JP6217242B2 - Method for producing porous support-zeolite membrane composite - Google Patents

Description

  The present invention relates to a method for producing a porous support-zeolite membrane composite. The porous support-zeolite membrane composite obtained by the production method of the present invention permeates and separates a highly permeable substance from a gas or liquid mixture composed of a plurality of components, and concentrates the low permeable substance. It is something that can be done.

Conventionally, separation or concentration of a gas or liquid mixture containing an organic compound is performed by distillation, azeotropic distillation, solvent extraction / distillation, adsorbent, etc., depending on the properties of the target substance. . However, these methods have drawbacks that they require a lot of energy or have a limited application range for separation and concentration.
In recent years, membrane separation and concentration methods using membranes such as polymer membranes and zeolite membranes have been proposed as separation methods instead of these methods. Polymer membranes such as flat membranes and hollow fiber membranes are excellent in processability, but have the disadvantage of low heat resistance. In addition, polymer membranes have low chemical resistance, and many of them swell when contacted with organic compounds such as organic solvents and organic acids, so that the range of application for separation and concentration is limited.

  Further, the zeolite membrane is usually used for separation and concentration as a zeolite membrane composite in which zeolite is formed into a membrane on a support. For example, the organic compound can be separated and concentrated by bringing a mixture of the organic compound and water into contact with the zeolite membrane composite and selectively permeating water. Separation and concentration using membranes of inorganic materials can reduce the amount of energy used compared to separation by distillation or adsorbent, and can be separated and concentrated in a wider temperature range than polymer membranes. It can also be applied to the separation of mixtures.

  As a separation method using a zeolite membrane, for example, a method of selectively permeating water using an A-type zeolite membrane composite to concentrate alcohol (Patent Document 1), and a mordenite-type zeolite membrane composite using alcohol A method of selectively permeating water from a mixed system of water (Patent Document 2) or selectively permeating water from a mixed system of acetic acid and water using a ferrierite-type zeolite membrane composite. A method for separating and concentrating acetic acid (Patent Document 3) has been proposed.

JP-A-7-185275 JP 2003-144871 A JP 2000-237561 A

It is generally known that in many zeolite membranes, when the concentration of the low-permeability substance constituting the mixture is high, the permeation of the low-permeability substance to the permeate side increases and the separation performance decreases. Therefore, it has been desired to realize a zeolite membrane having a high separation performance even when the concentration of a low-permeability substance is high.
The object of the present invention is to solve the problems of the prior art, and in the separation and concentration by an inorganic material separation membrane, a porous support-zeolite membrane composite that has both a practically sufficient throughput and separation performance, An object of the present invention is to provide a separation and concentration method using a zeolite membrane composite.

As a result of intensive studies to solve the above problems, the present inventors have found that the separation performance of the zeolite membrane is dramatically improved by treating the surface of the zeolite membrane with a specific compound. The present invention has been accomplished based on these findings.
That is, the gist of the present invention resides in the following (1) to ( 4 ).
(1) A method for producing a porous support-zeolite membrane composite having a zeolite membrane formed on a porous support , which is used for separation or concentration of a gas or liquid mixture , on the porous support A method for producing a porous support-zeolite membrane composite comprising: forming a zeolite membrane on the substrate, and then treating the zeolite membrane with a material having 2 or more Si atoms in the molecule.
(2) The method for producing a porous support-zeolite membrane composite according to (1), wherein the treatment is immersion treatment, dropping treatment or spraying treatment.
(3) The method for producing a porous support-zeolite membrane composite according to (1) or (2), wherein the treated zeolite membrane is heated at a temperature of 30 ° C. or higher.
(4) The porous support-zeolite membrane composite according to any one of (1) to (3), wherein the material having two or more Si atoms in the molecule is selected from alkoxysilanes, organosilicon compounds, and silicate oligomers. Manufacturing method.

  According to the present invention, when separating and concentrating a specific substance from a gas or liquid mixture composed of a plurality of components, a zeolite membrane having a sufficiently large processing amount for practical use and sufficient separation performance is obtained. A porous support-zeolite membrane composite is provided. By using this zeolite membrane composite as a separation means, it is possible to separate a highly permeable substance from a gas or liquid mixture consisting of a plurality of components and to concentrate the mixture, with both sufficient throughput and separation performance. Become.

Schematic diagram of measuring device used for gas separation Schematic diagram of the measuring device used for the vapor permeation method

Hereinafter, embodiments of the present invention will be described in more detail. However, the description of the constituent elements described below is an example of embodiments of the present invention, and the present invention is not limited to these contents. Various modifications can be made within the scope of the gist.
The method for producing a porous support-zeolite membrane composite of the present invention is a method for producing a porous support-zeolite membrane composite having a zeolite membrane formed on a porous support, the porous support After forming a zeolite membrane on the top, the zeolite membrane is treated with a material having 2 or more Si atoms in the molecule.

First, the zeolite membrane formed on the inorganic porous support, which is a feature of the present invention, will be described.
In the present specification, the inorganic porous support and the zeolite membrane formed thereon may be referred to as “zeolite membrane composite”, which may be abbreviated as “membrane composite”. In addition, the “inorganic porous support” may be abbreviated as “porous support” or “support”.

<Porous support>
In the present invention, the porous support has a chemical stability that allows the zeolite to be crystallized into a film on the surface thereof, and is a support made of an inorganic porous material (inorganic porous support). It can be anything. For example, sintered ceramics (ceramics support) such as silica, α-alumina, γ-alumina, mullite, zirconia, titania, yttria, silicon nitride, silicon carbide, sintered metals such as iron, bronze, and stainless steel, glass And carbon moldings.

