organic-inorganic hybrid films using rubber-based resins. This is because the performance of the matrix resin greatly influences the performance of the organic-inorganic hybrid film, and it is considered desirable for the matrix resin used in organic-inorganic hybrid films to have gas separation performance close to Robeson Upper Bound. On the other hand, rubber-based resins exhibit performance far removed from Robeson Upper Bound (Non-Patent Literature 4), and their separation performance is inferior to crystalline resins, so they are not often chosen as matrix resins for organic-inorganic hybrid films. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Patent No. 5957828 [Non-patent literature]

[0009] [Non-Patent Document 1] Journal of membrane science 320 (2008) 390-400. [Non-Patent Document 2] Progress in Materials Science 102 (2019) 222-295. [Non-Patent Document 3] Journal of Molecular Structure 739 (2005) 87-98. [Non-Patent Document 4] Current Opinion in Solid State and Materials Science, 4 (1999) 549-552. [Overview of the project] [Problems that the invention aims to solve]

[0010] The present invention aims to provide an organic-inorganic hybrid membrane that solves the problems of the prior art, has high gas permeability and separation coefficients, exhibits gas separation performance superior to Robeson Upper Bound, and has excellent processability. [Means for solving the problem]

[0011] As a result of diligent research to solve the above problems, the inventors of the present invention have found that an organic-inorganic hybrid film containing a certain proportion or more of a certain inorganic filler in a resin having certain physical properties exhibits a high gas permeability coefficient, a high gas separation coefficient, and excellent flexibility, making it suitable for processing, thus leading to the present invention.

[0012] In other words, the gist of the present invention is found in the following [1] to

[12] . [1] A resin having a glass transition temperature of 15°C or less and a CO2 permeability coefficient of 200 Barrer or more at 35°C, and an inorganic filler having gas selectivity, wherein the content of the inorganic filler having gas selectivity is 35% by mass or more. The inorganic filler having gas selectivity includes a zeolite. An organic-inorganic hybrid membrane in which the framework density is 16.0T / 1000Å or less, assuming that all of the T elements in the zeolite are silicon. [2] The organic-inorganic hybrid film of [1], wherein the SiO2 / Al2O3 molar ratio of the zeolite is 7 or higher. [3] A resin having a glass transition temperature of 15°C or less and a CO2 permeability coefficient of 200 Barrer or more at 35°C, and an inorganic filler having gas selectivity, wherein the content of the inorganic filler having gas selectivity is 35% by mass or more. The inorganic filler having gas selectivity includes a zeolite. An organic-inorganic hybrid film in which the SiO2 / Al2O3 molar ratio of the zeolite is 7 or higher. [4] The inorganic filler is an organic-inorganic hybrid film of any of [1] to [3] having a particle size distribution with at least two peaks. [5] A gas separation and concentration method using one of the organic-inorganic hybrid membranes described in [1] to [4]. [6] A gas separation membrane module using one of the organic-inorganic hybrid membranes described in [1] to [4]. [7] A method for producing an organic-inorganic hybrid film, comprising an organic-inorganic hybrid film comprising a matrix resin and an inorganic filler, and a curing step of curing the matrix resin under pressure. [8] A method for producing the organic-inorganic hybrid film of [7], wherein the curing step involves heating while applying pressure. [9] A method for producing an organic-inorganic hybrid film according to [7] or [8], wherein the glass transition temperature of the matrix resin is 15°C or lower, and the CO2 permeability coefficient at 35°C is 200 Barrer or higher.

[10] A method for producing an organic-inorganic hybrid film according to any one of [7] to [9], wherein the inorganic filler comprises at least zeolite. A method for producing an organic-inorganic hybrid film according to any one of [1] to [4], comprising a curing step of curing a matrix resin while applying pressure.

[12] A method for producing the organic-inorganic hybrid film of

[11] , wherein the curing step involves heating while applying pressure. [Effects of the Invention]

[0013] According to one aspect of the present invention, an organic-inorganic hybrid gas separation membrane is provided that has both a high gas permeability coefficient and a high gas separation coefficient, is highly flexible, and is suitable for processing. [Brief explanation of the drawing]

[0014] [Figure 1] This is a schematic diagram of the apparatus used for gas separation in the example. [Figure 2] This figure shows the CO2 gas permeability coefficient and CO2 / CH4 separation coefficient, which are the evaluation results of the example. [Modes for carrying out the invention]

[0015] The embodiments of the present invention will be described in more detail below. However, the description of the constituent elements described below is merely one example of an embodiment of the present invention, and the present invention is not limited to these contents. It can be implemented in various ways within the scope of its gist. In this specification, "rubber" and "gum" are considered synonymous.

[0016] <Organic-inorganic hybrid membrane> One embodiment of the organic-inorganic hybrid film of the present invention comprises a matrix resin having a glass transition temperature of 15°C or less and a CO2 permeability coefficient of 200 Barrer or more at 35°C, and a zeolite as an inorganic filler, wherein the content of the inorganic filler in the organic-inorganic hybrid film is 35% by mass or more, and the framework density when all of the T element of the zeolite is silicon is 15.5T / 1000Å or less. Another embodiment of the organic-inorganic hybrid film of the present invention comprises a matrix resin having a glass transition temperature of 15°C or lower and a CO2 permeability coefficient of 200 Barrer or higher at 35°C, and zeolite as an inorganic filler, wherein the content of the inorganic filler in the organic-inorganic hybrid film is 35% by mass or higher, and the SiO2 / Al2O3 molar ratio of the zeolite is 7 or higher.

[0017] In one embodiment of the present invention, the organic-inorganic hybrid membrane refers to the gas separation layer and does not include the support layer, underlayer, protective layer, etc. An organic-inorganic hybrid membrane according to one aspect of the present invention may be used as a self-supporting membrane without a support layer, or it may be formed on an inorganic porous support layer or a porous support layer made of an organic polymer or an inorganic polymer and used in the form of a support layer. Examples of porous support layers made of organic polymers or inorganic polymers include porous organic films such as porous membrane filters and resin hollow fiber membranes. A substrate layer may be present between the porous support layer and the organic-inorganic hybrid membrane, and a protective layer may be present on the surface of the organic-inorganic hybrid membrane. The porous support layer and the organic-inorganic hybrid membrane formed on the porous support layer, as well as the substrate layer and protective layer if present, are collectively referred to as the organic-inorganic hybrid membrane composite.

[0018] The performance of organic-inorganic hybrid membranes and organic-inorganic hybrid membrane composites is expressed by the membrane's permeability and separation performance. In an organic-inorganic hybrid membrane composite, it is difficult to measure the performance of only the organic-inorganic hybrid membrane. Moreover, since the gas separation performance highly depends on the performance of the organic-inorganic hybrid membrane and the performance of the porous support layer has little influence on the gas separation performance, the performance of the organic-inorganic hybrid membrane composite may be regarded as the performance of the organic-inorganic hybrid membrane.

[0019] The permeation performance of an organic-inorganic hybrid membrane and an organic-inorganic hybrid membrane composite is represented by the gas permeation coefficient (hereinafter sometimes referred to as the permeation coefficient) of the organic-inorganic hybrid membrane and the organic-inorganic hybrid membrane composite, that is, Permeability, or the gas permeability (hereinafter sometimes referred to as the permeability), that is, Permeance.

[0020] [Permeation Coefficient] The gas permeation coefficient P of gas A A [Barrer] = P A × 10 -10 [cm 3 ·cm / (cm 2 ·s·cmHg)] is the amount of permeation per unit area when gas A permeates through the membrane, divided by the difference between the supply pressure and the permeation pressure, and integrated with the membrane thickness, and is represented by the following formula (1). P A × 10 -10 = N A l / (p2 - p1) ··· (1) In formula (1), N A [[ID=�4]]: The steady-state permeation flux (the amount of permeation per unit time divided by the membrane area) [cm 3 (STP) / (cm 2 ·s)] when gas A permeates through the membrane l: Membrane thickness [cm] p1: Partial pressure of gas A on the permeation side [cmHg] p2: Partial pressure of gas A on the supply side [cmHg] means.

[0021] The preferred range for the CO2 permeability coefficient exhibited by an organic-inorganic hybrid membrane and an organic-inorganic hybrid membrane composite according to one embodiment of the present invention is typically 1000 Barrer or more, preferably 3000 Barrer or more, more preferably 5000 Barrer or more, particularly preferably 7000 Barrer or more, and most preferably 10000 Barrer or more. The upper limit is not particularly limited, but is typically 100,000,000 Barrer or less. When the gas permeability coefficient is within this range, the gas processing capacity of the organic-inorganic hybrid membrane and the organic-inorganic hybrid membrane composite is sufficient, making it a membrane usable in actual processes.

[0022] [Permience (Transparency)] Gas permeability R of gas A A [mol / (m 2 (·s·Pa) is the amount of gas A that permeates per unit area through the membrane, divided by the difference between the supply pressure and the permeation pressure, and is expressed by the following formula (2). R A =n A / (p2'-p1')···(2) In formula (2), n A : The steady-state permeation flux (amount of permeation per unit time divided by the membrane area) when gas A permeates through the membrane [mol / (m²)] 2 ·s)] p1': Partial pressure of gas A on the permeating side [Pa] p2': Partial pressure of supply gas A [Pa] It means... Furthermore, permience can also be expressed using [GPU] as a unit, and in this specification, 1 GPU = 3.35 × 10⁻¹⁵ -10 mol / (m 2 It is ·s·Pa).

[0023] The preferred range of CO2 permeability exhibited by an organic-inorganic hybrid membrane and an organic-inorganic hybrid membrane composite according to one aspect of the present invention is typically 5 × 10⁻⁶. -9 [mol / (m 2 (·s·Pa) or more, preferably 1 × 10 -8 [mol / (m 2(·s·Pa) or more, more preferably 2 × 10 -8 [mol / (m 2 (·s·Pa), more preferably 5×10 -8 [mol / (m 2 (·s·Pa) or more, especially preferably 1 × 10 -7 [mol / (m 2 (·s·Pa) or higher, and there is no particular upper limit, but usually 1 × 10 -4 [mol / (m 2 The value is less than or equal to (·s·Pa). When the CO2 permeability is within this range, the gas processing capacity of the organic-inorganic hybrid membrane is sufficient, and the membrane becomes usable in actual processes.

[0024] [Separation coefficient] Separation coefficient α of gas A relative to gas B AB P is the permeability coefficient of gas A. A and the permeability coefficient P of gas B B , or the permeability R of gas A A and the permeability R of gas B B Using this, it can be expressed by the following equation (3). α AB =P A / P B =R A / R B ...(3)

[0025] The preferred range of the separation coefficient exhibited by the organic-inorganic hybrid membrane and organic-inorganic hybrid membrane composite according to one embodiment of the present invention is, for example, in the case of the CO2 / CH4 separation coefficient, usually 5 or more, preferably 7 or more, more preferably 10 or more, even more preferably 14 or more, particularly preferably 17 or more, and most preferably 20 or more, with no particular upper limit, but usually 1000 or less. When the separation coefficient is within this range, in gas separation using the organic-inorganic hybrid membrane, the amount of unseparated gas mixed into the permeate side is reduced, enabling efficient separation.

[0026] Furthermore, the permeability coefficient, gas permeability, and separation coefficient of these gases are calculated by measuring the steady-state gas permeation flux of the membrane using the constant volume / valuable pressure method (Journal of Polymer Science: Part B: Polymer Physics, Vol.38, 2051-2062 (2000)) with single-component gases or mixed gases.

[0027] [Air permeability] The air permeability of the organic-inorganic hybrid membrane and organic-inorganic hybrid membrane composite of the present invention is 10,000 L / (m³). 2 ·h) is less than or equal to this. When the air permeability is within this range, the organic-inorganic hybrid membrane is suitable for use as a separation membrane because it is free of defects or has reduced defects. From a similar viewpoint, the air permeability of the organic-inorganic hybrid membrane and the organic-inorganic hybrid membrane composite is preferably 5000 L / (m³). 2 h) less than or equal to 2000 L / (m 2 h) less than or equal to 1000 L / (m 2 The transmission rate is preferably 0.0 L / (m³). 2 • h) or more, for example 20 L / (m 2 • h) or more, for example 50 L / (m 2 • h) may be greater than or equal to h. When the air permeability is within this range, high separation performance can be achieved because there are no defects or through-holes, or their influence is sufficiently small.

[0028] Here, air permeability refers to the amount of air that permeates when the organic-inorganic hybrid membrane set in the module is placed under atmospheric pressure and one side of the organic-inorganic hybrid membrane is connected to a 5 kPa vacuum line, as detailed in the Examples section [Unit: L / (m)]. 2 (H) (at 0°C and 1 atmosphere)

[0029] The amount of air permeability can be adjusted, for example, by adjusting the type of matrix resin, the thickness of the organic-inorganic hybrid film, and the content of inorganic fillers in the organic-inorganic hybrid film.

[0030] [Bending Test] In one aspect of the present invention, it is preferable that the values ​​of the gas permeability coefficient, gas permeability, and separation coefficient after a bending test, in which the film is folded once by 180° along a curved surface with a bending radius (radius of curvature) of 5 mm and then straightened, are within 10% of the values ​​before bending. Here, the bending radius (radius of curvature) when performing the aforementioned bending test is preferably 4 mm or less, more preferably 3 mm or less, particularly preferably 2 mm or less, and usually 0.1 mm or more, preferably 0.5 mm or more, and more preferably 1 mm or more. When the organic-inorganic hybrid film of the present invention satisfies the above performance, it becomes possible to bend the organic-inorganic hybrid film as needed, resulting in excellent processability, no cracks or pinholes occurring in the film, and it can be processed into spiral-type modules and pleated-type modules. Furthermore, when the above performance is satisfied, it means that the organic-inorganic hybrid film does not develop cracks or pinholes even when bent at a high curvature, so it can be manufactured in a hollow fiber shape without developing cracks or pinholes.

[0031] [film thickness] The thickness of the organic-inorganic hybrid film according to one embodiment of the present invention is typically 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, typically 1000 μm or less, preferably 500 μm or less, more preferably 200 μm or less, even more preferably 100 μm or less, and particularly preferably 50 μm or less, in the case of a self-supporting film. When the thickness of the self-supporting film of the organic-inorganic hybrid film is within this range, the organic-inorganic hybrid film has high permeability and a certain degree of durability. Furthermore, it becomes a film with sufficient flexibility, excellent processability, and resistance to bending, and can be modularized without cracks or pinholes occurring in the film.

[0032] In organic-inorganic hybrid membrane composites in which an organic-inorganic hybrid membrane is formed on a porous support layer, the film thickness of the organic-inorganic hybrid membrane is usually 0.05 μm or more, preferably 0.1 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, and usually 100 μm or less, preferably 50 μm or less, more preferably 30 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less. In organic-inorganic hybrid membrane composites, if there is a base layer and / or protective layer, it may be difficult to determine the thickness of each layer because the organic-inorganic hybrid membrane, base layer, and protective layer are integrated. Furthermore, when the organic-inorganic hybrid membrane and the base layer and / or protective layer are integrated, the base layer and protective layer also contribute to gas permeability and separation, so the film thickness of the portion excluding the porous support layer (hereinafter sometimes referred to as the separation-related layer) is important in organic-inorganic hybrid membrane composites. In organic-inorganic hybrid membrane composites, the thickness of the separation-related layer is typically 0.05 μm or more, preferably 0.1 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, and typically 100 μm or less, preferably 50 μm or less, more preferably 30 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less. When the thickness of the organic-inorganic hybrid membrane or separation-related layer in an organic-inorganic hybrid membrane composite falls within this range, the organic-inorganic hybrid membrane becomes a highly permeable and durable membrane. Furthermore, it becomes a sufficiently flexible membrane with excellent processability, resistant to bending and other processes, allowing for modularization without the formation of cracks or pinholes.

[0033] [Measuring film thickness] For organic-inorganic hybrid films, the film thickness was calculated using a digital standard outside micrometer (MDC-25M, manufactured by Mitutoyo Corporation) to measure the center of the film and three points slightly inward from the edge of the film, selected evenly on the circumference. The thickness was then calculated from the arithmetic mean of these four points. In the organic-inorganic hybrid membrane composite, the cross-section of the organic-inorganic hybrid membrane composite obtained by freeze-rupture was photographed using a scanning electron microscope, and the thickness of the separation-related layer, which is the part other than the porous support layer, was calculated by taking the arithmetic mean of multiple locations and defined as the thickness.

[0034] [Matrix resin] In one embodiment of the present invention, the glass transition temperature (Tg) of the matrix resin is typically 15°C or lower, preferably 0°C or lower, more preferably -20°C or lower, even more preferably -50°C or lower, particularly preferably -70°C or lower, and most preferably -100°C or lower. When Tg is below the above upper limit, when an organic-inorganic hybrid membrane containing the matrix resin is used for gas separation, even if the inorganic filler content is high, the matrix resin remains flexible at the operating temperature, so no gaps are formed between the inorganic filler and the matrix resin, and it tends to exhibit sufficient gas separation performance. Furthermore, when Tg is below the above upper limit, it becomes possible to highly fill the inorganic filler without creating gaps between the matrix resin and the inorganic filler, and a membrane exhibiting sufficient permeability and separation performance can be obtained. In addition, when Tg is below this upper limit, even when used under high pressure conditions or for long periods of time, the flexibility of the matrix resin can absorb the strain at the interface between the matrix resin and the inorganic filler, so gaps tend not to form. Moreover, because it is flexible, when the membrane is processed into a spiral or other shape to form modules, no gaps are formed between the matrix resin and the inorganic filler, and the membrane performance tends to be good. Furthermore, while there are no particular restrictions on the lower limit of Tg, it is preferably -250°C or higher, and more preferably -200°C or higher.

[0035] In one embodiment of the present invention, the matrix resin preferably has a CO2 gas permeability coefficient of 200 Barrer or more at 35°C, more preferably 500 Barrer or more, even more preferably 1000 Barrer or more, particularly preferably 1500 Barrer or more, and most preferably 2000 Barrer or more. By being above the aforementioned lower limit, the gas permeability coefficient of the matrix resin alone is sufficiently large, which allows for a high gas permeability coefficient after it has been made into an organic-inorganic hybrid membrane. The CO2 permeability coefficient at 35°C was measured using a membrane made of matrix resin alone (hereinafter sometimes referred to as the resin membrane) under a differential pressure of 0.1 MPa. Furthermore, the separation coefficient, permeability coefficient, and transmittance of the matrix resin are measured by preparing a film made solely from the matrix resin (hereinafter sometimes referred to as a resin film) and using the same method as the measurement method for organic-inorganic hybrid films of the present invention, under conditions of 35°C and a differential pressure of 0.1 MPa.

[0036] The matrix resin is a polymer compound (polymer, polymer), and is preferably a silicone rubber made of polyorganosiloxanes such as polydimethylsiloxane (hereinafter sometimes referred to as PDMS), rubbers such as styrene-butadiene rubber, butadiene rubber, isoprene rubber, ethylene-propylene rubber, natural rubber, acrylic rubber, ethylene-vinyl oxide rubber, or polyolefins such as poly(4-methyl-1-pentine). More preferably, it is a silicone rubber made of polyorganosiloxanes such as PDMS, rubbers such as styrene-butadiene rubber, butadiene rubber, isoprene rubber, ethylene-propylene rubber, natural rubber, acrylic rubber, or ethylene-vinyl oxide rubber, and is particularly preferred. By using these resins as the matrix resin to produce an organic-inorganic hybrid membrane, a gas separation membrane with excellent gas permeability and separation performance can be obtained.