Among these porous supports, there are inorganic porous supports (ceramic supports) including sintered ceramics, which are solid materials whose basic components or most of them are composed of inorganic nonmetallic substances. preferable. If this support is used, a part of the support is zeoliticized during the synthesis of the zeolite membrane, thereby improving the adhesion at the interface.
Specific examples include a ceramic sintered body (ceramic support) containing silica, α-alumina, γ-alumina, mullite, zirconia, titania, yttria, silicon nitride, silicon carbide, and the like. Among them, an inorganic porous support containing at least one of alumina, silica, and mullite is preferable. When these supports are used, partial zeolitization is easy, so that the bond between the support and the zeolite becomes strong, and a dense membrane with high separation performance is easily formed.

The shape of the porous support is not particularly limited as long as it can effectively separate a gas mixture or a liquid mixture, and specifically, for example, a flat plate shape, a tubular shape, a cylindrical shape, a cylindrical shape, a prismatic shape, or the like. Honeycomb-like ones having a large number of pores, monoliths and the like can be mentioned.
In the present invention, zeolite is formed into a film on such a porous support, that is, on the surface of the support. The surface of the support may be any surface or a plurality of surfaces depending on the shape of the support. For example, in the case of a cylindrical tube support, it may be the outer surface or the inner surface, and in some cases both the outer and inner surfaces.

  The average pore diameter on the surface of the porous support is not particularly limited, but those having a controlled pore diameter are preferred. The average pore diameter on the surface of the support is usually 0.02 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less. If the average pore diameter is too small, the amount of permeation tends to be small, and if it is too large, the strength of the support itself is insufficient, and the proportion of pores on the surface of the support increases, making it difficult to form a dense zeolite membrane. Tend.

  The average thickness (wall thickness) of the porous support is usually 0.1 mm or more, preferably 0.3 mm or more, more preferably 0.5 mm or more, usually 7 mm or less, preferably 5 mm or less, more preferably 3 mm. It is as follows. The support is used to give mechanical strength to the zeolite membrane, but if the average thickness of the support is too thin, the zeolite membrane composite will not have sufficient strength and There is a tendency to weaken. If the average thickness of the support is too thick, the diffusion of the permeated material tends to be poor and the permeability tends to be low.

The porosity of the porous support is usually 20% or more, preferably 25% or more, more preferably 30% or more, and usually 70% or less, preferably 60% or less, more preferably 50% or less. The porosity of the support influences the permeation flow rate when the gas is separated, and if it is less than the lower limit, it tends to inhibit the diffusion of the permeate, and if it exceeds the upper limit, the strength of the support tends to decrease.
The surface of the porous support may be polished with a file or the like as necessary. The surface of the porous support means the surface portion of the inorganic porous support that crystallizes the zeolite, and any surface of each shape may be used as long as the surface is a plurality of surfaces. Also good. For example, in the case of a cylindrical tube support, it may be the outer surface or the inner surface, and in some cases both the outer and inner surfaces.

<Zeolite membrane composite>
In the present invention, a zeolite membrane is formed on the porous support to obtain a zeolite membrane composite.
In addition to zeolite, the components constituting the zeolite membrane include inorganic binders such as silica and alumina, organic compounds such as polymers, or materials having two or more Si atoms that modify the zeolite surface as detailed below, or their reaction products, etc. May be included as necessary. Further, the zeolite membrane in the present invention may partially contain an amorphous component.

The thickness of the zeolite membrane is not particularly limited, but is usually 0.1 μm or more, preferably 0.6 μm or more, more preferably 1.0 μm or more, and usually 100 μm or less, preferably 60 μm or less, more preferably 20 μm or less. It is. If the film thickness is too large, the amount of permeation tends to decrease, and if it is too small, the selectivity tends to decrease or the film strength tends to decrease.
The particle diameter of the zeolite is not particularly limited, but if it is too small, the grain boundary tends to increase, and the permeation selectivity tends to decrease. Therefore, it is usually 30 nm or more, preferably 50 nm or more, more preferably 100 nm or more, and the upper limit is the film thickness or less. Furthermore, it is particularly preferred that the zeolite particle size is the same as the membrane thickness. When the zeolite particle size is the same as the membrane thickness, the zeolite grain boundary is smallest. Zeolite membranes obtained by hydrothermal synthesis described later are particularly preferred because the zeolite particle size and membrane thickness may be the same.

The shape of the zeolite membrane composite is not particularly limited, and any shape such as a tubular shape, a hollow fiber shape, a monolith type, and a honeycomb type can be adopted. Also, the size is not particularly limited. For example, in the case of a tubular shape, a length of 2 cm to 200 cm, an inner diameter of 0.05 cm to 2 cm, and a thickness of 0.5 mm to 4 mm are practical and preferable.
One of the separation functions of the zeolite membrane is separation as a molecular sieve, and gas molecules having a size greater than or equal to the effective pore diameter of the zeolite to be used can be suitably separated. There is no upper limit to the molecules used for separation, but the size of the molecules is usually about 100 mm or less.

The zeolite is preferably an aluminosilicate.
The SiO ₂ / Al ₂ O ₃ molar ratio on the zeolite membrane surface is a numerical value obtained by X-ray photoelectron spectroscopy (XPS). XPS is an analysis method for obtaining information on the film surface, and the SAR on the film surface can be obtained by this analysis method.
The SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite membrane surface is preferably 25 or more, more preferably 28 or more, further preferably 30 or more, particularly preferably 32 or more, and preferably 3000 or less, More preferably, it is 2000 or less, More preferably, it is 1000 or less, Most preferably, it is 500 or less. Zeolite membrane surface SiO ₂ / Al ₂ O
It is considered that when the ₃ molar ratio is 25 or more, the pore diameter of the membrane surface is narrowed and the separation performance is improved. Further, since the SAR on the film surface is not more than the upper limit, there is an advantage that the permeability is not reduced in terms of adsorptivity.

The SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite membrane itself is preferably 5 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, preferably 2000 or less, more preferably 1000 or less. More preferably, it is 500 or less, more preferably 100 or less, particularly preferably 50 or less. When the SAR of the membrane itself is equal to or higher than the lower limit, durability tends to be improved. When the SAR is equal to or lower than the upper limit, there is an advantage that the permeability is not reduced in terms of adsorptivity.

The SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite membrane itself is a numerical value obtained by scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDX). In SEM-EDX, information of only a film of several microns can be obtained by measuring the acceleration voltage of X-rays at about 10 kV. Since the zeolite membrane is uniformly formed, the SAR of the membrane itself can be obtained by this measurement.

  In the present invention, the SAR on the film surface is preferably 20 or more larger than the SAR on the film itself, but this value (a value obtained by subtracting the SAR on the film itself from the SAR on the film surface) is more preferably 22 Above, more preferably 25 or more, particularly preferably 30 or more. The upper limit of this value is not particularly limited, but is usually 1000 or less, preferably 700 or less, more preferably 500 or less, and particularly preferably 400 or less.

When the above value (the value obtained by subtracting the SAR of the membrane itself from the SAR of the membrane surface) is 20 or more, it is considered that the pore diameter on the membrane surface is narrowed and the separation performance is improved.
The main zeolite constituting the zeolite membrane preferably contains a zeolite having a pore structure with an oxygen 8-membered ring or less, and more preferably contains a zeolite having a pore structure with an oxygen 6- to 8-membered ring.

Here, the value of n of the zeolite having an oxygen n-membered ring has the largest number of oxygen in the pores composed of oxygen forming the zeolite skeleton and T element (element other than oxygen constituting the skeleton). Show things. For example, when there are 12-membered and 8-membered pores of oxygen, such as MOR type zeolite, it is regarded as a 12-membered ring zeolite.
Examples of the zeolite having a pore structure having an oxygen 8-membered ring or less include, for example, AEI, AFG, ANA, BRE, CAS, CDO, CHA, DDR, DOH, EAB, EPI, ERI, ESV, FAR, FRA, GIS, GIU , GOO, ITE, KFI, LEV, LIO, LOS, LTA, LTN, MAR, MEP, MER, MEL, MON, MSO, MTF, MTN, NON, PAU, PHI, RHO, RTE, RTH, RUT, SGT, SOD , TOL, TSC, UFI, VNI, YUG and the like.

Examples of the zeolite having an oxygen 6-8 membered ring structure include AEI, AFG, ANA, CHA, EAB, ERI, ESV, FAR, FRA, GIS, ITE, KFI, LEV, LIO, LOS, LTA, LTN, MAR. , PAU, RHO, RTH, SOD, TOL, UFI and the like.
In addition, in this specification, the structure of a zeolite is shown with the code | symbol which prescribes | regulates the structure of the zeolite which International Zeolite Association (IZA) defines as above-mentioned.

The oxygen n-membered ring structure determines the size of the pores of the zeolite. In the case of zeolite smaller than the oxygen 6-membered ring, the pore diameter is smaller than the kinetic diameter of the H ₂ O molecule. In some cases, the transmittance is small and not practical. In addition, when it is larger than the oxygen 8-membered ring structure, the pore diameter becomes large, and a gas component or liquid component having a small size may deteriorate the separation performance, and the use may be limited.

The framework density (T / 1000 ³ ) of the zeolite is not particularly limited, but is usually 17 or less, preferably 16 or less, more preferably 15.5 or less, particularly preferably 15 or less, usually 10 or more, preferably 11 or more. More preferably, it is 12 or more.
The framework density means the number of elements (T element) other than oxygen constituting the framework per 1000 ³ of the zeolite, and this value is determined by the structure of the zeolite. The relationship between the framework density and the structure of zeolite is shown in ATLAS OF ZEOLITE FRAMEWORK TYPES Sixth Revised Edition 2007 ELSEVIER.

In the present invention, preferred zeolite structures are AEI, AFG, CHA, EAB, ERI, ESV, FAR, FRA, GIS, ITE, KFI, LEV, LIO, LOS, LTN, MAR, PAU, RHO, RTH, SOD, TOL, UFI, more preferable structures are AEI, CHA, ERI, KFI, LEV, PAU, RHO, RTH, UFI, more preferable structures are CHA, LEV, RHO, and most preferable structure is CH.
A.

  Here, in the present invention, the CHA-type zeolite is a code that defines the structure of the zeolite defined by the International Zeolite Association (IZA) and indicates a CHA structure. This is a zeolite having a crystal structure equivalent to that of naturally occurring chabazite. The CHA-type zeolite has a structure characterized by having three-dimensional pores composed of 8-membered oxygen rings having a diameter of 3.8 × 3.8 mm, and the structure is characterized by X-ray diffraction data.

The framework density (T / 1000 ³ ) of the CHA-type zeolite is 14.5. The SiO ₂ / Al ₂ O ₃ molar ratio is the same as described above.
In the present invention, when the zeolite membrane contains CHA-type zeolite, the intensity of the peak around 2θ = 17.9 ° is the intensity of the peak around 2θ = 20.8 ° in the X-ray diffraction pattern. It is preferable that the size is 0.5 times or more.