[0037] The preferred silicone rubber as the matrix resin is not particularly limited, but a polyorganosiloxane having a siloxane skeleton represented by the following formula (1), or a commercially available silicone rubber precursor that has been crosslinked and cured is preferred. A commercially available silicone rubber precursor is SILPOT TM Examples include 184 Silicone Elastomer Base (manufactured by Dow Toray Corporation).

[0038] [ka] In formula (1), n ​​is an integer of 2 or more, and R1 and R2 may each have a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, a cycloalkyl group such as a cyclohexyl group, a polyether group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group or a fluorenyl group, or a heteroalkyl group such as a fluoroalkyl group, saturated and unsaturated alicyclic groups containing heteroatoms such as an oxyranyl group or an oxetanyl group, a substituent that undergoes a condensation reaction such as an alkosy group, a ketoxime group, an acetoxy group, or an aminooxy group, or a substituent such as an amino group, a carboxyl group, a carbinol group, or an epoxy group. In terms of substitution, R1 and R2 of the side chain may be substituted, both ends may be substituted, or both ends and the side chain may be substituted. R1 and R2 may be the same as each other, or they may be different, or only R1 and R2 of a part of the polyorganosiloxane may be substituted. In terms of polymerizing or condensing the polyorganosiloxane of formula (1) by a crosslinking reaction to produce silicone rubber, the polyorganosiloxane of formula (1) preferably has crosslinkable groups such as vinyl groups, alkenyl groups, silicon-hydrogen bonds, oxetanyl groups, alkosyl groups, ketoxime groups, acetoxy groups, aminooxy groups, and other substituents that undergo condensation reactions. It is particularly preferable that it has alkenyl groups in order to utilize addition reactions.

[0039] In one embodiment of the present invention, the mechanism of the crosslinking reaction when a polyorganosiloxane is crosslinked and cured to form a silicone rubber is not particularly limited, and conventionally known curing reactions using organic peroxides, condensation reactions, addition reactions, ultraviolet light, radiation, or electron beam irradiation can be used. From the viewpoint of productivity, it is preferable that the mixing of inorganic fillers and storage after mixing with inorganic fillers can be carried out stably in the atmosphere, and in this respect, types that cure by addition reactions or ultraviolet light, radiation, or electron beam irradiation are desirable, and the use of addition reactions is particularly preferable because it does not require atmospheric control during curing and is simple.

[0040] The weight-average molecular weight of the main polyorganosiloxane before curing, which is mixed with the inorganic filler used in one aspect of the present invention, as measured by GPC, is usually 5000 or more, preferably 10000 or more, more preferably 20000 or more, and even more preferably 25000 or more, and is usually 100000 or less. When the molecular weight of the main polyorganosiloxane before curing is within this range, mixing of the zeolite and resin is easy, and film-forming properties are also good, so the filling ratio of the inorganic filler in the organic-inorganic hybrid film can be improved. Examples of polyorganosiloxanes that can be suitably used in the present invention include SILPOT, manufactured by Dow-Toray Corporation. TM 184. ELASTOSIL RT601 manufactured by Asahi Kasei Wacker Silicone Co., Ltd. is one example.

[0041] In one aspect of the present invention, if the viscosity becomes high and film formation becomes difficult when an inorganic filler is added during mixing of an inorganic filler and a matrix resin, the viscosity can be controlled by adding an organically modified silicone resin or an organically modified silicone oil, as described in Japanese Patent Application Publication No. 2017-66364.

[0042] Examples of organic groups in organically modified silicone resins and / or organically modified silicone oils include epoxy groups, alcohol groups, carboxyl groups, acrylic groups, methacrylic groups, thiol groups, amino groups, ether groups, aralkyl groups, alkyl groups, and the like. Of these, it is preferable to use at least one of silicone resins and / or organically modified silicone oils modified with epoxy groups, alcohol groups, or carboxyl groups, and it is more preferable to include at least one silicone resin and / or organically modified silicone oil modified with epoxy groups.

[0043] The organically modified silicone resins and / or organically modified silicone oils described above have organic groups with appropriate polarity and are therefore easily adsorbed onto inorganic fillers. Consequently, by including such organically modified silicones in resin and / or organically modified silicone oil compositions, they are more likely to be present on the inorganic filler surface, and the structural viscosity caused by the inorganic fillers can be disrupted. Specifically, the silicone portion of the -Si-O-Si-bonded portion of the organically modified silicone resin and / or organically modified silicone oil may come into contact with the low-polarity portion of the inorganic filler, and the organic group portion may come into contact with the polar portion of the inorganic filler, thereby functioning as a surfactant that resolves the phase separation structure within the resin composition. This improves the dispersibility of the inorganic filler and thus improves the packing density of the inorganic filler in the organic-inorganic hybrid film.

[0044] The proportion of the organically modified silicone resin and / or organically modified silicone oil is typically 1% or more, preferably 3% or more, more preferably 5% or more, and typically 50% or less, preferably 30% or less, and more preferably 10% or less, relative to the mass of the organic-inorganic hybrid film. When the proportion of the organically modified silicone resin and / or organically modified silicone oil is within the above range, the viscosity of the organic-inorganic hybrid film during film formation can be reduced. Furthermore, the dispersibility of the inorganic filler can be improved, ensuring the long-term stability of the organic-inorganic hybrid film.

[0045] [Inorganic filler] In one aspect of the present invention, the gas-selective inorganic filler is an inorganic compound that exhibits gas selectivity through molecular sieving effect and / or adsorption selectivity, such that it allows certain gases to pass through but blocks or significantly reduces the permeation rate of other gases. The inorganic filler may be used alone or in combination of two or more types. It may also be used in combination with an inorganic compound that does not exhibit gas selectivity. Examples of gas-selective inorganic fillers include zeolites, organometallic structures (MOFs), and porous metal complexes (PCPs). The gas-selective inorganic filler used in the present invention preferably contains one or more of zeolites, MOFs, and PCPs, and it is desirable that it contains at least one zeolite.

[0046] In addition to the gas-selective inorganic filler, the inorganic compound may also include silica, α-alumina, γ-alumina, zirconia, titania, yttria, silicon nitride, boron nitride, silicon carbide, etc. Adding these inorganic compounds in addition to the gas-selective inorganic filler may make it easier to form films or improve the physical properties of the organic-inorganic hybrid film other than gas permeability.

[0047] When zeolite is used as an inorganic filler in one aspect of the present invention, the framework density (hereinafter referred to as FD) is such that all elements other than oxygen (T elements) constituting the framework are Si. Si (This can happen), but usually it is 16.0T / 1000Å 3 Preferably, 15.8T / 1000Å 3 More preferably, 15.5T / 1000Å 3 More preferably, 15.3T / 1000Å 3 The following is particularly preferred: 15.2T / 1000Å 3 Below, the most preferred is 15.1T / 1000Å. 3 The following applies, and is typically 10T / 1000Å. 3 Preferably, 11T / 1000Å 3 More preferably 12T / 1000Å 3 That's all. Here, assuming that all elements T are Si, the framework density is (T / 1000 Å). 3 ) refers to zeolite at 1000 Å 3This refers to the number of elements other than oxygen that make up the framework, namely silicon, and this value is determined by the structure of the zeolite. The relationship between framework density and zeolite structure is shown in the Zeolite Structure Database (https: / / asia.iza-structure.org / IZA-SC / ftc_table.php). Therefore, FD Si A smaller value indicates that there is more space within the zeolite structure.

[0048] When using zeolites as organic-inorganic hybrid films, the matrix resin may clog the surface or interior of the zeolite pores, but FD Si When the value is within the aforementioned range, there is ample space inside the zeolite, so even if a portion is blocked, the gas flow path can be secured, and the effect of mixing in zeolite is easily exerted, resulting in a tendency to exhibit a high gas permeability coefficient and high separation performance. Si When the value is within the aforementioned range, the zeolite skeleton has sufficient strength, making the zeolite less prone to breakage and more stable, which is preferable.

[0049] In one aspect of the present invention, preferred zeolite structures are typically AEI, AFR, AFS, AFT, AFV, AFX, AFY, AST, AVL, * BEA, BEC, BOZ, BPH, CHA, -CLO, CON, DFO, EAB, EMT, ETR, * -EWT, FAU, GME, -IFT, -IFU, IFW, IRN, IRR, -IRY, ISV, ITE, * -ITN, ITT, -ITV, IWR, IWS, IWV, JSR, JST, KFI, LEV, LTA, MEI, MWW, NPO, NPT, OBW, OSO, PAU, POS, PUN, PWN, RHO, RWY, SAO, SAS, SAV, SBE, SBS, SBT, SFO, SFW, SOV, * -SVY, -SYT, THO, TSC, UFI, USI, UTL, VFI, preferably AEI, AFR, AFS, AFT, AFV, AFX, AFY, AST, AVL, *BEA, BEC, BOZ, BPH, CHA, -CLO, CON, DFO, EMT, ETR, * -EWT, FAU, GME, -IFT, -IFU, IFW, IRN, IRR, -IRY, ISV, ITE, ITT, -ITV, IWR, IWS, IWV, JSR, JST, K FI, LTA, MEI, NPT, OBW, OSO, POS, PUN, PWN, RHO, RWY, SAO, SAS, SAV, SBE, SBS, SBT, SFO, SFW, SOV, * -SVY, -SYT, THO, TSC, UFI, UTL, VFI, more preferably AEI, AFR, AFS, AFT, AFX, AFY, * BEA, BEC, BOZ, BPH, CHA, -CLO, DFO, EMT, ETR, * -EWT, FAU, GME, -IFT, -IFU, IRN, IRR, -IRY, ISV, ITT, -ITV, IWS, IWV, JSR, JST, KFI, LTA, MEI, NPT, OBW, OSO, POS, PUN, RHO, RWY, SA O, SAS, SAV, SBE, SBS, SBT, SFO, SFW, SOV, -SYT, TSC, UFI, VFI, more preferably AEI, AFS, AFT, AFX, AFY, BEC, BOZ, BPH, CHA, -CLO, DFO, EMT, * -EWT, FAU, GME, -IFT, -IFU, IRR, -IRY, ISV, ITT, IWS, IWV, JSR, JST, KFI, LTA, MEI, NPT, OBW, OSO, PUN, RHO, RWY, SAO, SAS, SAV, SBE, SBS, SBT, SFW, SOV, -SYT, TSC, VFI, more preferably AEI, AFX, CHA, EMT, FAU, GME, KFI, LTA, MEI, NPT, RHO, VFI, particularly preferably AEI, AFX, CHA, FAU, and most preferably CHA. When the zeolite has the above structure, there is a lot of space inside the zeolite, so the matrix resin does not completely block the pores, and an organic-inorganic hybrid membrane exhibiting high permeability separation performance is obtained.

[0050] The main zeolite used in one aspect of the present invention is not particularly limited, but a zeolite with 12 or fewer oxygen rings is preferred, a zeolite with 10 or fewer oxygen rings is more preferred, and a zeolite with 8 or fewer oxygen rings is most preferred. Generally, a zeolite with 6 or more oxygen rings is preferred, and a zeolite with 8 or more oxygen rings is more preferred. In this context, the value of n in zeolites having an n-membered oxygen ring indicates the largest number of oxygen atoms in the pores composed of oxygen and T elements (elements other than oxygen that make up the zeolite framework). For example, if pores with both 12-membered and 8-membered oxygen rings exist, as in MOR-type zeolites, it is considered a zeolite with a 12-membered oxygen ring.

[0051] Zeolites with 12 or fewer oxygen rings include AEI, AFR, AFS, AFT, AFV, AFX, AFY, AST, AVL, * BEA, BEC, BOZ, BPH, CHA, CON, DFO, EAB, EMT, FAU, GME, IFW, IRN, ISV, ITE, * -ITN, IWR, IWS, IWV, JSR, JST, KFI, LEV, LTA, MEI, MWW, NPO, NPT, OBW, PAU, POS, PUN, PWN, RHO, RWY, SAO, SAS, SAV, SBE, SBS, SBT, SFO, SFW, SOV, THO, TSC, UFI, and USI are examples. Zeolites with oxygen rings of 10 members or less include AEI, AFT, AFV, AFX, AST, AVL, BOZ, CHA, EAB, IFW, IRN, ITE, JST, KFI, LEV, LTA, MWW, NPT, OBW, PAU, PWN, RHO, SAS, SAV, SFW, THO, TSC, and UFI. Zeolites with 8 or fewer oxygen rings include AEI, AFT, AFV, AFX, AST, AVL, CHA, EAB, IRN, ITE, KFI, LEV, LTA, NPT, PAU, PWN, RHO, SAS, SAV, SFW, THO, TSC, and UFI. The oxygen n-membered ring structure determines the pore size of the zeolite. When the oxygen n-membered ring structure is within the above range, the zeolite tends to exhibit high gas separation performance, and when used as an organic-inorganic hybrid membrane, it is easier to obtain an effect that makes the gas separation performance greater than that of the matrix resin.

[0052] The main zeolites used in one aspect of the present invention include aluminosilicate, aluminophosphate (AlPO), silicoaluminophosphate (SAPO), metallo-aluminophosphate (MeAPO), and metallo-silicoaluminophosphate (MeAPSO), with aluminosilicate and silicoaluminophosphate (SAPO) being preferred, and aluminosilicate being particularly preferred from the viewpoint of zeolite durability.

[0053] The SiO2 / Al2O3 molar ratio of aluminosilicate is usually 7 or higher, preferably 8 or higher, more preferably 10 or higher, even more preferably 12 or higher, particularly preferably 15 or higher, and most preferably 20 or higher. The upper limit is usually 2000 or less, preferably 1000 or less, more preferably 500 or less, even more preferably 100 or less, and particularly preferably 50 or less. The SiO2 / Al2O3 molar ratio of aluminosilicate is FD SiIf the SiO2 / Al2O3 molar ratio is within the above range, the lower limit may be even lower, usually 0.5 or higher, preferably 1 or higher, more preferably 3 or higher, even more preferably 8 or higher, even more preferably 10 or higher, even more preferably 12 or higher, particularly preferably 15 or higher, and most preferably 20 or higher. The upper limit is usually 2000 or less, preferably 1000 or less, more preferably 500 or less, even more preferably 100 or less, and particularly preferably 50 or less. When the SiO2 / Al2O3 molar ratio is within the above range, the durability of the zeolite is high, and the durability of the gas separation and permeation performance of the organic-inorganic hybrid membrane tends to be good. Furthermore, when the SiO2 / Al2O3 molar ratio is within the above range, the hygroscopicity of the zeolite is not too high, which is preferable because pretreatment before use of the organic-inorganic hybrid membrane is unnecessary or sufficient with low temperature and short-time heating. In addition, in the actual gas separation process, it is less affected by moisture in the actual gas, so pretreatment of the gas introduced into the organic-inorganic hybrid membrane in the gas separation process is lighter, making it economical.

[0054] The SiO2 / Al2O3 molar ratio is determined by XRF analysis after creating a calibration curve using ICP analysis and XRF. Specifically, it is as follows. After heating and dissolving the zeolite sample in an aqueous hydrochloric acid solution, the content (mass %) of silicon and aluminum atoms was determined by ICP analysis. Then, a calibration curve was created between the fluorescence X-ray intensity of the analyte elements in the standard sample and the atomic concentration of the analyte elements. Using this calibration curve, the content (mass %) of silicon and aluminum atoms in the zeolite sample was determined by XRF.

[0055] The average particle diameter of the inorganic filler used in one embodiment of the present invention is typically 0.05 μm or more, preferably 0.1 μm or more, more preferably 0.5 μm or more, even more preferably 1 μm or more, even more preferably 5 μm or more, particularly preferably 7 μm or more, and typically 100 μm or less, preferably 50 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less, particularly preferably 10 μm or less. When the average particle diameter of the inorganic filler is within this range, the dispersibility of the inorganic filler is good, making it easy to mix the inorganic filler with the matrix resin in any proportion, and it is also easier to form paths through the inorganic filler when gas permeates. As a result, the effect of improving separation and permeation performance by the inorganic filler is easily apparent, and it is easy to obtain an organic-inorganic hybrid film with excellent separation and permeation performance.

[0056] The method for measuring the average particle size, as used here, is specifically as follows:

[0057] [Method for measuring average particle size] The particle size of the inorganic filler used in organic-inorganic hybrid films is determined by thoroughly dispersing the synthesized powder to create a sample, capturing an image with a scanning electron microscope, measuring the particle sizes of 30 arbitrarily selected particles in the image, and taking the arithmetic mean of these measurements to determine the average particle size. In the case of secondary particles formed by the aggregation of small crystalline particles, the secondary particle size is used. The particle size of the inorganic filler in the obtained organic-inorganic hybrid film is determined by measuring the particle sizes of 30 arbitrarily selected inorganic filler particles in the cross-sectional image obtained by scanning electron microscopy of the cross-sectional image of the organic-inorganic hybrid film obtained by freeze-breaking, and taking the arithmetic mean of these measurements as the average particle size. In all methods, the particle diameter is defined as the diameter of a circle (equivalent diameter) that has an area equal to the projected area of ​​the particle.

[0058] In one embodiment of the present invention, the inorganic filler may be a secondary particle formed by the aggregation of small crystalline particles, or a primary particle in which crystalline particles exist individually, as long as the particle size is within the aforementioned range. However, primary particles are particularly preferred because they are less likely to form gaps called grain boundaries between crystals, thus reducing the occurrence of defects between the resin and particles called voids when an organic-inorganic hybrid film is made, and tend to exhibit a high separation coefficient.

[0059] In one embodiment of the present invention, when two types of inorganic fillers with different average particle diameters are used, the ratio of their respective average particle diameters is typically 1.5 or more, preferably 3 or more, more preferably 5 or more, and typically 100 or less, preferably 50 or less, even more preferably 20 or less, particularly preferably 15 or less, and more preferably 10 or less. When the particle diameter ratio is within this range, the space between the inorganic fillers is minimized when the inorganic fillers are mixed into the matrix resin, and the filling ratio of the inorganic fillers can be improved. When three or more types of inorganic fillers with different average particle diameters are used, it is preferable that two of them satisfy the particle diameter ratio described herein. Here, "large particles" refers to the particles of the inorganic filler with the larger average particle diameter among the two types of inorganic fillers with different average particle diameters, and "small particles" refers to the particles of the inorganic filler with the smaller average particle diameter, and so on.

[0060] [Particle size distribution] In one embodiment of the present invention, when two types of inorganic fillers with different average particle sizes are used, the inorganic fillers contained in the organic-inorganic hybrid membrane will have at least two peaks in their particle size distribution. In this invention, the particle size distribution refers to the volume-based particle size distribution. The method for determining the volume-based particle size distribution is not particularly limited, but for inorganic fillers in powder form before film formation, the laser diffraction / scattering method is preferred. In organic-inorganic hybrid films or organic-inorganic hybrid film composites after film formation, the particle size distribution of the inorganic fillers contained in the organic-inorganic hybrid film and separation-related layers can be determined by image analysis. That is, a cross-section created by freeze-fracture can be observed with a scanning electron microscope, and the particles observed can be selected and the volume-based particle size distribution can be determined by image analysis. In the present invention, when the particle size distribution of the inorganic filler contained in the organic-inorganic hybrid membrane has at least two peaks, it is more preferable that the peak with larger particle size is typically between 1.5 μm and 4 μm, preferably between 20 μm and 20 μm, preferably between 15 μm and 10 μm, and the peak with smaller particle size is typically between 0.1 μm and 0.2 μm and 1 μm. Having a particle size distribution within these ranges improves the packing efficiency of the inorganic filler in the organic-inorganic hybrid membrane. Therefore, an organic-inorganic hybrid membrane with higher separation and permeability performance is obtained, which fully utilizes the performance of the inorganic filler. In the present invention, when the particle size distribution of the inorganic filler contained in the organic-inorganic hybrid film has at least two peaks, when the particle size of the peak with the smaller particle size is set to 1, the particle size of the peak with the larger particle size is usually 1.5 or more, preferably 2.0 or more, more preferably 5.0 or more, even more preferably 7.0 or more, and usually 100 or less, preferably 50 or less, even more preferably 20 or less, and particularly preferably 15 or less. When the peak with larger particle size takes these values ​​relative to the peak with smaller particle size, particles smaller than the minimum particle size in the volume-based particle size distribution can efficiently fill the interparticle gaps between inorganic fillers with particle sizes larger than the minimum, thereby improving the packing efficiency of the inorganic filler in the organic-inorganic hybrid membrane. As a result, the organic-inorganic hybrid membrane exhibits the full potential of the inorganic filler and has higher separation and permeability performance.

[0061] In one embodiment of the present invention, in which two types of inorganic fillers with different average particle sizes are used, the preferred ranges for particle sizes are as follows: The average particle size of large particles is preferably 1 μm or more, more preferably 4 μm or more, particularly preferably 5 μm or more, and usually 100 μm or less, preferably 50 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less, and particularly preferably 10 μm or less. The average particle size of small particles is preferably 0.05 μm or more, preferably 0.1 μm or more, more preferably 0.5 μm or more, and also preferably 1 μm or less. Having average particle sizes within these ranges improves the packing efficiency of the inorganic filler in the organic-inorganic hybrid membrane. Therefore, an organic-inorganic hybrid membrane with higher separation and permeability performance is obtained, fully utilizing the performance of the inorganic filler. Furthermore, within these ranges, the inorganic filler is easily dispersed in the matrix resin. In one embodiment of the present invention, when two types of inorganic fillers with different average particle diameters are used, the average particle diameter of the larger filler is typically 1.5 or more, preferably 2.0 or more, more preferably 5.0 or more, even more preferably 7.0 or more, and typically 100 or less, preferably 50 or less, even more preferably 20 or less, and particularly preferably 15 or less. When two types of inorganic fillers with different average particle diameters are used, if the average particle diameter of the larger filler is within these ranges relative to the average particle diameter of the smaller filler, the inorganic filler with the smaller average particle diameter can efficiently fill the interparticle gaps between the inorganic fillers with the larger average particle diameter, thereby improving the packing efficiency of the inorganic filler in the organic-inorganic hybrid membrane. As a result, an organic-inorganic hybrid membrane with higher separation and permeability performance is obtained, fully utilizing the performance of the inorganic filler. The average particle diameters of large and small particles can be determined for each of the two types of inorganic fillers used, according to the average particle diameter measurement method described later. When large and small particles are mixed, a sample is prepared by thoroughly dispersing the inorganic filler powder to be used, and the particle diameters of 30 or more arbitrarily selected particles are measured in the image taken with a scanning electron microscope. The obtained volume-based particle size distribution is converted to a number-based particle size distribution, and the arithmetic mean of the particle diameters is taken for each particle larger than the minimum value and each particle smaller than the minimum value, respectively. The average particle diameters of large and small particles contained in the inorganic filler in the obtained organic-inorganic hybrid film can be calculated by taking a cross-section of the organic-inorganic hybrid film obtained by freeze-breaking using a scanning electron microscope, measuring the particle diameters of 30 or more arbitrarily selected particles of the inorganic filler observed in the image of the obtained cross-section, converting the obtained volume-based particle size distribution to a number-based particle size distribution, and taking the arithmetic mean of the particle diameters is taken for each particle larger than the minimum value and each particle smaller than the minimum value, respectively. When there are three or more peaks, the arithmetic mean of particle diameters is calculated by taking the particle size between the local minimums, based on the number of particles. In this specification, the term "particle diameter" refers to the secondary particle diameter in the case of secondary particles formed by the aggregation of small crystalline particles. In all methods, the particle diameter is defined as the diameter of a circle (equivalent circle diameter) having an area equal to the projected area of ​​the particle. The average particle diameter measured in the average particle diameter measurement method described later is also the average particle diameter based on the particle diameter described here.

[0062] In one embodiment of the present invention, in which two types of inorganic fillers with different average particle diameters are used, when the mass of the small particles is set to 1, the mass of the large particles is not particularly limited, but for example, it is preferably 3 or more, more preferably 4 or more, and even more preferably 4.5 or more. Usually, it is preferably 10 or less, preferably 8 or less, and more preferably 6 or less. When the mass ratio is within this range, the small particles can fill the gaps between the large particles, improving the packing efficiency of the inorganic filler. The mass ratio of large particles to small particles can be calculated from the area of ​​the peak of the volume-based particle size distribution of the inorganic filler.

[0063] To obtain an inorganic filler whose particle size distribution has at least two peaks, it is preferable to use two types of inorganic fillers with different average particle sizes as described above. For example, two types of inorganic fillers with different average particle sizes can be mixed into a matrix resin. In this case, the preferred average particle sizes of the two types of inorganic fillers with different average particle sizes are, for the larger particles, preferably 1 μm or more, more preferably 4 μm or more, and particularly preferably 5 μm or more, and usually 100 μm or less, preferably 50 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less, and particularly preferably 10 μm or less.

[0064] In one embodiment of the present invention, the proportion of the mass of gas-selective inorganic filler to the total mass of the organic-inorganic hybrid membrane is typically 35% by mass or more, preferably 37% by mass or more, more preferably 42% by mass or more, even more preferably 48% by mass or more, even more preferably 52% by mass or more, even more preferably 57% by mass or more, and particularly preferably 62% by mass or more, and typically 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, and particularly preferably 80% by mass or less. When the proportion of inorganic filler mass is within this range, the organic-inorganic hybrid membrane tends to be a membrane with excellent processability that maintains its flexible properties, and also exhibits high separation and permeability performance exceeding the Robeson Upper Bound.

[0065] The proportion of inorganic filler in an organic-inorganic hybrid film can be determined by selecting a standard analytical method based on the physical properties of the resin and the inorganic filler. For example, by burning off the entire resin portion using thermogravimetric analysis (TG), the ratio of inorganic filler to the total mass of the organic-inorganic hybrid film can be determined.

[0066] In organic-inorganic hybrid membranes of silicone resin and inorganic fillers, for example, the silicone resin in the organic-inorganic hybrid membrane can be decomposed using a silicone resin decomposition agent, and the mass of the inorganic filler can be determined by separating the solid components by filtration or centrifugation, thereby determining its ratio to the total mass of the organic-inorganic hybrid membrane. As silicone resin decomposition agents, commercially available silicone resin decomposition agents such as methyl orthoformate and Digesil NC manufactured by Ecosearch, Inc., and silicone solvents such as silicone cleaner manufactured by Nisshin Chemical Research Institute Co., Ltd. can be used.

[0067] In one embodiment of the present invention, when the organic-inorganic hybrid membrane also includes an inorganic filler that does not exhibit gas selectivity, the ratio of the inorganic filler mass (total mass of gas-selective and gas-inselective inorganic fillers) to the total mass of the organic-inorganic hybrid membrane is not particularly limited, and is, for example, 35% by mass or more, preferably 37% by mass or more, more preferably 42% by mass or more, even more preferably 48% by mass or more, even more preferably 52% by mass or more, even more preferably 57% by mass or more, particularly preferably 62% by mass or more, and is usually 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, particularly preferably 80% by mass or less. When the ratio of inorganic filler mass is within this range, the organic-inorganic hybrid membrane tends to be a membrane with excellent processability that maintains its flexible properties, and exhibits high separation and permeability performance exceeding the Robeson Upper Bound.

[0068] Furthermore, in one embodiment of the present invention, the filling ratio of zeolite in the organic-inorganic hybrid membrane is typically 20 vol% or more, more preferably 30 vol% or more, even more preferably 40 vol% or more, even more preferably 50 vol% or more, even more preferably 60 vol% or more, and typically 99 vol% or less, preferably 95 vol% or less, more preferably 90 vol% or less, even more preferably 85 vol% or less, and particularly preferably 80 vol% or less. When the volume fraction of zeolite is within this range relative to the volume of the organic-inorganic hybrid membrane, the organic-inorganic hybrid membrane tends to be a membrane with excellent processability that maintains its flexible properties, and also exhibits high separation and permeability performance exceeding the Robeson Upper Bound.

[0069] The volume fraction of zeolite in an organic-inorganic hybrid membrane can be determined by observing the membrane's cross-section with a scanning electron microscope (SEM). From the cross-sectional portion of the organic-inorganic hybrid membrane corresponding to the separation layer (not the support layer, substrate layer, or protective layer), the area fractions of inorganic fillers, gas-selective inorganic fillers, and zeolite are calculated for five or more fields of view. The arithmetic mean of these areas fractions is then taken as the volume fraction of inorganic fillers, gas-selective inorganic fillers, and zeolite in the organic-inorganic hybrid membrane. Since the inorganic fillers, gas-selective inorganic fillers, and zeolite are considered to be uniformly dispersed on average in the organic-inorganic hybrid membrane, it is assumed that the same area fraction as in a portion of the cross-section is maintained on average in the depth direction of the cross-section. Therefore, the area fraction can be considered equal to the volume fraction.

[0070] Inorganic fillers, gas-selective inorganic fillers, and zeolites can be distinguished by their shape and compositional analysis using SEM-EDX during cross-sectional SEM observation.

[0071] In one embodiment of the present invention, when zeolite and an inorganic filler other than zeolite are used in combination, the ratio of the mass of the inorganic filler other than zeolite to the mass of zeolite is usually 30% or less, preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less, with no particular lower limit, but usually 0.1% or more. When the mass % of the inorganic filler other than zeolite is within this range, the resulting organic-inorganic hybrid membrane tends to be a membrane with excellent processability that maintains its flexible properties, and also exhibits high separation and permeability performance exceeding the Robeson Upper Bound.

[0072] The shape of the inorganic filler used in one aspect of the present invention is not particularly limited, but spherical, cubic, rectangular, and hexagonal prism-shaped particles are preferred, with spherical and cubic shapes being particularly preferred, and spherical being the most preferred. When the inorganic filler has one of these shapes, the amount of inorganic filler packed into the film can be increased, and an organic-inorganic hybrid film with high separation and permeability can be obtained. Inorganic fillers with the shapes described above can be obtained by controlling the synthesis method of the inorganic filler, or by physically polishing the synthesized inorganic filler powder. When the inorganic filler is spherical, the high fluidity of the particles makes it possible to improve the particle packing density, especially when forming and curing the film under pressure. When the inorganic filler is cubic, the alignment of the particles reduces the interparticle gaps, thus improving the packing density of the inorganic filler in organic-inorganic hybrid films.

[0073] In one aspect of the present invention, the inorganic filler used preferably has an average circularity coefficient of 0.80 or higher, and particularly preferably 0.90 or higher. The average circularity coefficient is usually 1.0 or lower. When the average circularity coefficient is within this range, the fluidity of the particles is high, which makes it possible to improve the particle packing rate, and the packing rate can be improved especially when film formation and curing are performed under pressure. The circularity coefficient referred to here is 4πS / L, where S is the area of ​​the two-dimensional projection image of the inorganic filler particles used and L is the perimeter of the particles.2 It is expressed as follows, and its value is 1.0 when the particle is a perfect sphere, and the closer it is to a perfect sphere, the larger the value. The method for calculating the mean circularity coefficient referred to here is as follows.

[0074] [Method for calculating the average circularity coefficient diameter] The average circularity coefficient of the inorganic filler used in organic-inorganic hybrid films is calculated by thoroughly dispersing the synthesized powder to prepare a sample, imaging it with a scanning electron microscope, calculating the circularity coefficient for 30 arbitrarily selected particles, and taking the arithmetic mean of these coefficients. For secondary particles formed by the aggregation of small crystalline particles, the circularity coefficient is calculated for the secondary particles and the average value is taken. The average circularity coefficient of the inorganic filler in the obtained organic-inorganic hybrid film and organic-inorganic hybrid film composite is determined by taking a scan electron microscope image of the cross-section of the organic-inorganic hybrid film obtained by freeze-fracture, calculating the circularity coefficient of 30 arbitrarily selected inorganic filler particles visible in the cross-section, and taking the arithmetic mean of these coefficients as the average circularity coefficient. In embodiments where the inorganic filler contained in the organic-inorganic hybrid membrane and the organic-inorganic hybrid membrane composite has a particle size distribution with at least two peaks, the average circularity coefficient is calculated similarly for particles larger than the minimum value of the particle size distribution and for particles smaller than the minimum value.

[0075] Furthermore, in embodiments in which the inorganic filler contained in the organic-inorganic hybrid film has a particle size distribution with at least two peaks, it is preferable that the average circularity coefficient is 0.80 or higher, particularly preferably 0.90 or higher, for particles with a particularly large mass, and normally the average circularity coefficient is 1.0 or lower.

[0076] The inorganic filler used in one aspect of the present invention may have a modified surface. Here, surface modification means reacting a compound that can react with the OH groups on the surface of the inorganic filler (hereinafter sometimes referred to as a surface modifier) ​​to bond the surface modifier to the inorganic filler surface.

[0077] The surface modifier used here is not particularly limited as long as it is commonly used, but from the viewpoint of reactivity with OH groups, silazanes, siloxanes, alkoxysilanes, chlorosilanes, titanate coupling agents, silicate oligomers, etc., can be preferably used.

[0078] Examples of silazanes include hexamethyldisilazane and hexaethyldisilazane.

[0079] Examples of siloxanes include hexamethyldisiloxane, hexaethoxydisiloxane, 1,3-butyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, 1,3-divinyltetramethyldisiloxane, hexaethyldisiloxane, 3-glycidoxypropylpentamethyldisiloxane, methylhydrogenpolysiloxane, and 1,3-dichloro-1,1,3,3-tetra-i-propyldisiloxane.

[0080] Examples of alkoxysilanes include vinyltrimethoxysilane, vinyltriethoxysilane, propenyltrimethoxysilane, propenyltriethoxysilane, butenyltrimethoxysilane, butenyltriethoxysilane, pentenyltrimethoxysilane, pentenyltriethoxysilane, hexenyltrimethoxysilane, hexenyltriethoxysilane, heptenyltrimethoxysilane, heptenyltriethoxysilane, octenyltrimethoxysilane, octenyltriethoxysilane, nonenyltrimethoxysilane, nonenyltriethoxysilane, dekenyltrimethoxysilane, dekenyltriethoxysilane, undekenyltrimethoxysilane, undekenyltriethoxysilane, dodekenyltrimethoxysilane, and dodekenyltriethoxysilane, as well as β-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethyl Toxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltriethoxysilane, trimethylmethoxysilane, trimethyleth Xysilane, trimethylpropoxysilane, phenyldimethylmethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-octylmethyldiethoxysilane, n-decyltrimethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenethyltrimethoxysilane, dodecyltrimethoxysilane Examples include sisilane, n-octadecyltriethoxysilane, diphenyldimethoxysilane, vinyltris(β-methoxyethoxy)silane, 3-isocyanatetopropyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecatrifluoropropyltrimethoxysilane, n-decyltrimethoxysilane, dimethoxydiethoxysilane, bis(triethoxysilyl)ethane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, and 3-aminopropyldimethylethoxysilane.

[0081] Examples of chlorosilanes include vinyltrichlorosilane, trimethylsilyl chloride, triethylsilyl chloride, t-butyldimethylsilyl chloride, tri-i-propylsilyl chloride, and 3-isocyanopropyldimethylchlorosilane.

[0082] Examples of silicate oligomers include methyl silicate oligomers such as MS51, MS56, MS57, and MS56S manufactured by Mitsubishi Chemical Corporation.

[0083] By modifying the surface with these surface modifiers, the affinity between the organic solvent used in film formation and the inorganic filler is increased. This improves the dispersibility of the inorganic filler in the mixture of matrix resin, inorganic filler, and solvent used in film formation, making it easier to obtain an organic-inorganic hybrid film with a high inorganic filler packing density. Furthermore, modifying the surface of the inorganic filler with these surface modifiers improves the affinity between the inorganic filler and the matrix resin, reducing the likelihood of voids forming at the interface between the inorganic filler and the matrix resin. This makes it easier to obtain organic-inorganic hybrid films with high separation and permeability performance that fully utilize the properties of the inorganic filler. On the other hand, the pores of inorganic fillers, such as zeolites, which have a molecular sieving effect due to their pores, can be blocked by surface modifiers. Therefore, it is desirable to minimize the modification of inorganic fillers by surface modifiers, and surface modifiers with low molecular weight and short alkyl chains are preferable. In this respect, siloxanes are particularly preferred among these surface modifiers, and hexamethyldisiloxane is the most preferred.

[0084] The zeolite used in one aspect of the present invention may be ion-exchanged as needed. In the case of zeolites synthesized using a template, ion exchange is usually performed after the template is removed. Ions to be ion-exchanged include protons and Na. + , K + , Cs + Li + Alkali metal ions such as Ca 2+ Mg 2+ Sr 2+, Ba 2+ Examples include divalent metal ions such as Fe, Cu, Zn, Ag, etc. Since the pore size of zeolite and its affinity with gas molecules can be changed by ion exchange, the preferred ions vary depending on the type of gas to be separated. However, the permeation performance can be improved by using ions with high affinity for the gas to be permeated. In the case of organic-inorganic hybrid membranes for CO2 separation, from the perspective of affinity with CO2, Ca 2+ , K + , Ag + are preferred. When these ions are used, the permeation performance of CO2 improves, and the separation factor tends to increase.

[0085] Ion exchange of zeolite can be carried out by ordinary methods. However, in order to avoid clogging of zeolite pores, it is desirable to calcine after ion exchange to thermally decompose and remove counter anions such as NO3 - .

[0086] [Support layer] The organic-inorganic hybrid membrane in one aspect of the present invention may be a self-supporting membrane, but may also be formed on a support layer. From the perspective of not impairing the permeation performance of the organic-inorganic hybrid membrane, a porous support layer is preferable as the support layer. Forming the membrane on a porous support layer is preferable because it increases the durability of the membrane and its resistance to external forces compared to a self-supporting membrane, and the membrane thickness can be reduced. The shape of the support layer is not particularly limited, and examples include a porous planar membrane, a porous hollow fiber membrane, a non-woven fabric, etc. A porous hollow fiber membrane is preferable because it can increase the membrane area per unit volume.

[0087] The pore size of the porous support layer is usually 100 μm or less, preferably 50 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, still more preferably 1 μm or less, particularly preferably 0.5 μm or less, and usually 0.01 μm or more, preferably 0.1 μm or more, more preferably 0.2 μm or more. When the pore size of the porous support layer is within the aforementioned range, the support layer can provide the necessary strength to the organic-inorganic hybrid film without hindering gas permeation. The porous support layer may have a symmetrical structure or an asymmetrical structure with a rough support layer beneath the surface dense layer, but an asymmetrical structure is preferred because it reduces the resistance originating from the porous support layer during gas permeation.

[0088] The thickness of the porous support layer is typically 10 μm or more, preferably 30 μm or more, more preferably 50 μm or more, even more preferably 70 μm or more, and particularly preferably 100 μm or more. It is typically 2 mm or less, preferably 1 mm or less, more preferably 500 μm or less, even more preferably 200 μm or less, and particularly preferably 150 μm or less. When the thickness of the porous support layer is within this range, sufficient strength can be provided to the organic-inorganic hybrid film.