  Here, the peak intensity refers to a value obtained by subtracting the background value from the measured value. Peak intensity ratio represented by (Intensity of peak near 2θ = 17.9 °) / (Intensity of peak near 2θ = 20.8 °) (hereinafter, this may be referred to as “peak intensity ratio A”) In other words, it is usually 0.5 or more, preferably 1 or more, more preferably 1.2 or more, and particularly preferably 1.5 or more. Although an upper limit is not specifically limited, Usually, it is 1000 or less.

When the zeolite membrane contains CHA-type zeolite, the intensity of the peak near 2θ = 9.6 ° is 2 of the peak intensity around 2θ = 20.8 ° in the X-ray diffraction pattern. The size is preferably twice or more.
Peak intensity ratio represented by (Intensity of peak near 2θ = 9.6 °) / (Intensity of peak near 2θ = 20.8 °) (hereinafter, this may be referred to as “peak intensity ratio B”) In other words, it is usually 2 or more, preferably 2.5 or more, more preferably 3 or more, more preferably 4 or more, still more preferably 6 or more, particularly preferably 8 or more, and most preferably 10 or more. Although an upper limit is not specifically limited, Usually, it is 1000 or less.

  Here, the X-ray diffraction pattern is obtained by irradiating the surface on which zeolite is mainly attached with X-rays using CuKα as a radiation source to obtain a scanning axis of θ / 2θ. The shape of the sample to be measured may be any shape that can irradiate the surface of the membrane composite to which the zeolite is mainly attached, with X-ray irradiation. The body itself or the one cut into an appropriate size restricted by the apparatus is preferable.

Here, the X-ray diffraction pattern may be measured by fixing the irradiation width using an automatic variable slit when the surface of the zeolite membrane composite is a curved surface. An X-ray diffraction pattern using an automatic variable slit refers to a pattern in which variable → fixed slit correction is performed.
Here, the peak in the vicinity of 2θ = 17.9 ° refers to the maximum of the peaks present in the range of 17.9 ° ± 0.6 ° among the peaks not derived from the base material.

The peak in the vicinity of 2θ = 20.8 ° refers to the maximum peak in the range of 20.8 ° ± 0.6 ° among the peaks not derived from the base material.
The peak in the vicinity of 2θ = 9.6 ° refers to the maximum of the peaks present in the range of 9.6 ° ± 0.6 ° among the peaks not derived from the base material.
According to COLLECTION OF SIMULATED XRD POWTER PATTERNS FOR ZEOLITE Third Revised Edition 1996 ELSEVIER (hereinafter sometimes referred to as “Non-Patent Document 1”), the peak near 2θ = 9.6 ° in the X-ray diffraction pattern is rhombohedral. Set the space group

(No. 166), it is a peak derived from the plane having an index of (1, 0, 0) in the CHA structure.
Further, in the X-ray diffraction pattern, the peak around 2θ = 17.9 ° is a space group in rhombohedral setting according to Non-Patent Document 1.

(No. 166) is a peak derived from the (1,1,1) index in the CHA structure.
According to Non-Patent Document 1, the peak near 2θ = 20.8 ° in the X-ray diffraction pattern is a space group in the rhombohedral setting.

(No. 166) is a peak derived from the (2, 0, -1) index in the CHA structure.
The typical ratio (peak intensity ratio B) of the peak intensity derived from the (2, 0, -1) plane of the peak intensity derived from the (1, 0, 0) plane in the CHA type aluminosilicate zeolite membrane is Halil Kalipcilar et al., “Synthesis and Separation Performance of SSZ-13 Zeolite Membranes on Tubular Supports”, Chem. Mater. 2002, 14, 3458-3464 (hereinafter sometimes referred to as “Non-Patent Document 2”). ) Is less than 2.

Therefore, this ratio of 2 or more means that, for example, the zeolite crystal is oriented so that the (1, 0, 0) plane when the CHA structure is a hombohedral setting is oriented almost parallel to the surface of the membrane composite. Is considered to mean that the crystals are oriented and growing. Orientation and growth of zeolite crystals in the zeolite membrane composite is advantageous in that a dense membrane with high separation performance can be formed.

The typical ratio (peak intensity ratio A) of the peak intensity derived from the (1, 1, 1) plane and the peak intensity derived from the (2, 0, -1) plane in the CHA type aluminosilicate zeolite membrane is According to Non-Patent Document 2, it is less than 0.5.
Therefore, this ratio of 0.5 or more means, for example, that the (1, 1, 1) plane when the CHA structure is a rhombohedral setting is oriented so that the orientation is almost parallel to the surface of the membrane composite. It is thought to mean that the crystals are oriented and growing. Orientation and growth of zeolite crystals in the zeolite membrane composite is advantageous in that a dense membrane with high separation performance can be formed.

As described above, the fact that any one of the peak intensity ratios A and B is a value in the above-mentioned specific range means that the zeolite crystals are oriented and grow, and a dense membrane with high separation performance is formed. Is shown.
The peak intensity ratios A and B indicate that the larger the value, the stronger the degree of orientation, and generally the stronger the degree of orientation, the more dense the film is formed. In general, the stronger the orientation, the higher the separation performance tends to be. However, the optimum degree of orientation in which the separation performance becomes higher differs depending on the mixture to be separated. It is desirable to select and use the membrane complex.

<Method for producing zeolite membrane composite>
In the present invention, for example, a zeolite membrane is formed on an inorganic porous support by hydrothermal synthesis, and then the zeolite membrane is treated with a material having two or more Si atoms in the molecule.
Specifically, for example, a zeolite membrane composite is prepared by mixing a reaction mixture for hydrothermal synthesis (hereinafter sometimes referred to as an “aqueous reaction mixture”) having a uniform composition and a porous support. It can be prepared by placing in a heat-resistant pressure-resistant container such as an autoclave, which is gently fixed inside, and sealing and heating for a certain time.