[0089] The material of the porous support layer is not particularly limited, but is usually a polymer, preferably polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethersulfone (PES), polysulfone (PSU), cellulose acetate (CA), polyethylene (PE), polypropylene (PP), polycarbonate (PC), polyimide (PI), or polyamide, more preferably polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethersulfone (PES), or cellulose acetate (CA), and particularly preferably polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE). When the material of the porous support layer is within this range, the porous support layer has sufficient flexibility and strength and does not impose any restrictions on the method of forming the organic-inorganic hybrid film, thus providing sufficient strength to the organic-inorganic hybrid film and excellent processability.

[0090] [Base layer] In one aspect of the present invention, the organic-inorganic hybrid film may be formed on a porous support layer, but when forming it on a porous support layer, it may also be formed on a base layer (=gutter layer) formed on the porous support layer. By forming the organic-inorganic hybrid film on the porous support layer via the base layer, it is possible to avoid or reduce the occurrence of defects in the organic-inorganic hybrid film due to excessive penetration of the matrix resin and the solvent used for film formation into the porous support layer during film formation. Furthermore, since the matrix resin and the solvent used for film formation do not excessively penetrate into the porous support layer, it becomes possible to form a thin and dense organic-inorganic hybrid film. The material forming the underlayer is not particularly limited, but typically silicone resin, polytrimethylsilylpropyne (PTMSP), polyethersulfone (PES), polysulfone (PSU), and polyethylene oxide (PEO) are used, preferably silicone resin, polytrimethylsilylpropyne (PTMSP), and polyethylene oxide (PEO), and especially preferably silicone resin, because it has high solvent resistance and is easy to handle with fewer restrictions on the film formation method when forming a film on the underlayer. The thickness of the underlayer is preferable as it reduces the transmission resistance of layers unrelated to separation, but is usually 1 nm or more, preferably 10 nm or more, and usually 3 μm or less, preferably 1.5 μm or less, and more preferably 500 nm or less. Furthermore, the underlayer may be solubilized in the solvent used to form the organic-inorganic hybrid film, so that in the resulting organic-inorganic hybrid film, it may be at least partially integrated with the organic-inorganic hybrid film.

[0091] [Protective layer] In one embodiment of the present invention, a protective layer can be formed on an organic-inorganic hybrid membrane, which is a separation layer, and used for separation. The material forming the protective layer is not particularly limited, but typically silicone resin, polytrimethylsilylpropyne (PTMSP), polyethersulfone (PES), polysulfone (PSU), and polyethylene oxide (PEO) are preferred, with silicone resin, polytrimethylsilylpropyne (PTMSP), and polyethylene oxide (PEO) being preferred, and silicone resin being particularly preferred, as these have high gas permeability and have little impact on the performance of the organic-inorganic hybrid membrane, which is the separation layer. The protective layer is preferably absent because it does not hinder the permeation of the separation layer. However, if it is necessary to protect the separation layer, it is desirable to make it as thin as possible to adequately protect the separation layer without hindering its permeation. It is typically 1 nm, preferably 10 nm, more preferably 100 nm or more, and typically 100 μm or less, preferably 10 μm, more preferably 1 μm or less.

[0092] <Gas separation membrane module> When an organic-inorganic hybrid membrane according to one aspect of the present invention is used for industrial gas separation, it is desirable to modularize it as a membrane composited with a support layer. Examples of modules include spiral type, hollow fiber type, pleated type, tubular type, and plate and frame type, with spiral type (spiral wound type or SW type) or hollow fiber type being preferred.

[0093] <Method for manufacturing organic-inorganic hybrid membranes> A method for producing an organic-inorganic hybrid film according to one aspect of the present invention comprises a dispersion step of dispersing an inorganic filler in a matrix resin and, if necessary, a solvent; a casting step of supporting the dispersion of the inorganic filler in the matrix resin and, if necessary, a solvent, on a flat or curved surface; and a curing step of removing the solvent from the cast dispersion and curing the resin. A kneading step of solidifying the matrix resin and the gas-selective inorganic filler may be further included as a step prior to the dispersion step. The curing step of curing the resin may further include a step of curing the matrix resin while applying pressure. In the step of curing the matrix resin while applying pressure, heating is preferable to accelerate the curing of the resin. Specifically, after thoroughly drying the inorganic filler, the matrix resin dissolved in a solvent, or the raw material of the matrix resin before polymerization and curing without a solvent, and the inorganic filler are thoroughly mixed to disperse the inorganic filler. If a resin requiring a curing agent is used, the curing agent is added and mixed well to disperse the inorganic filler. At this time, it is also possible to disperse the inorganic filler in the solvent first, then add the matrix resin and mix well again to disperse the inorganic filler. Methods for dispersing the inorganic filler include stirring with a conventional mixer, bead mill, ball mill, etc., kneading with a twin-screw kneader or triple-roll kneader, as well as using ultrasonic crushing and dispersion, and rotating / revolving mixers. An organic-inorganic hybrid film is obtained by mixing an inorganic filler, a matrix resin or matrix resin raw material, and, in some cases, a curing agent and solvent in a slurry, placing a predetermined amount of the slurry into a Teflon® petri dish in the case of a self-supporting film, or by forming a film of a certain thickness on a release film using a blade, bar coater, die coater, or spin coater, then removing the solvent in a vacuum dryer, and curing it at a predetermined curing temperature for a predetermined curing time, or by curing the resin in an inert oven while evaporating the solvent under a nitrogen stream. The temperature conditions of the vacuum dryer should be adjusted as appropriate depending on the solvent used. The curing temperature and curing time should also be set to conditions suitable for the resin being used.

[0094] When using a flat porous support layer, a film of a constant thickness is formed on the support layer using a blade, die coater, bar coater, or spin coater. If necessary, a base layer can be prepared on the porous support layer beforehand, and then the film can be formed on the base layer. As a method for forming the base layer, a method known to those skilled in the art can be used. For example, one of the above-mentioned substances may be applied to the porous support layer as the substance for forming the base layer, and then heated to cure the substance. Alternatively, the above-mentioned mixed slurry can be supported on the support layer by impregnation, suction, pressurization, etc., to form the film. After that, the solvent is removed in a vacuum dryer, and then the resin is cured at a predetermined curing temperature for a predetermined curing time, or the resin is cured in an inert oven while the solvent is evaporated under a nitrogen stream to obtain an organic-inorganic hybrid film.

[0095] When using a hollow fiber porous support layer, the above-mentioned mixed slurry is supported on the support layer by methods such as immersion, impregnation, suction, or pressurization to form the film. If necessary, a base layer can be prepared on the porous support layer beforehand, and the film can then be formed on the base layer. As a method for forming the base layer, methods known to those skilled in the art can be used. For example, one of the above-mentioned substances may be applied to the porous support layer as the substance for forming the base layer, and then heated to cure the substance. After film formation, the solvent is removed in a vacuum dryer, and then the film is cured at a predetermined curing temperature for a predetermined curing time, or the resin is cured in an inert oven while volatilizing the solvent under a nitrogen stream to obtain an organic-inorganic hybrid film. The temperature conditions and nitrogen flow conditions of the vacuum dryer or inert oven should be adjusted as appropriate depending on the solvent used. The curing temperature and curing time should also be set to conditions suitable for the resin being used.

[0096] When using silicone rubber cured from polyorganosiloxane as the matrix resin, the inorganic filler is usually mixed with the polyorganosiloxane before curing. The means for curing the curable polyorganosiloxane are not particularly limited, and conventionally known methods can be employed. However, from the viewpoint of productivity, it is preferable to have a method that allows for stable mixing of inorganic fillers and storage after mixing in the atmosphere. In this respect, types that cure by addition reaction, ultraviolet light, radiation, or electron beam irradiation are desirable, and the use of an addition reaction is particularly preferable because it does not require atmospheric control during curing and is simple.

[0097] Here, the temperature for drying the inorganic filler before mixing the matrix resin and the inorganic filler is usually 100°C or higher, preferably 120°C or higher, more preferably 150°C or higher, even more preferably 200°C or higher, and usually 300°C or lower. The drying time is usually 3 hours or more, preferably 5 hours or more, more preferably 8 hours or more, even more preferably 12 hours or more, and usually 48 hours or less, preferably 30 hours or less, and more preferably 20 hours or less. When the drying temperature and time are within this range, moisture in the zeolite can be sufficiently removed in an economical amount of time.

[0098] The solvent used for film formation is not particularly limited as long as it is a solvent in which the matrix resin or the raw materials of the matrix resin are soluble. Toluene, hexane, ethyl acetate, methyl ethyl ketone, N-methylpyrrolidone, etc., can be used, but a solvent with good dispersibility of inorganic fillers is preferred. Since the matrix resin or the raw materials of the matrix resin are mostly hydrophobic, while the surface of inorganic fillers such as zeolites is hydrophilic, a solvent with moderate polarity, such as ethyl acetate or methyl ethyl ketone, is preferred.

[0099] The ratio of solvent to inorganic filler varies depending on the amount of inorganic filler and the type of resin, but it is preferable to adjust the amount of solvent so that the viscosity is suitable for film formation, depending on the film formation method.

[0100] <Solid paste> In one aspect of the present invention, a method for producing an organic-inorganic hybrid film includes a kneading step of kneading a matrix resin and the inorganic filler together, and a dilution step of mixing a solvent with the mixture obtained in the kneading step to dilute it and obtain a dispersion, wherein in the curing step described later, it is preferable to use the dispersion obtained in the dispersion step.

[0101] [Mixing process] In one aspect of the present invention, the kneading step is a step of solid kneading a matrix resin with a gas-selective inorganic filler. In this specification, solid kneading has the meaning generally understood by those skilled in the art, and means, for example, the operation of kneading a matrix resin and an inorganic filler under conditions in which at least a portion of the matrix resin is not dissolved in the solvent, but is not limited thereto. In the mixing process, solid kneading applies high shear force to the inorganic filler, causing aggregated secondary particles to disperse as primary particles, thereby improving the dispersibility of the inorganic filler. Conventionally, when a composition containing resin and particles is manufactured by solid kneading, a large amount of resin is adsorbed onto the particle surface, coating the particles, which can prevent the composition from exhibiting properties derived from the particles, such as conductivity and heat transfer. However, in the present invention, since the matrix resin has a certain degree of gas permeability, even when the inorganic filler particles are coated in the organic-inorganic hybrid membrane, the gas permeability and separation performance derived from the inorganic filler are fully exhibited.

[0102] In the kneading process, the mixing ratio of the matrix resin and the inorganic filler can be adjusted as appropriate, and it is preferable to adjust it to achieve the desired content of the inorganic filler as described above. Furthermore, the mixing ratio of the matrix resin and the inorganic filler may be adjusted during the kneading process so that the viscosity of the resulting mixture falls within a desired numerical range. By adjusting the viscosity of the resulting mixture, the shear force applied to the inorganic filler during the kneading process can be adjusted, thereby further improving the dispersibility of the inorganic filler. For example, the kneading process may yield a mixture with a viscosity of preferably 30 Pa·s or higher, more preferably 40 Pa·s or higher, and even more preferably 50 Pa·s or higher. The upper limit of the viscosity of the resulting mixture is not particularly limited from the viewpoint of applying a high shear force to the inorganic filler. For example, from the viewpoint of reducing the load on the equipment used in the kneading process, the kneading process may yield a mixture with a viscosity of preferably 500 Pa·s or less, more preferably 300 Pa·s or less. In this specification, viscosity refers to the viscosity measured at 25°C using a cone-plate viscometer.

[0103] Methods for achieving a solid consistency during the mixing process include using mixers, bead mills / ball mills, twin-screw mixers, triple-roll mixers, and rotary / revolving mixers. Additionally, during the mixing process, additives such as hardening agents may be added, provided that the shear force applied to the inorganic filler is not reduced excessively.

[0104] [Dilution process] In one embodiment of the present invention, the dilution step is a step of mixing a solvent with the mixture obtained by the kneading step. The mixture obtained by the kneading step may have high viscosity, making it difficult to form a film. However, by performing the dilution step, the viscosity of the mixture obtained by the kneading step, in which primary particles of inorganic filler are dispersed, can be adjusted, making it easier to form a film.

[0105] The solvent is not particularly limited as long as it is a solvent in which the matrix resin or the raw materials of the matrix resin are soluble. Toluene, hexane, ethyl acetate, methyl ethyl ketone, N-methylpyrrolidone, etc., can be used, but a solvent that has good dispersibility of the inorganic filler is preferred. Since the matrix resin or the raw materials of the matrix resin are mostly hydrophobic, while the surface of inorganic fillers such as zeolites is hydrophilic, a solvent with moderate polarity such as ethyl acetate or methyl ethyl ketone is preferred.

[0106] The ratio of solvent to inorganic filler varies depending on the amount of inorganic filler and the type of resin, but it is preferable to adjust the amount of solvent so that the viscosity is suitable for film formation, depending on the film formation method.

[0107] Methods for mixing a solvent into a mixture include conventional stirring and kneading, as well as the use of ultrasonic crushing and dispersion, and rotary / revolving mixers. Furthermore, additives such as curing agents may be added to the mixture during the dilution process.

[0108] [Dispersion process] In one aspect of the present invention, the dispersion step refers to the step of dispersing an inorganic filler in a matrix resin and, if necessary, a solvent. Specifically, after thoroughly drying the inorganic filler, the inorganic filler is thoroughly mixed with the matrix resin dissolved in a solvent, or the raw material of the matrix resin before polymerization and curing without a solvent, and after the inorganic filler is thoroughly dispersed, if a resin requiring a curing agent is used, the curing agent is further added and mixed well to disperse the inorganic filler. At this time, it is also possible to disperse the inorganic filler in the solvent first, then add the matrix resin and mix well again to disperse the inorganic filler. Methods for dispersing the inorganic filler include stirring with a conventional mixer, bead mill, ball mill, etc., kneading with a twin-screw kneader or three-roll kneader, etc., as well as using ultrasonic crushing and dispersion, and rotating / revolving mixers. Furthermore, the dispersion step includes the kneading step and the dilution step.

[0109] The solvent is not particularly limited as long as it is a solvent in which the matrix resin or the raw materials of the matrix resin are soluble. Toluene, hexane, ethyl acetate, methyl ethyl ketone, N-methylpyrrolidone, etc., can be used, but a solvent that has good dispersibility of the inorganic filler is preferred. Since the matrix resin or the raw materials of the matrix resin are mostly hydrophobic, while the surface of inorganic fillers such as zeolites is hydrophilic, a solvent with moderate polarity such as ethyl acetate or methyl ethyl ketone is preferred.

[0110] [Casting Process] The casting process involves supporting the dispersion of inorganic filler, matrix resin, and solvent obtained in the dispersion process onto a flat or curved surface. Examples of flat or curved surfaces include the inner surface of a container such as a petri dish, the upper surface of a release film, the upper surface of a smooth plate such as a release-treated glass plate if necessary, the inner or outer surface of a porous support layer, or the upper surface of a base layer formed on a porous support layer. Furthermore, the material may be applied, supported, and cast by methods such as a die coater, blade or bar coater, spin coater, immersion, immersion and suction, on a smooth plate such as a Teflon® petri dish, a release film, or a glass plate that has been treated for release as needed, or on a porous support layer (the base layer may be formed on a porous support layer). As for the method of application or support, application by a die coater, blade or bar coater, or spin coater is preferred, with die coaters, blades or bar coaters being more preferred, and die coaters or blades being particularly preferred.

[0111] [Curing process] In film formation, after the casting process, the solvent is removed, followed by a curing process to harden the matrix resin. In the curing process, a pressure curing process is preferably performed, in which the organic-inorganic hybrid film is hardened under pressure. By hardening the resin under pressure, a void-free film can be created even with a large amount of zeolite filling.

[0112] There are various methods for applying pressure in the pressure curing process, but it is preferable to apply pressure while heating. Furthermore, a preferred method for applying pressure while heating is to use a hot press, vacuum hot press, vacuum laminating device, double belt press, etc., to apply pressure to the film while heating and curing it. The pressure is typically 1 MPa or higher, preferably 2 MPa or higher, more preferably 3 MPa or higher, even more preferably 4 MPa or higher, and particularly preferably 5 MPa or higher, and typically 30 MPa or lower, preferably 20 MPa or lower, more preferably 10 MPa or lower, and even more preferably 8 MPa or lower. When the pressure is within the above range, a film can be obtained in which there are no voids between the zeolite, inorganic filler and matrix resin, and a large amount of zeolite is packed in, without destroying the pores of the zeolite in the organic-inorganic hybrid film. The heating temperature and heating time can be appropriately determined according to the curing conditions of the matrix resin used, but the heating time under pressure is usually 1 minute or more, preferably 5 minutes or more, more preferably 10 minutes or more, and usually 2 hours or less, preferably 1 hour or less. Within this range, a film without voids can be efficiently produced.

[0113] [Underlying layer formation process] In one aspect of the present invention, the base layer formation step is a step of forming a base layer on a porous support layer before the casting step. As a method for forming the base layer, a method known to those skilled in the art can be used. For example, a method may be used in which any of the above-mentioned substances is applied to the porous support layer as the substance for forming the base layer, and then heated to harden the substance.

[0114] <Gas Separation and Concentration Methods> An organic-inorganic hybrid membrane according to one aspect of the present invention can separate and concentrate a gas mixture. Examples of gas mixtures used in the gas separation and concentration method of the present invention include those containing at least one component selected from carbon dioxide, hydrogen, oxygen, nitrogen, methane, ethane, ethylene, propane, propylene, n-butane, isobutane, 1-butene, 2-butene, isobutene, sulfur hexafluoride, helium, carbon monoxide, nitric oxide, and water. Of the components of the gas mixture containing the gas, gas components with high permeance (hereinafter sometimes referred to as gas permeability) permeate through the organic-inorganic hybrid membrane and are separated and concentrated, while gas components with low gas permeability are concentrated on the supply gas side.

[0115] Furthermore, the gas mixture is more preferably one that contains at least two of the above components. In this case, the two components are preferably a combination of a component with high gas permeability and a component with low gas permeability.

[0116] One embodiment of the present invention is preferably used for the separation and concentration of CO2, H2, oxygen, and nitrogen, and is particularly preferred for the separation and concentration of CO2.

[0117] CO2 separation and concentration methods include the removal of carbon dioxide from natural gas (CO2, CH4 mixture), CO2 recovery from landfill gas (CO2, CH4 mixture), CO2 recovery from artificial fermentation gas (CO2, CH4 mixture), and CO2 recovery from combustion exhaust gas (CO2, N2 mixture) from thermal power plants, etc.

[0118] Examples of hydrogen separation and concentration include hydrogen recovery in the petroleum refining industry, hydrogen recovery and purification (H2, CO, CO2, hydrocarbon mixtures) in various reaction processes in the chemical industry, and the production of high-purity hydrogen for fuel cells. Hydrogen for fuel cells is obtained by the steam reforming reaction of methane, and requires the separation of hydrogen from a mixed gas of hydrogen, carbon monoxide, methane, and water.

[0119] In addition, oxygen separation and concentration can be used to produce oxygen-enriched gas from air (for medical and combustion purposes, etc.), and it is also suitably used to produce nitrogen-enriched gas from air through nitrogen separation and concentration (for explosion prevention, oxidation prevention, etc.). A known method can be used for separating the gases. A pressure difference is created between the gas supply side and the gas permeate side of the membrane, allowing the easily permeable gas from the supply side mixed gas to permeate to the permeate side. At this time, the gas supply side mixed gas may be pressurized, the permeate side may be depressurized using a vacuum pump or the like, or both may be used.

[0120] The pressure difference between the gas supply side and the permeate side should ideally be set to the optimal pressure for the applied process, but is typically 0.01 MPa or higher, preferably 0.05 MPa or higher, more preferably 0.08 MPa or higher, even more preferably 0.1 MPa or higher, and typically 20 MPa or lower, preferably 10 MPa or lower, more preferably 5 MPa or lower, even more preferably 1 MPa or lower, even more preferably 0.5 MPa or lower, and particularly preferably 0.2 MPa or lower.

[0121] In one embodiment of the present invention, a sweep gas may be used in the gas separation and concentration method. The sweep gas method involves flowing some gas through the permeate side and recovering the gas that has permeated the membrane. The sweep gas pressure is usually atmospheric pressure, but there are no particular restrictions. It is usually 10 MPa or less, preferably 5 MPa or less, more preferably 1 MPa or less, even more preferably 0.5 MPa or less, particularly preferably 0.1 MPa or less, and most preferably 0.05 MPa or less, with a lower limit of usually 0.0 MPa or more.

[0122] In a gas separation method according to one embodiment of the present invention, the temperature of the supply gas and membrane may be set to the optimal temperature for each process, but is usually 100°C or lower, preferably 80°C or lower, more preferably 50°C or lower, even more preferably 40°C or lower, and is usually -30°C or higher, preferably -15°C or higher, more preferably 0°C or higher, even more preferably 5°C or higher, particularly preferably 10°C or higher, and most preferably 20°C or higher. [Examples]

[0123] The present invention will be described in more detail below based on examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. The method for preparing, measuring, and evaluating samples in this invention is as follows.

[0124] [Powder X-ray Diffraction (XRD) Measurement Method] XRD measurements were performed under the following conditions. Equipment: BRUKER D2 PHASER X-ray source: Cu-Kα ray Output settings: 30kV·10mA Divergence slit: 0.3° Incident solar slit: 2.5° Solar slit on the light-receiving side: 2.5° Detection section opening angle: 5.69° Ni filter: 2.5% Diffraction peak position: 2θ (diffraction angle) Measurement range: 2θ = 5~50° Scan speed: 0.05° (2θ / sec)

[0125] [Method for measuring the SiO2 / Al2O3 molar ratio] The SiO2 / Al2O3 molar ratio was determined by XRF analysis after creating a calibration curve using ICP analysis and XRF. After heating and dissolving the zeolite sample in an aqueous hydrochloric acid solution, the content (mass %) of silicon and aluminum atoms was determined by ICP analysis. Then, a calibration curve was created between the fluorescence X-ray intensity of the analyte elements in standard samples and the atomic concentration of the analyte elements. Using this calibration curve, the content (mass %) of silicon and aluminum atoms in the zeolite sample was determined by XRF. ICP analysis was performed using a ULTIMA 2C manufactured by Horiba, Ltd. XRF measurements were performed using an EDX-700 manufactured by Shimadzu Corporation or a Supermini200 X-ray fluorescence analyzer manufactured by Rigaku Corporation.

[0126] [Method for measuring average particle size] The particle size of the inorganic filler used in the organic-inorganic hybrid membrane was determined by thoroughly dispersing the synthesized powder to create a sample, imaging it with a JEOL scanning electron microscope (JSM-6010LV) at an acceleration voltage of 10kV, and then analyzing the image of 30 arbitrarily selected particles using Mac-View, an image analysis-based particle size distribution measurement software from Mountec Co., Ltd. The particle size was determined, and the arithmetic mean of these particle sizes was used as the average particle size. In the case of secondary particles formed by the aggregation of small crystalline particles, this refers to the secondary particle size. The particle size of the inorganic filler in the obtained organic-inorganic hybrid film was determined by photographing a cross-section of the organic-inorganic hybrid film obtained by freeze-rupture using a FE-SEM Hitachi:S-4500 at an acceleration voltage of 10kV. The particle size of 30 arbitrarily selected inorganic filler particles visible in the cross-section was analyzed using Mac-View, an image analysis type particle size distribution measurement software manufactured by Mountec Co., Ltd., to determine the particle size, and the arithmetic mean of these particle sizes was taken as the average particle size. In all methods, the particle diameter is defined as the diameter of a circle (equivalent diameter) that has an area equal to the projected area of ​​the particle.

[0127] [Method for measuring the mean circularity coefficient] The particle size of the inorganic filler used in the organic-inorganic hybrid membrane was determined by thoroughly dispersing the synthesized powder to prepare a sample, imaging it with a JEOL scanning electron microscope JSM-6010LV at an acceleration voltage of 10kV, and analyzing the image of 30 arbitrarily selected particles using Mac-View, an image analysis-based particle size distribution measurement software from Mountec Co., Ltd., to determine the circularity coefficient. The arithmetic mean of these circularity coefficients was used as the average circularity coefficient. For secondary particles formed by the aggregation of small crystalline particles, the average of the circularity coefficients of the secondary particles was used as the average circularity coefficient. The circularity coefficient used here is 4πS / L, where S is the area of ​​the two-dimensional projection image of the inorganic filler particles used and L is the perimeter of the particles. 2 This is the value represented by [formula].

[0128] [Method for measuring particle size distribution] The particle size distribution of the inorganic filler used in the organic-inorganic hybrid film was measured under the following conditions. • Device name: Laser diffraction / scattering particle size distribution analyzer LA-950 (manufactured by Horiba, Ltd.) ·Measurement method: Mie scattering theory • Measurement range: 0.01 to 3000 μm • Light source: Semiconductor laser (650nm) • Detector: Ring-shaped silicon photodiode • Dispersing solvent: Water A dispersion of inorganic filler, prepared using an ultrasonic cleaner, was dropped into a flow cell filled with water, and the particle size distribution was measured within the range of appropriate light intensity. The peak particle size was determined from the obtained volume-based particle size distribution.

[0129] [Single-component gas permeation test] The single-component gas permeation test was performed using the constant volume / valuable pressure method with the apparatus schematically shown in Figure 1. The permeation side of the membrane (the lower side of the membrane in Figure 1) was reduced to 13 Pa (absolute pressure) or less, and gas was supplied at a constant pressure of approximately 35 kPa (G). The permeation coefficient was determined from the rate of pressure increase on the permeation side when the pressure difference between the supply side and the permeation side of the membrane was 0.1 MPa. The temperature of the constant temperature bath was set to 35°C, and the permeation coefficient of the membrane at 35°C was determined.

[0130] Gas was supplied from the gas cylinder 18, and the manual valve 17 and the valve 13 on the secondary side of the mass flow controller 5 were opened to supply gas through the mass flow controller 5. After filling the supply gas reservoir 3 with approximately 35 kPa(G) of gas for the permeation test, valve 12 was closed and valve 11 was opened to supply gas to the membrane. At this time, valve 14 was open and valve 15 was closed. To ensure that the supply gas pressure remained constant, a fixed amount of gas was supplied through the mass flow controller 5 with valve 13 open, and the pressure was kept constant by the exhaust valve 6.

[0131] The permeability coefficient was calculated from the pressure increase rate measured by pressure gauge 7 after it reached a steady state, as well as the volume from the bottom of the membrane to valve 12, the membrane thickness, and the membrane area. For the gas reservoir for the permeate gas, the internal volume was measured from the amount of water after filling it with water, and for the piping section, the volume was calculated from the pipe length and inner diameter to pre-calculate the volume from the bottom of the membrane to valve 12. An absolute pressure transducer (MKS Baratron (registered trademark) 0-10 Tor (626C11TBE)) was used as the pressure gauge.

[0132] For self-supporting films, the film thickness was calculated using a Digimatic standard outside micrometer (MDC-25M, Mitutoyo Corporation). Measurements were taken at the center of the film and at three points slightly inward from the edge, selected evenly along the circumference, for a total of four points, and the average was calculated from these four points. The area of ​​the portion through which the gas permeates was defined as the film area. In the organic-inorganic hybrid membrane composite, the cross-section of the organic-inorganic hybrid membrane composite obtained by freeze-rupture was photographed using a scanning electron microscope, and the thickness of the separation-related layer, which is the part other than the porous support layer, was calculated by taking the arithmetic mean of multiple locations and defined as the thickness. The gases used were carbon dioxide (99.9% purity, manufactured by Toho Oxygen Industries Co., Ltd.), methane (99.999% purity, manufactured by Japan Fine Products Co., Ltd.), and hydrogen (99.99% purity, manufactured by Showa Denko Gas Products Co., Ltd.).

[0133] (Membrane pretreatment) As a pretreatment of the membrane before the gas permeation test, the membrane 1 set in the separation membrane module 2 was heated in a constant temperature bath at 80°C or higher for 2 hours while reducing the pressure on both the supply line and the permeation line. After 2 hours, the temperature of the constant temperature bath was lowered to 35°C and held there for 1 hour to remove water and gas dissolved or adsorbed on the membrane.

[0134] [Measurement of glass transition temperature] The glass transition temperature was measured using a differential scanning calorimeter (DSC) or a thermomechanical analyzer (TMA). The glass transition temperature was measured using a differential scanning calorimeter DSC6220 (Au sensor) manufactured by Hitachi High-Tech Science Corporation. Approximately 10 mg of resin sample was placed in an aluminum sample container and sealed. The sample was heated from room temperature to 150°C at a heating rate of 10°C / min under a nitrogen flow of 50 mL / min. After maintaining the temperature for 5 minutes, it was removed from the furnace and rapidly cooled in liquid nitrogen. The sample was then heated again from -150°C to 150°C at a rate of 10°C / min. The inflection point of the DSC data obtained during the second heating cycle was defined as the glass transition temperature. The glass transition temperature was determined using a thermomechanical analyzer (TMA / SS6100) manufactured by SII Nanotechnology, Inc., by analyzing the change point of the thermal expansion coefficient. The sample shape was 4 mm in width and 20 mm in distance between chucks. A tensile load of 49 mN was applied, and the temperature was increased from 30°C to 325°C at a heating rate of 10°C / min before measurement.

[0135] [Bending Test Method] A SUS tube of a specific outer diameter was placed in the center of a flat membrane placed on a flat surface. The membrane was then folded back once at a 180° angle along the tube, and then returned to its original position.

[0136] [Measurement of air permeability] A self-supporting membrane consisting of an organic-inorganic hybrid membrane composite, or an organic-inorganic hybrid membrane alone, is set in a module with a 1 cm diameter circular shape exposed. One end of the module is connected to a 5 kPa vacuum line, and the airflow rate is measured using a mass flow meter installed between the vacuum line and the module, and the air permeability [L / (m³] is measured. 2The following values ​​were calculated: (at 0°C and 1 atm). A Lintec MM-2100M mass flow meter for air gas with a maximum flow rate of 20 mL / min (at 0°C and 1 atm) was used for measurement. When the flow rate exceeded the maximum flow rate of the Lintec MM-2100M, a KOFLOC 8300 mass flow meter for N2 gas with a maximum flow rate of 500 ml / min (at 20°C and 1 atm) was used. When setting the organic-inorganic hybrid membrane supported on the porous support layer into the module, the side with the porous support layer was designated as the reduced pressure side, i.e., the permeable side, and the side where the organic-inorganic hybrid membrane was formed was designated as the atmospheric pressure side or the pressurized side, i.e., the gas supply side.

[0137] [Synthesis of gas-selective inorganic fillers] Zeolites (Z-1) to (Z-5) were synthesized as inorganic fillers with gas selectivity.

[0138] (Synthesis of zeolite (Z-1)) Sodium hydroxide, potassium hydroxide, aqueous solution of N,N,N-trimethyl-1-adamantaammonium hydroxide (TMADAOH) (manufactured by Seichem Co., Ltd.), aluminum hydroxide hydrate (manufactured by Aldrich Co., Ltd.), and silica aqueous dispersion sol were sequentially added to a container. N,N,N-trimethyl-1-adamantaammonium hydroxide was used as a structural controlling agent (SDA). The composition ratio of the resulting mixture was 1.0SiO2 / 0.033Al2O3 / 0.1NaOH / 0.06KOH / 0.07TMADAOH / 20H2O. Subsequently, 2% by mass of CHA-type zeolite powder, prepared in the same manner as in Japanese Patent Application Publication No. 2016-104486, was added to the mixture relative to the SiO2 in the mixture and mixed well. The resulting reaction mixture was then placed in a pressure vessel and hydrothermally synthesized in an oven at 160°C for 48 hours while rotating at 15 rpm. After the reaction was complete, the mixture was filtered by suction, the resulting solid was washed with water, dried overnight in a constant temperature bath at 100°C, and then calcined at 550°C for 6 hours under an air atmosphere to thermally decompose the SDA and obtain zeolite (Z-1). Powder X-ray diffraction was measured on the obtained zeolite (Z-1) to confirm that zeolite (Z-1) is a CHA-type zeolite. Since zeolite (Z-1) is a CHA-type zeolite, it is an 8-membered oxygen ring zeolite, and the framework density (FD) when all T elements are Si is calculated. Si The ratio is 15.1. The average particle size of the obtained zeolite (Z-1) was 0.6 μm as observed by SEM, and the SiO2 / Al2O3 ratio was found to be 25.

[0139] (Synthesis of zeolite (Z-2)) Tetraethylammonium bromide (TEABr) manufactured by Tokyo Chemical Industry Co., Ltd. was used as the structural controlling agent (SDA), and colloidal silica (Ludox® AS-40 Sigma-Aldrich) was used as the silica source. The composition ratio of the mixture was 1.0SiO2 / 0.1388Al2O3 / 0.53NaOH / 0.72TEABr / 54H2O. The reaction mixture was prepared in the same manner as in the synthesis of zeolite (Z-1), except that MWF-type zeolite, prepared in the same manner as in Comparative Example 1 of Japanese Patent Application No. 2020-53876, was added to the mixture at a concentration of 2% by mass relative to SiO2 as a seed crystal. The resulting reaction mixture was placed in a pressure vessel and aged at room temperature for 10 days while rotating at 15 rpm, followed by hydrothermal synthesis at 135°C for 6 days. After the reaction was complete, the resulting solid was filtered by suction, washed with demineralized water, dried overnight in a constant temperature bath at 100°C, and then calcined at 550°C for 6 hours under an air atmosphere to thermally decompose the SDA and obtain zeolite (Z-2). Powder X-ray diffraction was measured on the obtained zeolite (Z-2), confirming that zeolite (Z-2) is an MWF-type zeolite. Since zeolite (Z-2) is an MWF-type zeolite, it is an 8-membered oxygen ring zeolite, and the framework density (FD) when all T elements are Si is calculated. Si ) is 16.1. The SiO2 / Al2O3 ratio of the obtained zeolite (Z-2) was determined to be 6 using a Rigaku Supermini200 X-ray fluorescence analyzer, and SEM observation revealed an average particle size of 1 μm.

[0140] (Synthesis of zeolite (Z-3)) In a container, 0.4 g of sodium hydroxide (manufactured by Kishida Chemical Co., Ltd.), 0.75 g of aluminum hydroxide (manufactured by Kyoward, Al2O3 54.3%), and 7.2 g of water were mixed. 6 g of silica sol (manufactured by Nissan Chemical, Snowtex 40) was added, and the mixture was stirred for 1 hour. This mixture was placed in a pressure-resistant container and heated in an 80°C oven for 2 hours while standing. After cooling to room temperature, 7.1 g of water, 16.9 g of a 25% by mass aqueous solution of N,N,N-trimethyl-1-adamantaammonium hydroxide (TMADAOH, manufactured by Seichem Co., Ltd.) as a structural controlling agent (SDA), and 9 g of silica sol (Nissan Chemical Corporation, Snowtec 40) were added to the mixture and stirred. The composition ratio of the resulting mixture was 1.0SiO2 / 0.04Al2O3 / 0.1NaOH / 0.2TMADAOH / 20H2O. Furthermore, 0.12 g of CHA-type zeolite (Z-1) was added as a seed crystal and stirred. This mixture was placed in a pressure vessel and heated in a 160°C oven for 4 days in a static state to perform hydrothermal synthesis. After the reaction was completed, the obtained solid was suction filtered, washed with deionized water, dried in a thermostatic bath at 100 °C overnight, and calcined at 550 °C for 6 hours in an air atmosphere to thermally decompose SDA, thereby obtaining zeolite (Z-3). As a result of measuring the powder X-ray diffraction of the obtained zeolite (Z-3), it was confirmed that zeolite (Z-3) is a CHA-type zeolite. Further, as a result of SEM observation, the average particle diameter was 7 μm. Since zeolite (Z-3) is a CHA-type zeolite, it is an oxygen 8-membered ring zeolite, and when all T elements are Si, the framework density (FD Si ) is 15.1. The SiO2 / Al2O3 ratio of the obtained zeolite (Z-3) was 22.

[0141] (Preparation of Zeolite (Z-4)) 10 g of zeolite (Z-1) dried at 150 °C for 12 hours or more was put into a 500 mL flask containing 100 g of hexamethyldisiloxane (HMDS) measured, and while stirring, heated under reflux at 110 °C for 5 hours in an oil bath. After suction filtration, it was thoroughly washed with acetone and dried to obtain zeolite (Z-4). The SiO2 / Al2O3 ratio of the obtained zeolite (Z-4) was 26.

[0142] (Preparation of Zeolite (Z-5)) Except for using zeolite (Z-2), the surface of zeolite (Z-2) was modified with hexamethyldisiloxane in the same manner as the preparation method of zeolite (Z-4) to obtain zeolite (Z-5). The SiO2 / Al2O3 ratio of the obtained zeolite (Z-5) was 7. <​​​​​​​0.10 g of 184 Silicone Elastomer Curing Agent (manufactured by Dow Toray Industries, Inc.) (hereinafter sometimes referred to as Silpot curing agent) was added and mixed thoroughly. 1.0 g of the resulting liquid was dropped into a 30 mm inner diameter Teflon® petri dish, and the Teflon® petri dish was placed in a vacuum dryer. After the hexane was evaporated, the temperature was raised to 80°C and held for 30 minutes. Subsequently, the Teflon® petri dish was placed in a circulating constant temperature bath and held at 80°C for 5 hours to cure the silicone resin. The matrix resin consisting of the cured product of Silpot main agent and Silpot curing agent will hereinafter be referred to as matrix resin (P-1). A silicone resin film (M-1) was obtained by peeling the film from a Teflon® petri dish. The film thickness was 135 μm. The glass transition temperature of the silicone resin film (M-1) was measured using DSC and found to be -126°C. The silicone resin film (M-1) was measured using the above evaluation method. At 35°C, the CO2 permeability coefficient was 2500 Barrer, and the CH4 permeability coefficient was 800 Barrer. The CO2 / CH4 separation coefficient of the silicone resin film (M-1) was 3.1.

[0144] (Comparative Example 2) In a four-necked flask equipped with a nitrogen gas inlet tube, a condenser, and a stirrer, 311 g (1.06 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 324 g (1.06 mol) of 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, and 3700 g of N-methylpyrrolidone were added and heated and stirred at 80°C for 8 hours to obtain a polyimide precursor-containing composition (I-1) containing 25% by mass of the polyimide precursor. Composition I-1 containing a polyimide precursor was diluted with N-methyl-2-pyrrolidone to adjust the polyimide precursor content to 20% by mass. The resulting mixture was applied to glass by spin coating and dried and fired at 330°C for 30 minutes to obtain a polyimide resin film (M-2). The thickness of the resulting film was 8 μm. The matrix resin obtained by heating, firing, and curing the polyimide precursor-containing composition (I-1) is hereinafter referred to as the matrix resin (P-2). The glass transition temperature of the polyimide resin film (P-2) was measured using a TMA and found to be 316°C.