The aqueous reaction mixture preferably contains an Si element source, an Al element source, an alkali source, and water, and further contains an organic template as necessary.
Examples of the Si element source used in the aqueous reaction mixture include amorphous silica, colloidal silica, silica gel, sodium silicate, amorphous aluminum silicate gel, tetraethoxysilane (TEOS), trimethylethoxysilane, and the like.

As the Al element source, for example, sodium aluminate, aluminum hydroxide, aluminum sulfate, aluminum nitrate, aluminum oxide, amorphous aluminosilicate gel, or the like can be used. In addition to the Al element source, other element sources, for example, element sources such as Ga, Fe, B, Ti, Zr, Sn, and Zn may be included.
In crystallization of zeolite, an organic template (structure directing agent) can be used as necessary, but those synthesized using an organic template are preferred. By synthesizing using an organic template, the ratio of silicon atoms to aluminum atoms of crystallized zeolite is increased, and acid resistance and water vapor resistance are improved.

The organic template may be any type as long as it can form a desired zeolite membrane. Further, one type of template or a combination of two or more types may be used.
When the zeolite is of the CHA type, amines and quaternary ammonium salts are usually used as the organic template. For example, organic templates described in U.S. Pat. No. 4,544,538 and U.S. Patent Publication No. 2008/0075656 are preferred.

  Specific examples include cations derived from alicyclic amines such as cations derived from 1-adamantanamine, cations derived from 3-quinacridinal, and cations derived from 3-exo-aminonorbornene. It is done. Among these, a cation derived from 1-adamantanamine is more preferable. When a cation derived from 1-adamantanamine is used as an organic template, CHA-type zeolite capable of forming a dense film is crystallized. By forming a dense membrane, a CHA-type zeolite with high separation performance can be obtained.

  Of the cations derived from 1-adamantanamine, the N, N, N-trialkyl-1-adamantanammonium cation is more preferred. The three alkyl groups of the N, N, N-trialkyl-1-adamantanammonium cation are usually independent alkyl groups, preferably a lower alkyl group, more preferably a methyl group. The most preferred compound among them is the N, N, N-trimethyl-1-adamantanammonium cation.

Such cations are accompanied by anions that do not harm the formation of CHA-type zeolite. Representative examples of such anions include halogen ions such as Cl ⁻ , Br ⁻ and I ⁻ , hydroxide ions, acetates, sulfates, and carboxylates. Of these, hydroxide ions are particularly preferably used.
As another organic template, N, N, N-trialkylbenzylammonium cation can also be used. Also in this case, the alkyl group is an independent alkyl group, preferably a lower alkyl group, more preferably a methyl group. Among them, the most preferred compound is N, N, N-trimethylbenzylammonium cation. The anion accompanied by this cation is the same as described above.

As the alkali source used in the aqueous reaction mixture, a hydroxide ion of a counter anion of an organic template, an alkali metal hydroxide such as NaOH or KOH, or an alkaline earth metal hydroxide such as Ca (OH) ₂ is used. Can do. The type of alkali is not particularly limited, and Na, K, Li, Rb, Cs, Ca, Mg, Sr, Ba and the like are usually used. Among these, Li, Na, and K are preferable, and K is more preferable. In addition, two or more alkalis may be used in combination, and specifically, Na and K, and Li and K 2 are preferably used in combination.

The ratio of Si element source to Al element source in the aqueous reaction mixture is usually expressed as the molar ratio of the oxides of the respective elements, that is, the SiO ₂ / Al ₂ O ₃ molar ratio. The SiO ₂ / Al ₂ O ₃ molar ratio is not particularly limited, but is usually 5 or more, preferably 8 or more, more preferably 10 or more, and further preferably 15 or more. Further, it is usually 10,000 or less, preferably 1000 or less, more preferably 300 or less, and still more preferably 100 or less.

When the SiO ₂ / Al ₂ O ₃ molar ratio is within this range, the zeolite membrane is densely formed, and the membrane has high separation performance. In addition, since moderately Al atoms are present in the produced zeolite, the separation performance is improved with a gas component or a liquid component exhibiting adsorptivity to Al. When Al is within this range, a zeolite membrane having high acid resistance and high water vapor resistance can be obtained.
The ratio of the silica source and an organic template in the aqueous reaction mixture, the molar ratio of the organic template for SiO ₂ (organic template / SiO ₂ molar ratio), usually 0.005 or higher, preferably at least 0.01, more preferably 0 0.02 or more, usually 1 or less, preferably 0.4 or less, more preferably 0.2 or less.

When the organic template / SiO ₂ molar ratio is in the above range, in addition to being able to produce a dense zeolite membrane, the produced zeolite has strong acid resistance and water vapor resistance.
The ratio of the Si element source to the alkali source is M _{(2 / n) 2} O / SiO ₂ (where M represents an alkali metal or alkaline earth metal, and n represents the valence 1 or 2). In general, it is 0.02 or more, preferably 0.04 or more, more preferably 0.05 or more, and usually 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less.

In the case of forming a CHA-type zeolite membrane, it is preferable that K is contained in the alkali metal because a denser and highly crystalline membrane is formed. In this case, the molar ratio of K to all alkali metals and / or alkaline earth metals containing K is usually 0.01 or more and 1 or less, preferably 0.1 or more and 1 or less, more preferably 0.3 or more. 1 or less.
As described above, the addition of K to the aqueous reaction mixture is performed by changing the space group in the rhombohedral setting.