[0145] (Example 1) 0.33 g of zeolite (Z-1), dried overnight at 150°C, was mixed with 5.04 g of hexane and dispersed using an ultrasonic cleaner. Then, 0.50 g of Silpot main agent was added and thoroughly stirred, and the zeolite (Z-1) was further dispersed using an ultrasonic cleaner. Subsequently, 0.056 g of Silpot curing agent was added and stirred to mix. The resulting mixture (hereinafter sometimes referred to as the film raw material slurry) was used to produce a film in the same manner as the silicone resin film (M-1), resulting in an organic-inorganic hybrid film (M-3) consisting of matrix resin (P-1) and CHA-type zeolite (Z-1). The film thickness of the organic-inorganic hybrid film (M-3) was 136 μm. The ratio of zeolite (Z-1) to the total mass of the organic-inorganic hybrid film (M-23) was 37.2 wt%. The organic-inorganic hybrid membrane (M-3) exhibited a CO2 permeability coefficient of 11,000 Barrers and a CH4 permeability coefficient of 990 Barrers at 35°C, with an ideal separation coefficient of 11. Compared to the silicone resin membrane (M-1) without zeolite (Z-1), both the permeability coefficient and separation coefficient were higher, demonstrating gas permeation and separation performance exceeding that of the Robeson Upper Bound. The evaluation results are shown in Table 1.

[0146] (Example 2) Using zeolite (Z-4) dried overnight at 150°C, a membrane raw material slurry was obtained by mixing 0.53 g of zeolite (Z-4), 1.41 g of hexane, 0.503 g of Silpot main agent, and 0.051 g of Silpot curing agent in the same manner as in Example 1. Except for using this slurry, an organic-inorganic hybrid membrane (M-4) consisting of a matrix resin (P-1) and CHA-type zeolite (Z-4) was obtained in the same manner as in Example 1. The proportion of zeolite (Z-4) in the organic-inorganic hybrid membrane (M-4) was 48.9 wt%, and the film thickness was 167 μm. At 35°C, the CO2 permeability coefficient was 10000 Barrer, the CH4 permeability coefficient was 720 Barrer, and the separation coefficient was 15. Compared to the silicone resin membrane (M-1) without added zeolite (Z-4), both the permeability coefficient and separation coefficient were higher, and as shown in Figure 2, it exhibited gas permeation and separation performance exceeding the Robeson Upper Bound. The evaluation results are shown in Table 1.

[0147] (Example 3) 1.50 g of zeolite (Z-1) dried overnight at 150°C, 2.02 g of hexane, 1.00 g of Silpot main agent, and 0.101 g of Silpot curing agent were mixed in the same manner as in Example 1 to obtain a film raw material slurry. The film raw material slurry was dripped in a circular shape with a diameter of approximately 3 cm onto a 10 cm x 10 cm, 0.5 mm thick Teflon® sheet attached to an aluminum plate, and the solvent was completely evaporated at room temperature using a vacuum dryer. After removing this sample, it was sandwiched between aluminum plates with Teflon® sheets attached in the same manner, and pressurized using an IMC-180C-C small-scale heated manual press manufactured by Imoto Seisakusho until the pressure gauge showed 10 MPa. The pressure gauge reading was maintained at 10 MPa, and the film was held at 78°C for 10 minutes, then the temperature was raised to 100°C, and it was cured under pressure at 100°C for 30 minutes to obtain an organic-inorganic hybrid film (M-5) consisting of a matrix resin (P-1) and CHA-type zeolite (Z-1). The proportion of zeolite in the organic-inorganic hybrid film (M-5) was 57.6 wt%, and the film thickness was 436 μm. At 26°C, the CO2 permeability coefficient was 7100 Barrer, the CH4 permeability coefficient was 390 Barrer, and the separation coefficient was 18. Compared to the silicone resin film (M-1) without zeolite (Z-1), both the permeability coefficient and separation coefficient were higher, demonstrating gas permeation and separation performance exceeding the Robeson Upper Bound. The evaluation results are shown in Table 1.

[0148] (Example 4) An organic-inorganic hybrid membrane (M-6) consisting of a matrix resin (P-1) and CHA-type zeolite (Z-3) was obtained in the same manner as in Example 1, except that a membrane raw material slurry was used, which was obtained by mixing 0.34 g of zeolite (Z-3) dried overnight at 150°C, 2.22 g of ethyl acetate, 0.310 g of Silpot main agent, and 0.034 g of Silpot curing agent in the same manner as in Example 1. The proportion of zeolite in the organic-inorganic hybrid membrane (M-6) was 49.6 wt%, and the film thickness was 154 μm. The CO2 permeability coefficient at 35°C was 9400 Barrer, the CH4 permeability coefficient was 530 Barrer, and the CO2 / CH4 separation coefficient was 18. Compared to the silicone resin membrane (M-1) without added zeolite (Z-3), both the permeability coefficient and separation coefficient were higher, showing gas permeation and separation performance exceeding the Robeson Upper Bound. Furthermore, although the zeolite content was 49.6 wt%, which is lower than that of the organic-inorganic hybrid membrane (M-5) in Example 3, the CO2 / CH4 separation coefficient was 18, which is equivalent to that of the organic-inorganic hybrid membrane (M-5) in Example 3. A SUS tube with an outer diameter of 1 / 16 inch was placed in the center of the obtained organic-inorganic hybrid membrane (M-6), and a bending test was performed by folding the membrane 180° along the tube and then unfolding it. After that, the gas permeability performance was measured in the same manner as before the bending test. At 35°C, the CO2 permeability coefficient was 9300 Barrer, the CH4 permeability coefficient was 530 Barrer, and the CO2 / CH4 separation coefficient was 17. The performance difference compared to before the bending test was within 2.0%, indicating that the organic-inorganic hybrid membrane (M-6) using a flexible resin (P-1) with a low glass transition temperature, even with 49.6 wt% zeolite content, shows that bending has almost no effect on performance, resulting in a membrane with sufficient flexibility and excellent processability.

[0149] (Comparative Example 3) An organic-inorganic hybrid membrane (M-7) consisting of P-1 and CHA-type zeolite (Z-1) was obtained in the same manner as in Example 1, except that a membrane raw material slurry was used, obtained by mixing 0.126 g of zeolite (Z-1), 2.73 g of hexane, 0.505 g of Silpot main agent, and 0.053 g of Silpot curing agent in the same manner as in Example 1. The proportion of zeolite in the organic-inorganic hybrid membrane (M-7) was 18.4 wt%, and the film thickness was 96.3 μm. The CO2 permeability coefficient at 35°C was 3600 Barrer, the CH4 permeability coefficient was 650 Barrer, and the CO2 / CH4 separation coefficient was 5.5. Although both the permeability coefficient and separation coefficient were higher than those of the silicone resin membrane (M-1) of Comparative Example 1 without the addition of zeolite (Z-1), gas permeation and separation performance exceeding the Robeson Upper Bound was not obtained. The evaluation results are shown in Tables 1 and 2.

[0150] (Comparative Example 4) An organic-inorganic hybrid membrane (M-8) consisting of a matrix resin (P-1) and MWF-type zeolite (Z-2) was obtained in the same manner as in Example 1, except that a membrane raw material slurry was used, which was obtained by mixing 0.335 g of zeolite (Z-2) dried overnight at 150°C, 2.75 g of hexane, 0.501 g of Silpot main agent, and 0.050 g of Silpot curing agent in the same manner as in Example 1. The proportion of zeolite in the organic-inorganic hybrid membrane (M-8) was 37.8 wt%, and the film thickness was 125 μm. The CO2 permeation coefficient at 35°C was 1800 Barrer, the CH4 permeation coefficient was 550 Barrer, and the separation coefficient was 3.2. The permeation coefficient was smaller than that of the silicone resin membrane (M-1) of Comparative Example 1 without the addition of zeolite (Z-2), and the separation coefficient was about the same, showing gas permeation and separation performance significantly below the Robeson Upper Bound. Therefore, it is considered that the mixing of zeolite did not have any effect in the organic-inorganic hybrid membrane (M-8). The evaluation results are shown in Table 1.

[0151] (Comparative Example 5) An organic-inorganic hybrid membrane (M-9) consisting of a matrix resin (P-1) and MWF-type zeolite (Z-5) was obtained in the same manner as in Example 1, except that a membrane raw material slurry was used, which was obtained by mixing 0.554 g of zeolite (Z-5) dried overnight at 200°C, 1.43 g of hexane, 0.50 g of Silpot main agent, and 0.050 g of Silpot curing agent in the same manner as in Example 1. The proportion of zeolite in the organic-inorganic hybrid membrane (M-9) was 50.2 wt%, and the film thickness was 149 μm. The CO2 permeability coefficient at 35°C was 1400 Barrer, the CH4 permeability coefficient was 440 Barrer, and the separation coefficient was 3.2. The permeability coefficient was smaller than that of the silicone resin membrane (M-1) of Comparative Example 1 without the addition of zeolite (Z-5), and the separation coefficient was about the same, showing gas permeability and separation performance significantly below the Robeson Upper Bound. Therefore, it is considered that the mixing of zeolite did not have any effect in the organic-inorganic hybrid membrane (M-9). The evaluation results are shown in Table 1.

[0152] (Comparative Example 6) 0.556 g of zeolite (Z-1) and 1.019 g of N-methyl-2-pyrrolidone were mixed and dispersed in an ultrasonic cleaner for 5 minutes. Then, polyimide precursor-containing composition (I-1) was added and mixed with a stirring bar to obtain a mixture of zeolite (Z-1) and polyimide precursor-containing composition (I-1). An appropriate amount of the obtained mixture was dropped onto a glass substrate and coated using a blade with a gap width of 8 mil to form a film. The glass substrate coated with the mixture was placed in a Yamato Scientific inert oven DN411I and dried and baked at 330°C for 30 minutes under a nitrogen flow of 15 L / min to obtain an organic-inorganic hybrid film (M-10) with polyimide resin P-2 as the matrix resin. The proportion of zeolite in the organic-inorganic hybrid film (M-10) was 35.7 wt%, and the film thickness was 47.3 μm. When this membrane was bent 180° along a 1 / 8-inch pipe, it cracked. Organic-inorganic hybrid membranes (M-10) using P-2, which has a high glass transition temperature, have poor flexibility and are difficult to process.

[0153] [Table 1]

[0154] As shown in Table 1, in Examples 1 to 5, a silicone resin (P-1) with a glass transition temperature of 15°C or less and a gas permeability of 200 Barrer or more in the resin film was used as the matrix resin, and the framework density FD was determined when all T elements were Si. Si In membranes containing 35% or more by mass of CHA-type zeolite with a rating of 15.1, it exhibits higher permeability and separation performance than Robeson Upper Bound.

[0155] On the other hand, as shown in Table 1, in Comparative Examples 4 and 5, FD Si Even when using 16.1 MWF-type zeolite, and even with a zeolite filling amount of 35 wt% or more, the CO2 permeability coefficient is lower than that of a matrix resin-only membrane, and the separation coefficient remains almost unchanged, indicating no effect from the zeolite mixture. Since there is no effect from the zeolite mixture, but no significant increase in the permeability coefficient is observed, it is thought that there is a gap between the matrix resin and the zeolite, and that the zeolite is not ineffective, but rather that the resin is blocking the pores of the zeolite, preventing gas from passing through the pores. From these results, FD Si If the ratio is 15.5 or less, even if the matrix resin partially blocks the surface or interior of the zeolite pores, the large amount of space inside the zeolite ensures that a gas flow path can be secured, and it is thought that an organic-inorganic hybrid membrane that fully exhibits the gas separation performance of the zeolite can be stably obtained.

[0156] [Synthesis of gas-selective inorganic fillers] As inorganic fillers with gas selectivity, the following zeolites were further synthesized.

[0157] (Synthesis of zeolite (Z-6)) 150 g of 1 mol / L NaOH aqueous solution (manufactured by Kishida Chemical Co., Ltd.) and 90 g of 1 mol / L KOH aqueous solution (manufactured by Kishida Chemical Co., Ltd.) were mixed, and 9.4 g of aluminum hydroxide hydrate (manufactured by Kyoward Co., Ltd.) was added and stirred to dissolve it. Then 98 g of water was added and stirred to obtain a clear solution. To this, 88.8 g of N,N,N-trimethyl-1-adamantaammonium hydroxide (TMADAOH) aqueous solution (containing 25% by mass of TMADAOH, manufactured by Seichem Co., Ltd.) was added, followed by 225 g of colloidal silica (Nissan Chemical Co., Ltd. Snowtech-40). Finally, 1.8 g of uncalcined CHA-type zeolite synthesized in the same manner as in Production Example 9 of JP 2016-104486 was added as a seed crystal, and the mixture was stirred for 2 hours to obtain a reaction mixture. TMADAOH was used as a structural controlling agent (SDA). The composition ratio of the resulting reaction mixture is 1.0SiO2 / 0.033Al2O3 / 0.1NaOH / 0.06KOH / 0.07TMADAOH / 20H2O, and the mass of the seed crystal is 2% by mass relative to the SiO2 in the reaction mixture. A 1L Teflon® inner cylinder containing the above reaction mixture was placed in a 1L induction-type autoclave, sealed, and stirred at 100 rpm using an anchor blade. The mixture was heated at 160°C for 48 hours under self-synthesizing pressure. After the predetermined time, the mixture was allowed to cool, the reaction mixture was removed, filtered, washed, and dried at 100°C for more than 5 hours to obtain as-made zeolite crystals. These as-made zeolite crystals were calcined at 550°C for 6 hours in an air atmosphere to thermally decompose SDA and obtain zeolite (Z-6). Powder X-ray diffraction was measured on the obtained zeolite (Z-6) to confirm that zeolite (Z-6) is a CHA-type zeolite. Since zeolite (Z-6) is a CHA-type zeolite, it is an 8-membered oxygen ring zeolite, and the framework density (FD) when all T elements are Si is calculated. Si The ratio was 15.1. The average particle size of the obtained zeolite (Z-6) was 0.7 μm as observed by SEM, and the SiO2 / Al2O3 ratio was found to be 24. The average circularity coefficient was 0.87.

[0158] (Synthesis of zeolite (Z-7)) Zeolite (Z-7) was synthesized in the same manner as Z-6, except that a 200 mL pressure vessel was used as the reaction vessel and the mixture was rotated at 15 rpm in an oven at 160 °C. Zeolite (Z-7) was obtained by calcining to remove SDA. Powder X-ray diffraction was measured on the obtained zeolite (Z-7) to confirm that zeolite (Z-7) is a CHA-type zeolite. Since zeolite (Z-7) is a CHA-type zeolite, it is an 8-membered oxygen ring zeolite, and the framework density (FD) when all T elements are Si is calculated. Si The ratio was 15.1. The average particle size of the obtained zeolite (Z-7) was 1 μm as observed by SEM, and the SiO2 / Al2O3 ratio was found to be 26. The average circularity coefficient was 0.94. The mode diameter in the volume-based particle size distribution of Z-7 was 1.19 μm.

[0159] (Synthesis of zeolite (Z-8)) Zeolite was synthesized in the same manner as Z-7, except that Z-11 before calcination was used as the seed crystal, and Z-8 was obtained by calcining to remove SDA. Powder X-ray diffraction was measured on the obtained zeolite (Z-8) and it was confirmed that zeolite (Z-8) is a CHA-type zeolite. Since zeolite (Z-8) is a CHA-type zeolite, it is an 8-membered oxygen ring zeolite, and the framework density (FD) when all T elements are Si is calculated. Si The ratio was 15.1. The average particle size of the obtained zeolite (Z-8) was 0.8 μm as observed by SEM, and the SiO2 / Al2O3 ratio was found to be 24. The average circularity coefficient was 0.92.

[0160] (Synthesis of zeolite (Z-9)) Zeolite (Z-9) was synthesized in the same manner as Z-7, except that the reaction mixture composition ratio was 1.0SiO2 / 0.033Al2O3 / 0.1NaOH / 0.06KOH / 0.1TMADAOH / 15H2O and hydrothermal synthesis was carried out in an oven at 160°C at 15 rpm for 96 hours. Zeolite (Z-9) was obtained by calcining to remove SDA. Powder X-ray diffraction was measured on the obtained zeolite (Z-9) to confirm that zeolite (Z-9) is a CHA-type zeolite. Since zeolite (Z-9) is a CHA-type zeolite, it is an 8-membered oxygen ring zeolite, and the framework density (FD) when all T elements are Si is calculated. Si The ratio was 15.1. The average particle size of the obtained zeolite (Z-9) was 0.2 μm as observed by SEM, and the SiO2 / Al2O3 ratio was found to be 25. The average circularity coefficient was 0.89. The mode diameter in the volume-based particle size distribution of Z-9 was 0.31 μm.

[0161] (Synthesis of zeolite (Z-10)) Zeolite (Z-10) was synthesized in the same manner as Z-7, except that hydrothermal synthesis was performed by setting the reaction mixture composition ratio to 1.0SiO2 / 0.04Al2O3 / 0.15KOH / 0.2TMADAOH / 20H2O and leaving a 200 ml pressure vessel containing the reaction mixture in an oven at 160°C for 96 hours. Zeolite (Z-10) was obtained by calcining to remove SDA. Powder X-ray diffraction was measured on the obtained zeolite (Z-10) to confirm that zeolite (Z-10) is a CHA-type zeolite. Since zeolite (Z-10) is a CHA-type zeolite, it is an 8-membered oxygen ring zeolite, and the framework density (FD) when all T elements are Si is calculated. Si The ratio was 15.1. The average particle size of the obtained zeolite (Z-10), as observed by SEM, was 5 μm, its shape was cubic, and its average circularity coefficient was 0.77. The SiO2 / Al2O3 ratio was found to be 20. The mode diameter in the volume-based particle size distribution of Z-10 was 7.3 μm.

[0162] (Synthesis of zeolite (Z-11)) Zeolite (Z-11) was synthesized in the same manner as Z-6, except that the composition ratio of the reaction mixture was 1.0SiO2 / 0.033Al2O3 / 0.1NaOH / 0.04KOH / 0.07TMADAOH / 20H2O. Zeolite (Z-11) was obtained by calcining to remove SDA. Powder X-ray diffraction was measured on the obtained zeolite (Z-11) to confirm that zeolite (Z-11) is a CHA-type zeolite. Since zeolite (Z-11) is a CHA-type zeolite, it is an 8-membered oxygen ring zeolite, and the framework density (FD) when all T elements are Si is calculated. Si The ratio was 15.1. The average particle size of the obtained zeolite (Z-11) was 2 μm as observed by SEM, its shape was spherical, and the average circularity coefficient was 0.94. The SiO2 / Al2O3 ratio of the obtained zeolite (Z-11) was found to be 26.

[0163] (Synthesis of zeolite (Z-12)) Zeolite (Z-12) was synthesized in the same manner as Z-10, except that hydrothermal synthesis was performed by placing a 200 ml pressure vessel containing the reaction mixture in a 160°C oven with a reaction mixture composition ratio of 1.0SiO2 / 0.033Al2O3 / 0.4TMADAOH / 20H2O and holding it for 48 hours. Zeolite (Z-12) was obtained by calcining to remove SDA. Powder X-ray diffraction was measured on the obtained zeolite (Z-12) to confirm that zeolite (Z-12) is a CHA-type zeolite. Since zeolite (Z-12) is a CHA-type zeolite, it is an 8-membered oxygen ring zeolite, and the framework density (FD) when all T elements are Si is calculated. Si The ratio was 15.1. The average particle size of the obtained zeolite (Z-12) was 5 μm as observed by SEM, its shape was spherical, and the average circularity coefficient was 0.94. The SiO2 / Al2O3 ratio of the obtained zeolite (Z-12) was found to be 23.