(No. 166), the peak intensity in the vicinity of 2θ = 9.6 °, which is a peak derived from the (1, 0, 0) index surface in the CHA structure, and the (2, 0, −1) surface The peak intensity ratio in the vicinity of 2θ = 20.8 ° (peak intensity ratio B), which is a peak derived from the above, or the peak derived from the plane of (1,1,1), in the vicinity of 2θ = 17.9 ° There is a tendency to increase the ratio between the peak intensity and the peak intensity in the vicinity of 2θ = 20.8 ° (peak intensity ratio A), which is a peak derived from the (2, 0, −1) plane.

The ratio of Si element source to water is the molar ratio of water to SiO ₂ (H ₂ O / SiO ₂ molar ratio), which is usually 10 or more, preferably 30 or more, more preferably 40 or more, and particularly preferably 50 or more. Usually, it is 1000 or less, preferably 500 or less, more preferably 200 or less, and particularly preferably 150 or less.
When the molar ratio of materials in the aqueous reaction mixture is in these ranges, a dense zeolite membrane can be formed. The amount of water is particularly important in the formation of a dense zeolite membrane, and a denser membrane tends to be formed more easily under conditions where the amount of water is greater than that of the general powder synthesis method.

In general, the amount of water in the synthesis of powdered CHA-type zeolite is about 15 to 50 in terms of H ₂ O / SiO ₂ molar ratio. Zeolite membrane composite with high separation performance in which CHA-type zeolite is crystallized into a dense membrane on the support by using a high H ₂ O / SiO ₂ molar ratio (50 to 1000), that is, water-rich conditions. You can get a body.
Further, in the hydrothermal synthesis, it is not always necessary to have a seed crystal in the reaction system, but the crystallization of zeolite can be promoted on the support by adding the seed crystal. The method of adding the seed crystal is not particularly limited, and a method of adding the seed crystal to the aqueous reaction mixture or the method of attaching the seed crystal on the support as in the synthesis of the powdered zeolite is used. Can do.

When producing a zeolite membrane composite, it is preferable to attach a seed crystal on the support. By attaching a seed crystal in advance to the support, a dense zeolite membrane with good separation performance can be easily formed.
The seed crystal to be used is not limited as long as it is a zeolite that promotes crystallization, but it is preferably the same crystal type as the zeolite membrane to be formed for efficient crystallization. When forming a CHA type zeolite membrane, it is preferable to use seed crystals of CHA type zeolite.

The particle diameter of the seed crystal is usually 0.5 nm or more, preferably 1 nm or more, more preferably 2 nm or more, and is usually 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less.
The method for attaching the seed crystal on the support is not particularly limited. For example, a dip method in which the seed crystal is dispersed in a solvent such as water and the support is immersed in the dispersion to attach the seed crystal, or a seed crystal is attached. For example, a slurry mixed with a solvent such as water or a seed crystal itself may be coated on a support. The dip method is desirable for controlling the amount of seed crystals attached and producing a membrane composite with good reproducibility.

The solvent for dispersing the seed crystal is not particularly limited, but water is particularly preferable.
The amount of the seed crystal to be dispersed is not particularly limited, and is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, based on the total mass of the dispersion. Usually, it is 20 mass% or less, Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 4 mass% or less, Most preferably, it is 3 mass% or less.

If the amount of seed crystals to be dispersed is too small, the amount of seed crystals adhering to the support is small, so that a portion where no zeolite is generated on the support during hydrothermal synthesis is created, resulting in a defective film. there is a possibility. The amount of seed crystals adhering to the support by the dip method becomes almost constant when the amount of seed crystals in the dispersion is higher than a certain level, so if the amount of seed crystals in the dispersion is too large, the seed crystals are wasted. It is more disadvantageous in terms of cost.

It is desirable to deposit the seed crystal on the support by dipping or slurry coating, and after drying, form a zeolite membrane.
The amount of the seed crystal to be preliminarily deposited on the support is not particularly limited, and is usually 0.01 g or more, preferably 0.05 g or more, more preferably 0.1 g or more, by mass per 1 m ^{2 of} the base material. Usually, it is 100 g or less, preferably 50 g or less, more preferably 10 g or less, still more preferably 8 g or less.

  When the amount of the seed crystal is less than the lower limit, it becomes difficult to form a crystal, and there is a tendency that the film growth becomes insufficient or the film growth becomes uneven. In addition, when the amount of the seed crystal exceeds the upper limit, surface irregularities are increased by the seed crystal, or spontaneous nuclei are likely to grow due to the seed crystal falling from the support, thereby inhibiting film growth on the support. Sometimes. In either case, it tends to be difficult to form a dense zeolite membrane.

When a zeolite membrane is formed on a support by hydrothermal synthesis, there are no particular limitations on the method for immobilizing the support, and it can take any form such as vertical or horizontal placement. In this case, the zeolite membrane may be formed by a stationary method, or the aqueous reaction mixture may be stirred to form a zeolite membrane.
The temperature at which the zeolite membrane is formed is not particularly limited, but is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 ° C. or higher, usually 200 ° C. or lower, preferably 190 ° C. or lower, more preferably 180 ° C. It is as follows. If the reaction temperature is too low, the zeolite may be difficult to crystallize. If the reaction temperature is too high, a zeolite of a type different from the zeolite in the present invention may be easily generated.

  The heating time is not particularly limited, but is usually 1 hour or more, preferably 5 hours or more, more preferably 10 hours or more, and usually 10 days or less, preferably 5 days or less, more preferably 3 days or less, and even more preferably 2 Less than a day. If the reaction time is too short, the zeolite may be difficult to crystallize. If the reaction time is too long, a zeolite of a type different from the desired zeolite may be easily generated.

The pressure at the time of forming the zeolite membrane is not particularly limited, and the self-generated pressure generated when the aqueous reaction mixture placed in the closed vessel is heated to this temperature range is sufficient. Further, an inert gas such as nitrogen may be added as necessary.
The zeolite membrane composite obtained by hydrothermal synthesis is washed with water, then heated and dried. Here, the heat treatment means that the template is fired when heat is applied to dry the zeolite membrane composite or the template is used.

  The temperature of the heat treatment is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 200 ° C. or lower, preferably 150 ° C. or lower, for the purpose of drying. Moreover, when aiming at baking of a template, it is 350 degreeC or more normally, Preferably it is 400 degreeC or more, More preferably, it is 430 degreeC or more, More preferably, it is 480 degreeC or more, Usually 900 degrees C or less, Preferably it is 850 degrees C or less, and more Preferably it is 800 degrees C or less, More preferably, it is 750 degrees C or less.

When firing the template, if the temperature of the heat treatment is too low, the proportion of the remaining organic template tends to increase, and the zeolite has fewer pores, and therefore the permeability during separation and concentration. May decrease. If the heat treatment temperature is too high, the difference in coefficient of thermal expansion between the support and the zeolite becomes large, so the zeolite membrane may be easily cracked, and the denseness of the zeolite membrane may be lost, resulting in poor separation performance. .

The heating time is not particularly limited as long as the zeolite membrane is sufficiently dried or the template is calcined, and is preferably 0.5 hours or more, more preferably 1 hour or more. The upper limit is not particularly limited, and is usually within 200 hours, preferably within 150 hours, and more preferably within 100 hours. The heat treatment for the purpose of firing the template may be performed in an air atmosphere, but may be performed in an atmosphere to which an inert gas such as N ₂ or oxygen is added.

When hydrothermal synthesis is performed in the presence of an organic template, the obtained zeolite membrane composite can be washed with water, and then the organic template can be removed by, for example, heat treatment or extraction, preferably by heat treatment, that is, baking. Is appropriate.
It is desirable that the temperature increase rate during the heat treatment for firing the template is as slow as possible in order to reduce the difference in the thermal expansion coefficient between the support and the zeolite from causing cracks in the zeolite membrane. The temperature rising rate is usually 5 ° C./min or less, preferably 2 ° C./min or less, more preferably 1 ° C./min or less, and particularly preferably 0.5 ° C./min or less. Usually, it is 0.1 ° C./min or more in consideration of workability.

Moreover, it is necessary to control the temperature drop rate after firing in order to avoid cracks in the zeolite membrane. Similar to the rate of temperature increase, the slower the better. The temperature lowering rate is usually 5 ° C./min or less, preferably 2 ° C./min or less, more preferably 1 ° C./min or less, and particularly preferably 0.5 ° C./min or less. Usually, it is 0.1 ° C./min or more in consideration of workability.
The zeolite membrane may be ion exchanged as necessary. In the case of synthesizing using a template, ion exchange is usually performed after removing the template. Ions to be ion-exchanged include protons, alkali metal ions such as Na ⁺ , K ⁺ and Li ⁺ , Group 2 element ions such as Ca ²⁺ , Mg ²⁺ , Sr ²⁺ and Ba ^2+, and transition metals such as Fe and Cu. Examples include ions, ions of other metals such as Al, Ga, and Zn. Among these, protons, alkali metal ions such as Na ⁺ , K ⁺ , and Li ^+, and ions of Fe, Al, and Ga are preferable.

In ion exchange, the zeolite membrane after calcination (such as when a template is used) is replaced with an ammonium salt such as NH ₄ NO ₃ or NaNO ₃ or an aqueous solution containing ions to be exchanged, and in some cases an acid such as hydrochloric acid. What is necessary is just to perform by the method of washing with water after processing at the temperature of 100 degreeC. Furthermore, you may bake at 200 to 500 degreeC as needed.
The air permeation [L / (m ² · h)] of the porous support-zeolite membrane composite (zeolite membrane composite after heat treatment) thus obtained is usually 1400 L / (m ² · h) or less, preferably Is 1000 L / · BR> Im ² · h) or less, more preferably 700 L / (m ² · h) or less, more preferably 600 L / (m ² · h) or less, and even more preferably 500 L / (m ² · h). Hereinafter, it is particularly preferably 300 L / (m ² · h) or less, most preferably 200 L / (m ² · h) or less. In lower limit of the transmission amount is not particularly limited, it is generally 0.01L / ^(m 2 · h) or more, preferably 0.1L / ^(m 2 · h) or more, more preferably 1L / ^(m 2 · h) or higher is there.
Here, the air permeation amount is the air permeation amount [L / (m ² · h)] when the zeolite membrane composite is connected to a vacuum line having an absolute pressure of 5 kPa, as will be described later.

<Treatment with a material containing two or more Si atoms>
Subsequently, the formed zeolite is treated with a material containing two or more Si atoms. Thereby, the zeolite membrane surface is modified with a material containing two or more Si atoms such as a Si compound.

  For example, by forming a Si layer on the zeolite membrane surface, it is considered that the opening diameter is smaller than the pore diameter originally possessed by the zeolite and the separation performance can be improved. A material containing two or more Si atoms in the molecule often has a larger molecular size than a material having one Si atom in the molecule, and the aperture diameter can be effectively narrowed. In order to make the aperture diameter smaller, Si needs to form a bond with other Si via, for example, O atoms to form a Si network, but it is efficient for a material containing two or more Si atoms in the molecule. It is thought that processing will progress.