[0164] (Synthesis of zeolite (Z-14)) Zeolite (Z-14) was synthesized in the same manner as Z-8, except that the composition ratio of the reaction mixture was 1.0SiO2 / 0.033Al2O3 / 0.1NaOH / 0.06KOH / 0.07TMADAOH / 100H2O. Zeolite (Z-14) was obtained by calcining to remove SDA. Powder X-ray diffraction was measured on the obtained zeolite (Z-14) to confirm that zeolite (Z-14) is a CHA-type zeolite. Since zeolite (Z-14) is a CHA-type zeolite, it is an 8-membered oxygen ring zeolite, and the framework density (FD) when all T elements are Si is calculated. Si The ratio was 15.1. The average particle size of the obtained zeolite (Z-14) was 6 μm as observed by SEM, its shape was rugby ball-shaped, and its average circularity coefficient was 0.91. The SiO2 / Al2O3 ratio of the obtained zeolite (Z-14) was found to be 25.

[0165] (Synthesis of zeolite (Z-15)) To obtain zeolite (Z-15), 15 g of dried zeolite (Z-7) was added to a solution prepared by adding 5 g of silane coupling agent (KBM-1083, Shin-Etsu Chemical Co., Ltd.) to 100 g of acetone measured in an eggplant flask. The solution was heated under reflux at 55°C for 5 hours with stirring in an oil bath, and after suction filtration, it was thoroughly washed with acetone and dried. The average particle size, SiO2 / Al2O3 ratio, and average circularity coefficient of the obtained zeolite (Z-15) were the same as those of the raw material zeolite (Z-7).

[0166] (Synthesis of zeolite (Z-16)) To obtain zeolite (Z-16), 15 g of dried zeolite (Z-8) was added to a solution prepared by adding 5 g of silane coupling agent (KBM-1083, Shin-Etsu Chemical Co., Ltd.) to 100 g of acetone measured in an eggplant flask. The solution was heated under reflux at 55°C for 5 hours with stirring, and after suction filtration, it was thoroughly washed with acetone and dried. The average particle size, SiO2 / Al2O3 ratio, and average circularity coefficient of the obtained zeolite (Z-16) were the same as those of the raw material zeolite (Z-8).

[0167] (Synthesis of zeolite (Z-17)) To obtain zeolite (Z-17), 15 g of dried zeolite (Z-11) was added to a solution prepared by adding 5 g of silane coupling agent (KBM-1083, Shin-Etsu Chemical Co., Ltd.) to 100 g of acetone measured in an eggplant flask. The solution was heated under reflux at 55°C for 5 hours while stirring in an oil bath, and after suction filtration, it was thoroughly washed with acetone and dried. The average particle size, SiO2 / Al2O3 ratio, and average circularity coefficient of the obtained zeolite (Z-17) were the same as those of the raw material zeolite (Z-11).

[0168] (Example 5) 0.249 g of zeolite (Z-10) (mode diameter 7.3 μm) and 0.05 g of zeolite (Z-9) (mode diameter 0.31 μm), dried overnight at 150°C, were added to 0.200 g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), dispersed using an ultrasonic cleaner, and then a silicone rubber precursor (SILPOT) was added. TM 184 Silicone Elastomer Base (manufactured by Dow Toray Industries, Inc.) (hereinafter sometimes referred to as Silpot main component) 0.21g and hardener (SILPOT TM0.025 g of 184 Silicone Elastomer Curing Agent (manufactured by Dow Toray Industries, Inc.) (hereinafter sometimes referred to as Silpot curing agent) and 0.209 g of hexane were added and mixed by stirring with a stirring bar. The resulting mixture was applied onto a release film using an applicator with a gap width of 8 mil. After the solvent was evaporated in a vacuum dryer, another release film was placed on top to sandwich the mixture, and pressure was applied using an IMC-180C-C small heated manual press manufactured by Imoto Seisakusho until the pressure gauge showed 20 MPa. The mixture was then cured under pressure by holding it at 100°C for 10 minutes, and the release film was removed to obtain an organic-inorganic hybrid film (M-18) consisting of a matrix resin (P-1) and CHA-type zeolite (Z-10) and zeolite (Z-9). The zeolite content in the organic-inorganic hybrid membrane (M-18) was 56.0 wt%, and the content of zeolite (Z-10) was 5.0 times that of zeolite (Z-9). The organic-inorganic hybrid membrane (M-18) contains two types of zeolite: Z-10, which has a peak at 7.27 μm in the volume-based particle size distribution, and Z-9, which has a peak at 0.31 μm in the volume-based particle size distribution. The film thickness of the organic-inorganic hybrid membrane (M-18) was 60 μm. The air permeability of the organic-inorganic hybrid membrane (M-18) was measured using the above evaluation method and was found to be 0.0 [L / (m³)]. 2 The results were as follows: At 35°C, the permeability coefficient for CO2 was 8100 Barrer, the permeability coefficient for CH4 was 510 Barrer, and the ideal separation coefficient for CO2 / CH4 was 16. These values ​​demonstrate gas permeation and separation performance superior to that of Robeson Upper Bound.

[0169] (Example 6) 0.325g of zeolite (Z-14) dried overnight at 150℃, 0.068g of zeolite (Z-6), and silicone rubber precursor (SILPOT TM 184 Silicone Elastomer Base (manufactured by Dow Toray Industries, Inc.) (hereinafter sometimes referred to as Silpot main component) 0.162g and hardener (SILPOT TM0.012g of 184 Silicone Elastomer Curing Agent (manufactured by Dow Toray Industries, Inc.) (hereinafter sometimes referred to as Silpot curing agent) was added, and the mixture was stirred for 15 minutes and degassed for 1 minute using a rotation / revolution type mixer Awatori Rentaro (AR-250, manufactured by Thinky Co., Ltd.). After mixing with 0.334g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the resulting liquid was applied onto a release film using an applicator with a gap width of 8 mil. After evaporating the solvent in a vacuum dryer, another release film was placed on top to sandwich the mixture, and pressure was applied using an Imoto Seisakusho small heated manual press IMC-180C-C until the pressure gauge showed 20 MPa. The mixture was then cured under pressure by holding it at 100°C for 10 minutes, and the release film was removed to obtain an organic-inorganic hybrid film (M-22) consisting of matrix resin (P-1) and CHA-type zeolite (Z-14) and zeolite (Z-6). The proportion of zeolite in the organic-inorganic hybrid membrane (M-22) was 69.3 wt%, and the content of zeolite (Z-14) was 4.8 times that of zeolite (Z-6). The film thickness of the organic-inorganic hybrid membrane (M-22) was 47 μm. When the particle size distribution of a mixture of zeolite (Z-14) and zeolite (Z-6) was measured, two peaks were observed in the volume-based particle size distribution: 3.6 μm and 0.36 μm. The air permeability of the organic-inorganic hybrid membrane (M-22) was measured using the above evaluation method and found to be 0.0 [L / (m³)]. 2 The results were as follows: At 35°C, the permeability coefficient for CO2 was 12,000 Barrer, and for CH4 it was 340 Barrer, resulting in an ideal CO2 / CH4 separation coefficient of 34. These values ​​demonstrate gas permeation and separation performance superior to that of Robeson Upper Bound.

[0170] (Example 7) 0.323g of zeolite (Z-12) dried overnight at 150℃, 0.067g of zeolite (Z-6), 0.151g of Silpot main agent, and 0.024g of Silpot hardener were added and mixed in a rotation / revolution type mixer Awatori Rentaro (AR-250, manufactured by Shinky Co., Ltd.) for 15 minutes, followed by degassing for 1 minute. After mixing with 0.34g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the resulting liquid was applied onto a release film using an applicator with a gap width of 8mil. After evaporating the solvent in a vacuum dryer, a release film was placed on top and sandwiched between the layers. The mixture was then pressurized using an Imoto Seisakusho IMC-180C-C small-scale heated manual press until the pressure gauge showed 20 MPa. It was then cured under pressure at 100°C for 10 minutes, and the release film was removed to obtain an organic-inorganic hybrid film (M-19) consisting of matrix resin (P-1), CHA-type zeolite (Z-12), and zeolite (Z-6). The proportion of zeolite in the organic-inorganic hybrid film (M-19) was 69.0 wt%, and the content of zeolite (Z-12) was 4.8 times that of zeolite (Z-6). The film thickness of the organic-inorganic hybrid film (M-19) was 53 μm. The air permeability of the organic-inorganic hybrid film (M-19) was measured using the above evaluation method and was found to be 0.0 [L / (m³)]. 2 The results were as follows: At 35°C, the permeability coefficient for CO2 was 12,000 Barrer, the permeability coefficient for CH4 was 450 Barrer, and the ideal separation coefficient for CO2 / CH4 was 26. These values ​​demonstrate gas permeation and separation performance superior to that of Robeson Upper Bound.

[0171] (Example 8) 0.323g of zeolite (Z-12) dried overnight at 150℃, 0.067g of zeolite (Z-6), 0.151g of Silpot main agent, and 0.024g of Silpot hardener were added and mixed in a rotation / revolution type mixer Awatori Rentaro (AR-250, manufactured by Shinky Co., Ltd.) for 15 minutes, followed by 1 minute of degassing. After mixing with 0.340g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the resulting solution was applied onto a release film using an applicator with a gap width of 8 mil. After evaporating the solvent in a vacuum dryer, the film was heated in a circulating constant temperature bath at 80℃ for 5 hours to cure, and the release film was removed to obtain an organic-inorganic hybrid film (M-20) consisting of a matrix resin (P-1) and CHA-type zeolite (Z-12) and zeolite (Z-6). The proportion of zeolite in the organic-inorganic hybrid membrane (M-20) was 69.0 wt%, and the content of zeolite (Z-12) was 4.8 times that of zeolite (Z-6). The film thickness of the organic-inorganic hybrid membrane (M-20) was 64.3 μm. The air permeability of the organic-inorganic hybrid membrane (M-20) was measured using the above evaluation method and was found to be 0.0 [L / (m³)]. 2 The results were as follows: At 35°C, the permeability coefficient for CO2 was 17,000 Barrer, and for CH4 it was 910 Barrer, resulting in an ideal CO2 / CH4 separation coefficient of 19. These values ​​demonstrate gas permeation and separation performance superior to that of Robeson Upper Bound.

[0172] (Example 9) 0.374g of zeolite (Z-11) dried overnight at 150℃, 0.078g of zeolite (Z-8), 0.173g of Silpot main agent, and 0.020g of Silpot hardener were added and mixed using a rotation / revolution type mixer Awatori Rentaro (AR-250, manufactured by Shinky Co., Ltd.) for 15 minutes and degassing for 1 minute. After mixing with 0.38g of methyl ethyl ketone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the resulting liquid was applied onto a release film using an applicator with a gap width of 8mil. After evaporating the solvent in a vacuum dryer, a release film was placed on top and sandwiched between the layers. The mixture was then pressurized using an Imoto Seisakusho IMC-180C-C small-scale heated manual press until the pressure gauge showed 20 MPa. It was then cured under pressure at 100°C for 10 minutes, and the release film was removed to obtain an organic-inorganic hybrid film (M-15) consisting of matrix resin (P-1), CHA-type zeolite (Z-11), and zeolite (Z-8). The proportion of zeolite in the organic-inorganic hybrid film (M-15) was 70.1 wt%, and the content of zeolite (Z-11) was 4.8 times that of zeolite (Z-8). The film thickness of the organic-inorganic hybrid film (M-15) was 65 μm. The air permeability of the organic-inorganic hybrid film (M-15) was measured using the above evaluation method and was found to be 0.0 [L / (m³)]. 2 The results were as follows: At 35°C, the permeability coefficient for CO2 was 14,000 Barrer, the permeability coefficient for CH4 was 480 Barrer, and the ideal separation coefficient for CO2 / CH4 was 28. These values ​​demonstrate gas permeation and separation performance superior to that of Robeson Upper Bound.

[0173] (Example 10) 0.554 g of zeolite (Z-11) dried overnight at 150 °C, 0.111 g of zeolite (Z-8), 0.245 g of Silpot main agent, and 0.025 g of Silpot curing agent were added. Further, 0.011 g of modified silicone oil (X-22-163B (manufactured by Shin-Etsu Chemical Co., Ltd.)) was added as a dispersant, and the mixture was stirred for 15 minutes and defoamed for 1 minute using a rotation and revolution mixer Awatori Renkotor (AR-250, manufactured by Shinku Corporation). After mixing, the resulting liquid was mixed with 0.600 g of hexane (manufactured by Fujifilm Wako Pure Chemical Corporation) and then applied onto a release film using an applicator with a gap width of 8 mil. After volatilizing the solvent using a vacuum dryer, another release film was placed on top and sandwiched, and then pressurized using a small heating manual press IMC-180C-C type manufactured by Imoto Seisakusho until the pressure gauge showed 20 MPa, and cured at 100 °C for 10 minutes while applying pressure. By removing the release film, an organic-inorganic hybrid membrane (M-16) composed of a matrix resin (P-1), CHA-type zeolite (Z-11), and zeolite (Z-8) was obtained. The proportion of zeolite in the organic-inorganic hybrid membrane (M-16) was 70.3 wt%, and among the zeolites, the content of zeolite (Z-11) was 5.0 times the content of zeolite (Z-8). The film thickness of the organic-inorganic hybrid membrane (M-16) was 56 μm. When the air permeation rate of the organic-inorganic hybrid membrane (M-16) was measured by the above evaluation method, it was 0.0 [L / (m 2 ·h)]. The permeation coefficient of CO2 at 35 °C was 13000 Barrer, the permeation coefficient of CH4 was 480 Barrer, and the CO2 / CH4 ideal separation coefficient was 27. From these values, gas permeation and separation performance exceeding the Robeson Upper Bound was shown.

[0174] (Example 11) 0.319g of zeolite (Z-11) dried overnight at 150℃, 0.068g of zeolite (Z-9), 0.162g of Silpot main agent, and 0.016g of Silpot hardener were added and mixed using a rotation / revolution type mixer Awatori Rentaro (AR-250, manufactured by Shinky Co., Ltd.) for 15 minutes, followed by 1 minute of degassing. The mixture was then mixed with 0.427g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and applied to a release film using an applicator with a gap width of 8mil. After evaporating the solvent in a vacuum dryer, a release film was placed on top and sandwiched between the layers. Using an Imoto Seisakusho IMC-180C-C small-scale heated manual press, pressure was applied until the pressure gauge showed 20 MPa. The mixture was then cured under pressure at 100°C for 10 minutes. The release film was then removed to obtain an organic-inorganic hybrid film (M-14) consisting of matrix resin (P-1), CHA-type zeolite (Z-11), and zeolite (Z-9). The proportion of zeolite in the organic-inorganic hybrid film (M-19) was 68.5 wt%, and the content of zeolite (Z-11) was 4.7 times that of zeolite (Z-9). The film thickness of the organic-inorganic hybrid film (M-14) was 49 μm. The air permeability of the organic-inorganic hybrid film (M-14) was measured using the above evaluation method and was found to be 0.0 [L / (m³)]. 2 The results were as follows: At 35°C, the permeability coefficient for CO2 was 12,000 Barrer, and for CH4 it was 460 Barrer, resulting in an ideal CO2 / CH4 separation coefficient of 27. These values ​​demonstrate gas permeation and separation performance superior to that of Robeson Upper Bound.

[0175] (Example 12) 0.662 g of zeolite (Z-6) dried overnight at 150 °C, 0.452 g of Silpot main agent, and 0.040 g of Silpot curing agent were added, and they were mixed with a rotation / revolution type mixer, Awatori Renjiro (AR-250, manufactured by Shinki Co., Ltd.) for 15 minutes of stirring and 1 minute of defoaming. After that, 0.6734 g of hexane (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added and mixed. The resulting liquid was applied onto a release film with an applicator having a gap width of 8 mil. After the solvent was volatilized with a vacuum dryer, another release film was placed on top and sandwiched, and it was pressed with a small heating manual press IMC-180C-C type manufactured by Imoto Seisakusho until the pressure gauge showed 20 MPa, and it was cured while maintaining the pressure at 100 °C for 10 minutes. By removing the release film, an organic-inorganic hybrid membrane (M-11) composed of a matrix resin (P-1) and a CHA type zeolite (Z-6) was obtained. The proportion of zeolite in the organic-inorganic hybrid membrane (M-11) was 57.4 wt%, and the film thickness was 43 μm. When the air permeation rate of the organic-inorganic hybrid membrane (M-11) was measured by the above evaluation method, it was 0.0 [L / (m 2 ·h)]. The permeation coefficient of CO2 at 35 °C was 11000 Barrer, the permeation coefficient of CH4 was 550 Barrer, and the CO2 / CH4 ideal separation coefficient was 20. From these values, gas permeation and separation performance exceeding the Robeson Upper Bound was shown.

[0176] (Example 13) 0.662 g of zeolite (Z-6) dried overnight at 150°C, 0.452 g of Silpot main agent, and 0.040 g of Silpot hardener were added and mixed in a rotation / revolution type mixer Awatori Rentaro (AR-250, manufactured by Shinki Co., Ltd.) for 15 minutes, followed by degassing for 1 minute. After mixing with 0.6734 g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the resulting solution was applied onto a release film using an applicator with a gap width of 8 mil. After evaporating the solvent in a vacuum dryer, the film was heated in a circulating constant temperature bath at 80°C for 5 hours to cure, and the release film was removed to obtain an organic-inorganic hybrid film (M-12) consisting of a matrix resin (P-1) and CHA-type zeolite (Z-6). The proportion of zeolite in the organic-inorganic hybrid film (M-12) was 57.4 wt%, and the film thickness was 68 μm. The air permeability of the organic-inorganic hybrid membrane (M-12) was measured using the above evaluation method and found to be 0.0 [L / (m³)]. 2 The results were as follows: At 35°C, the permeability coefficient for CO2 was 16,000 Barrer, and the permeability coefficient for CH4 was 800 Barrer, resulting in an ideal CO2 / CH4 separation coefficient of 20. These values ​​demonstrate gas permeation and separation performance superior to that of Robeson Upper Bound.

[0177] (Example 14) 0.304 g of zeolite (Z-14) dried overnight at 150°C, 0.127 g of Silpot main agent, and 0.015 g of Silpot hardener were added and mixed in a rotation / revolution type mixer Awatori Rentaro (AR-250, manufactured by Shinky Co., Ltd.) for 15 minutes, followed by degassing for 1 minute. After mixing with 0.283 g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the resulting solution was applied onto a release film using an applicator with a gap width of 8 mil. After evaporating the solvent in a vacuum dryer, the film was heated in a circulating constant temperature bath at 80°C for 5 hours to cure, and the release film was removed to obtain an organic-inorganic hybrid film (M-21) consisting of a matrix resin (P-1) and CHA-type zeolite (Z-14). The proportion of zeolite in the organic-inorganic hybrid film (M-21) was 68.2 wt%, and the film thickness was 50 μm. The air permeability of the organic-inorganic hybrid membrane (M-21) was measured using the above evaluation method and found to be 0.0 [L / (m³)]. 2 The results were as follows: At 35°C, the permeability coefficient for CO2 was 17,000 Barrer, and for CH4 it was 510 Barrer, resulting in an ideal CO2 / CH4 separation coefficient of 34. These values ​​demonstrate gas permeation and separation performance superior to that of Robeson Upper Bound.

[0178] (Example 15) 0.368 g of zeolite (Z-11) dried overnight at 150°C, 0.163 g of Silpot main agent, and 0.027 g of Silpot hardener were added and mixed in a rotation / revolution type mixer Awatori Rentaro (AR-250, manufactured by Shinky Co., Ltd.) for 15 minutes, followed by 1 minute of degassing. After mixing with 0.3705 g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the resulting solution was applied onto a release film using an applicator with a gap width of 8 mil. After evaporating the solvent in a vacuum dryer, the film was heated in a circulating constant temperature bath at 80°C for 5 hours to cure, and the release film was removed to obtain an organic-inorganic hybrid film (M-13) consisting of a matrix resin (P-1) and CHA-type zeolite (Z-11). The proportion of zeolite in the organic-inorganic hybrid film (M-13) was 65.9 wt%, and the film thickness was 47 μm. The air permeability of the organic-inorganic hybrid membrane (M-13) was measured using the above evaluation method and found to be 0.0 [L / (m³)]. 2 The results were as follows: At 35°C, the permeability coefficient for CO2 was 11,000 Barrer, and for CH4 it was 460 Barrer, resulting in an ideal CO2 / CH4 separation coefficient of 24. These values ​​demonstrate gas permeation and separation performance superior to that of Robeson Upper Bound.

[0179] (Example 16) 0.249 g of zeolite (Z-10) (mode diameter 7.3 μm) dried overnight at 150°C, 0.052 g of zeolite (Z-9) (mode diameter 0.31 μm), 0.107 g of Silpot main agent, and 0.012 g of Silpot curing agent were added. Further, 0.031 g of modified silicone oil (X-22-163B (manufactured by Shin-Etsu Chemical Co., Ltd.)) was added as a dispersant. The mixture was stirred for 15 minutes and degassed for 1 minute using a rotation / revolution type mixer, Awatori Rentaro (AR-250, manufactured by Shin-Kee Co., Ltd.). After mixing with 0.314 g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the resulting liquid was applied onto a release film using an applicator with a gap width of 8 mil. After evaporating the solvent in a vacuum dryer, a release film was placed on top and sandwiched between the layers. The mixture was then pressurized using an IMC-180C-C small-scale heated manual press manufactured by Imoto Seisakusho until the pressure gauge showed 20 MPa, and cured under pressure by holding it at 100°C for 10 minutes. By removing the release film, an organic-inorganic hybrid film (M-17) was obtained, consisting of a matrix resin (P-1) and CHA-type zeolite (Z-10) and zeolite (Z-9). The proportion of zeolite in the organic-inorganic hybrid film (M-17) was 66.7 wt%, and the content of zeolite (Z-10) was 4.6 times that of zeolite (Z-9). The organic-inorganic hybrid film (M-17) contains two types of zeolite: Z-10, which has a peak at 7.3 μm in the volume-based particle size distribution, and Z-9, which has a peak at 0.31 μm in the volume-based particle size distribution. The thickness of the organic-inorganic hybrid film (M-17) was 61 μm. The air permeability of the organic-inorganic hybrid film (M-17) was measured using the evaluation method described above and was found to be 0.0 [L / (m³)]. 2 The results were as follows: At 35°C, the permeability coefficient for CO2 was 13,000 Barrer, and for CH4 it was 510 Barrer, resulting in an ideal CO2 / CH4 separation coefficient of 25. These values ​​demonstrate gas permeation and separation performance superior to that of Robeson Upper Bound.

[0180] (Manufacturing Example 1: Fabrication of Silicone Resin / PVDF Composite Film (GL-1)) A porous PVDF membrane support layer with a pore size of 0.45 μm (Immobilon®-P membrane manufactured by Merck Millipore) was placed on a smooth plate, and silicone resin was applied using an applicator with a gap width of 1 mil. The resulting film was heated at 100°C for 30 minutes to form a silicone resin underlayer. The composite film of the porous PVDF support layer and the silicone resin will be hereafter referred to as the silicone resin / PVDF composite film (GL-1). The thickness of the silicone resin layer in the silicone resin / PVDF composite film (GL-1) was determined to be 2 μm by observing the cross-section obtained by freeze-breaking with a scanning electron microscope.

[0181] (Manufacturing Example 2: Fabrication of Silicone Resin / PVDF Composite Film (GL-2)) A porous PVDF membrane support layer with a pore size of 0.45 μm (Immobilon®-P membrane manufactured by Merck Millipore) was placed on a smooth plate, and silicone resin was applied using an autocoater equipped with an applicator with a gap width of 0.5 mil. The resulting film was heated at 100°C for 30 minutes to form a silicone resin underlayer. The composite film of the porous PVDF support layer and the silicone resin will be hereafter referred to as the silicone resin / PVDF composite film (GL-2). The thickness of the silicone resin layer in the silicone resin / PVDF composite film (GL-2), determined by observing the cross-section obtained by freeze-breaking with a scanning electron microscope, was 1 μm.

[0182] (Example 17) Weigh 0.99g of zeolite (Z-7) dried overnight at 150℃, and prepare the silicone rubber precursor (SILPOT TM 0.602g of 184 Silicone Elastomer Base (manufactured by Dow Toray Industries, Inc., hereafter sometimes referred to as Silpot main component) and hardener (SILPOT TM0.063 g of 184 Silicone Elastomer Curing Agent (manufactured by Dow Toray Industries, Inc., sometimes referred to as Silpot curing agent) was added, and the mixture was stirred for 14 minutes using a foam remover (manufactured by Thinky Co., Ltd.), followed by degassing for 1 minute. Then, 1.348 g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and stirred with a stirrer to prepare the mixture for film formation. A silicone resin / PVDF composite film (GL-1) was placed on a smooth plate, and the mixture was dropped onto it and applied using an applicator with a gap width of 5 mil. After the solvent was removed in a vacuum dryer, the matrix resin was further cured by heating in a 100°C constant temperature bath for 30 minutes to obtain an organic-inorganic hybrid film composite (M-23). ​​The matrix resin consisting of the cured product of the Silpot main agent and Silpot curing agent is hereinafter referred to as the matrix resin (P-1). The solid content of the mixed solution used for film formation was 55 wt%, and the zeolite content in the organic-inorganic hybrid film was 59.8 wt%. A cross-section obtained by freeze-fracturing M-23 was observed with a scanning electron microscope, and the thickness of the separation-related layer, which is the portion of the organic-inorganic hybrid membrane composite (M-23) that combines the organic-inorganic hybrid membrane and the underlying layer, excluding the porous support layer, was measured to be 17 μm. The air permeability of the organic-inorganic hybrid membrane composite (M-23) was measured using the above evaluation method and was found to be 76 L / (m³). 2 It was h). The organic-inorganic hybrid membrane composite (M-23) exhibited a CO2 permeability coefficient of 7400 Barrer and a CH4 permeability coefficient of 440 Barrer at 35°C, resulting in a CO2 permeability of 436 GPU at 35°C. The ideal CO2 / CH4 separation coefficient was 17. These values ​​demonstrate gas permeation and separation performance superior to that of the Robeson Upper Bound.

[0183] (Example 18) 0.662 g of zeolite (Z-7) dried overnight at 150°C was weighed, and 0.398 g of Silpot main agent and 0.041 g of Silpot curing agent were added. The mixture was stirred for 15 minutes using a foam remover (Sinky Co., Ltd.), and then degassed for 1 minute. 0.897 g of hexane (Fujifilm Wako Pure Chemical Industries, Ltd.) was then added and stirred with a stirrer to prepare the mixture for film formation. A silicone resin / PVDF composite film (GL-2) was placed on a smooth plate, and the mixture was dropped onto it and applied using an applicator with a gap width of 5 mil. After the solvent was removed in a vacuum dryer, a release film was placed on top, and pressure was applied using an Imoto Seisakusho IMC-180C-C small heated manual press until the pressure gauge showed 10 MPa. The matrix resin was cured by raising the temperature to 100°C and holding it for 10 minutes, and the release film was removed to obtain an organic-inorganic hybrid film composite (M-24). The solid content of the mixed solution used for film formation was 55 wt%, and the zeolite content in the organic-inorganic hybrid film was 60.1 wt%. The cross-section obtained by freeze-fracturing M-24 was observed with a scanning electron microscope, and the thickness of the separation-related layer, which is the combined portion of the organic-inorganic hybrid membrane and the underlying layer after removing the porous support layer from the organic-inorganic hybrid membrane composite (M-24), was measured to be 25.5 μm. The air permeability of the organic-inorganic hybrid membrane composite (M-24) was measured using the above evaluation method and was found to be 0.0 L / (m³). 2 It was h). The organic-inorganic hybrid membrane composite (M-24) exhibited a CO2 permeability coefficient of 6600 Barrer and a CH4 permeability coefficient of 430 Barrer at 35°C, resulting in a CO2 permeability of 258 GPU at 35°C. The ideal CO2 / CH4 separation coefficient was 15. These values ​​demonstrate gas permeation and separation performance superior to that of the Robeson Upper Bound.

[0184] (Example 19) 0.662 g of zeolite (Z-15) dried overnight at 120°C was weighed, and 0.422 g of Silpot main agent and 0.040 g of Silpot curing agent were added. The mixture was stirred for 15 minutes using a foam remover (manufactured by Thinky Co., Ltd.), and then degassed for 1 minute. Furthermore, 0.893 g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and stirred with a stirrer to prepare the mixture for film formation. A silicone resin / PVDF composite film (GL-2) was placed on a smooth plate, and the mixture was dropped onto it. The film was then coated using an applicator with a gap width of 4 mil. After the solvent was removed in a vacuum dryer, the matrix resin was cured under pressure in the same manner as for the organic-inorganic hybrid film composite (M-24), yielding the organic-inorganic hybrid film composite (M-25). The solid content concentration of the mixture used for film formation was 56 wt%, and the zeolite content in the organic-inorganic hybrid film was 58.9 wt%. The cross-section obtained by freeze-fracturing M-25 was observed with a scanning electron microscope, and the thickness of the separation-related layer, which is the combined portion of the organic-inorganic hybrid membrane and the underlying layer after removing the porous support layer from the organic-inorganic hybrid membrane composite (M-25), was measured to be 24 μm. The air permeability of the organic-inorganic hybrid membrane composite (M-25) was measured using the above evaluation method and was found to be 0.0 L / (m³). 2 It was h). The organic-inorganic hybrid membrane composite (M-25) exhibited a CO2 permeability coefficient of 7700 Barrer and a CH4 permeability coefficient of 570 Barrer at 35°C, resulting in a CO2 permeability of 322 GPU at 35°C. The ideal CO2 / CH4 separation coefficient was 14. These values ​​demonstrate gas permeation and separation performance superior to that of the Robeson Upper Bound.

[0185] (Example 20) 0.366 g of zeolite (Z-17) and 0.079 g of zeolite (Z-16), dried overnight at 120°C, were weighed. 0.174 g of Silpot main agent and 0.025 g of Silpot curing agent were added, and the mixture was stirred for 15 minutes using a foam remover (manufactured by Thinky Co., Ltd.), followed by 1 minute of degassing. 0.445 g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was then added and stirred with a stirrer to prepare the mixture for film formation. A silicone resin / PVDF composite film (GL-2) was placed on a smooth plate, and the mixture was dropped onto it. The film was then coated using an applicator with a gap width of 5 mil. After the solvent was removed in a vacuum dryer, the matrix resin was cured under pressure in the same manner as for the organic-inorganic hybrid film composite (M-24), except that the holding time was 5 minutes, to obtain the organic-inorganic hybrid film composite (M-26). The solid content of the mixed solution used for film formation was 59 wt%, and the zeolite content in the organic-inorganic hybrid film was 69.1 wt%. Of the zeolites, the content of zeolite (Z-17) was 4.6 times that of zeolite (Z-16). A cross-section obtained by freeze-fracturing M-26 was observed with a scanning electron microscope, and the thickness of the separation-related layer, which is the combined portion of the organic-inorganic hybrid membrane and the underlying layer after removing the porous support layer from the organic-inorganic hybrid membrane composite (M-26), was measured to be 28 μm. The air permeability of the organic-inorganic hybrid membrane composite (M-26) was measured using the above evaluation method and was found to be 0.0 L / (m³). 2 It was h). The organic-inorganic hybrid membrane composite (M-26) exhibited a CO2 permeability coefficient of 8700 Barrer and a CH4 permeability coefficient of 450 Barrer at 35°C, resulting in a CO2 permeability of 312 GPU at 35°C. The ideal CO2 / CH4 separation coefficient was 20. These values ​​demonstrate gas permeation and separation performance superior to that of the Robeson Upper Bound.

[0186] (Example 21) 0.393 g of zeolite (Z-14) and 0.083 g of zeolite (Z-8), dried overnight at 150°C, were weighed. 0.162 g of Silpot main agent and 0.025 g of Silpot curing agent were added, and the mixture was stirred for 15 minutes using a foam remover (manufactured by Thinky Co., Ltd.), followed by 1 minute of degassing. 0.400 g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was then added and stirred with a stirrer to prepare the mixture for film formation. A silicone resin / PVDF composite film (GL-2) was placed on a smooth plate, and the mixture was dropped onto it. The film was then coated using an applicator with a gap width of 5 mil. After the solvent was removed in a vacuum dryer, the matrix resin was cured under pressure in the same manner as for the organic-inorganic hybrid film composite (M-24), except that the holding time was 5 minutes, to obtain the organic-inorganic hybrid film composite (M-27). The solid content of the mixed solution used for film formation was 62 wt%, and the zeolite content in the organic-inorganic hybrid film was 71.8 wt%. Of the zeolites, the content of zeolite (Z-14) was 4.7 times that of zeolite (Z-8). A cross-section obtained by freeze-fracturing M-27 was observed with a scanning electron microscope, and the thickness of the separation-related layer, which is the combined portion of the organic-inorganic hybrid membrane and the underlying layer after removing the porous support layer from the organic-inorganic hybrid membrane composite (M-27), was measured to be 36 μm. The air permeability of the organic-inorganic hybrid membrane composite (M-27) was measured using the above evaluation method and was found to be 0.0 L / (m³). 2 It was h). The organic-inorganic hybrid membrane composite (M-27) exhibited a CO2 permeability coefficient of 12,000 Barrer and a CH4 permeability coefficient of 440 Barrer at 35°C, resulting in a CO2 permeability of 322 GPU at 35°C. The ideal CO2 / CH4 separation coefficient was 26. These values ​​demonstrate gas permeation and separation performance superior to that of the Robeson Upper Bound.

[0187] (Example 22) Weighed 1.005 g of zeolite (Z-15) dried overnight at 120 °C, added 0.607 g of Silpot main agent and 0.06 g of Silpot curing agent, stirred with a whisk (manufactured by Shinki Co., Ltd.) for 14 minutes, and then defoamed for 1 minute. Further added 1.35 g of hexane (manufactured by Fujifilm Wako Pure Chemical Corporation) and stirred with a stirrer to prepare a mixed solution for film formation. Affixed a silicone resin / PVDF composite membrane (GL-1) on a smooth plate and placed it on the sample stage of a spin coater (Mikasa Co., Ltd., 1H-DX2). Then dropped the mixed solution onto it and rotated and coated it at 3000 rpm for 30 seconds. After removing the solvent with a vacuum dryer, further heated it in a constant temperature bath at 100 °C for 30 minutes to cure the matrix resin, and obtained an organic-inorganic hybrid membrane composite (M-28). The solid content concentration of the mixed solution used for film formation was 55 wt%, and the content of zeolite in the organic-inorganic hybrid membrane was 60.1 wt%. The cross-section obtained by freeze-fracturing M-28 was observed with a scanning electron microscope, and the film thickness of the combined part of the organic-inorganic hybrid membrane and the base layer, that is, the separation-related layer, excluding the porous support layer from the organic-inorganic hybrid membrane composite (M-28), was measured. The film thickness was 17 μm. When the air permeation rate of the organic-inorganic hybrid membrane composite (M-28) was measured by the above evaluation method, it was 76 L / (m 2 ·h). The CO2 permeation coefficient of the organic-inorganic hybrid membrane composite (M-28) at 35 °C was 6400 Barrer, the permeation coefficient of CH4 was 470 Barrer, and the permeability of CO2 at 35 °C was 377 GPU. The CO2 / CH4 ideal separation factor was 14. From these values, a gas permeation and separation performance exceeding the Robeson Upper Bound was shown.

[0188] The results of Examples 4 to 22 are shown in Tables 2 and 3.

[0189]

Table 2

[0190]

Table 3

[0191] One aspect of the present invention can be used in any industrial field, but the organic-inorganic hybrid membrane, gas separation membrane module, and gas separation method of one aspect of the present invention can be suitably used for CO2 separation and recovery, such as the removal of carbon dioxide from natural gas, CO2 recovery from landfill gas, and CO2 recovery (CO2, N2 mixture) from combustion exhaust gas of thermal power plants, etc., as well as hydrogen recovery and purification in various reaction processes in the petroleum refining industry and the chemical industry, and the production of oxygen-enriched gas. [Explanation of symbols]

[0192] 1. Organic-inorganic hybrid film 2 Separation membrane module 3. Gas reservoir for supplying and maintaining the temperature of the gas. 4. Pressure gauge 5 Mass Flow Controller 6. Pressure relief valve 7. Balatron pressure gauge 8. Gas reservoir for permeate gas 9. Liquid nitrogen trap 10 Vacuum pump 11, 12, 13, 14, 15 valves 16 Temperature bath 17 Valve 17 (Handheld Valve) 18 gas cylinders

Claims

1. Glass transition temperature of 15°C or lower, and CO at 35°C ２ The material comprises a resin with a permeability coefficient of 200 Barre or more and an inorganic filler having gas selectivity, wherein the content of the inorganic filler having gas selectivity is 35% by mass or more. The inorganic filler having gas selectivity includes a zeolite. The framework density of the aforementioned zeolite, assuming that all of the T elements are silicon, is 16.0 T / 1000 Å or less. The aforementioned zeolite is an organic-inorganic hybrid membrane in which the zeolite is an oxygen ring with 8 or fewer members.

2. The SiO of the zeolite ２ / Al ２ O ３ The organic-inorganic hybrid film according to claim 1, wherein the molar ratio is 7 or greater.

3. Glass transition temperature of 15°C or lower, and CO at 35°C ２ The material comprises a resin with a permeability coefficient of 200 Barre or more and an inorganic filler having gas selectivity, wherein the content of the inorganic filler having gas selectivity is 35% by mass or more. The inorganic filler having gas selectivity includes a zeolite. The SiO of the zeolite ２ / Al ２ O ３ The molar ratio is 7 or higher. The aforementioned zeolite is an organic-inorganic hybrid membrane in which the zeolite is an oxygen ring with 8 or fewer members.

4. The organic-inorganic hybrid film according to any one of claims 1 to 3, wherein the inorganic filler has a particle size distribution with at least two peaks.

5. A method for separating and concentrating gases using an organic-inorganic hybrid membrane according to any one of claims 1 to 4.

6. A gas separation membrane module using an organic-inorganic hybrid membrane according to any one of claims 1 to 4.

7. A method for producing an organic-inorganic hybrid film according to any one of claims 1 to 4, comprising a curing step of curing a matrix resin while applying pressure.

8. The method for producing an organic-inorganic hybrid film according to claim 7, wherein the curing step involves heating while applying pressure.

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