Further, by modifying the zeolite membrane surface with a material containing two or more Si atoms, an effect of closing fine defects present on the membrane surface may be obtained as a secondary effect. The defects are larger in size than the pores of the zeolite. For example, if the film has a CHA structure, it is considered to be larger than 3.8 mm, but the distance between Si of Si-0-Si bonds is TECHNO-COSMOS 2007 Mar. According to Vol.20, it is 3.1 Å, so two or more Si atoms are required to close the defect. For this reason, it is considered that defects are more efficiently blocked by treating with a material containing two or more Si atoms in the molecule than a molecule containing one Si.
Here, the material containing two or more Si atoms is a substance composed of two or more Si atoms and at least one atom other than Si atoms, and each atom is chemically coupled with any atom. Forming a natural bond.

  The number of Si atoms in the molecule is not particularly limited as long as it is 2 or more, and an appropriate one may be selected depending on the required opening diameter and the size of the defect to be blocked, but is preferably 3 or more, more preferably 4 or more. . Moreover, it is 120 or less normally, Preferably it is 90 or less, More preferably, it is 70 or less, Most preferably, it is 50 or less. When the Si in the molecule is within this range, the aperture diameter can be effectively narrowed and defects can be closed. If the number of Si atoms in the molecule is too small, the opening diameter may not be sufficiently small, and defects may not be sufficiently blocked. If the number of Si atoms in the molecule is too large, the pore entrance may be blocked, and the permeability of highly permeable gas and liquid components may be reduced. In addition, depending on the defect size, the molecules are large, so that they cannot enter the inside of the defect, and the defect may not be sufficiently blocked.

  The viscosity of the material containing 2 or more Si atoms is usually 0.5 mPas or more, preferably 2 mPas or more, and more preferably 3 mPas. Moreover, it is 150 mPas or less normally, Preferably it is 120 mPas or less, More preferably, it is 100 mPas or less, Most preferably, it is 80 mPas or less. If the viscosity is too low, the surface of the zeolite membrane has a Si compound that is immersed in a liquid containing at least a material containing two or more Si atoms, which will be described later, or heated by dropping or spraying a liquid containing a Si compound. May not stay on the surface. If the viscosity is too high, there may be a difference in the amount of Si compound adhering between the upper part and the lower part of the zeolite membrane at the time of pulling up or thereafter, and the uniform treatment may not be achieved. The viscosity can be adjusted as a solution containing a Si compound by adding a solvent.

  Specifically, as a material containing two or more Si atoms, an organosilicon compound having an alkoxysilane such as 1,1,3,3-tetramethoxy-1,3-dimethylpropanedisiloxane and a siloxane such as hexamethyldisiloxane Further, organosilicon compounds having silazane such as hexamethyldisilazane, silicate oligomers such as methyl silicate oligomer and ethyl silicate oligomer can be used. From the viewpoint of reactivity and the formation of a Si network, alkoxysilanes and silicate oligomers are preferred.

The method of treatment (hereinafter may be referred to as surface treatment) is not limited, but a zeolite membrane composite in a solution or dispersion containing a material containing 2 or more Si atoms (hereinafter also referred to as Si compound) There are dipping treatment for dipping, a dropping treatment for dropping a solution containing a material containing two or more Si atoms into the zeolite membrane composite, or a spraying treatment for spraying.
When surface treatment using a liquid such as immersion treatment is performed, the liquid used for the surface treatment is not particularly limited as long as the zeolite membrane composite can be treated under the condition of the surface treatment. It may be a solution to which a solvent is added, a liquid to which no solvent is added, or a sol or gel. Here, the solvent may be water or an organic solvent. In addition, solvents that are liquid under pressure at temperatures above the boiling point are also included in the solvent. The pressure in this case may be an autogenous pressure or a pressurization. Furthermore, the surface treatment liquid only needs to contain at least a Si compound, and as another element source (compound), for example, an Al compound may be contained.

When the immersion treatment is performed, the treatment may be performed by immersing in a liquid and forming a chemical bond with the Si compound in the immersed liquid. After immersion, the zeolite membrane is taken out of the liquid to the surface. Chemical bonds may be formed with the Si compound adhered, or chemical bonds may be formed both during and after immersion.
The case where water is used as a solvent in the immersion treatment will be described.

  When water is used as a solvent, the temperature of the solution is usually 20 ° C. or higher, preferably 60 ° C. or higher, more preferably 80 ° C. or higher, usually 200 ° C. or lower, preferably 150 ° C. or lower, more preferably 130 ° C. or lower. It is. If the temperature is too low, the progress of the dehydration condensation reaction and hydrolysis reaction performed between the Si compound and the film surface and the Si compound is insufficient, and the modification with the Si compound is not performed sufficiently, and the hydrophilicity of the film surface is not sufficiently improved. Sometimes. If the temperature is too high, a part of the zeolite may elute in water and the zeolite membrane may be broken.

  The immersion time is usually 1 hour or longer, preferably 4 hours or longer, more preferably 8 hours or longer, and is usually 100 hours or shorter, preferably 50 hours or shorter, more preferably 24 hours or shorter. If the immersion time is too short, the change of the film surface does not proceed sufficiently and a sufficient effect may not be obtained. If the soaking time is too long, the zeolite may partially dissolve in water and break the zeolite.

The pressure during the surface treatment is not particularly limited, and the atmospheric pressure or the self-generated pressure generated when the treatment solution placed in the sealed container is heated to the above temperature range is sufficient. Further, an inert gas such as nitrogen may be added as necessary.
The content of the Si compound in the solution is usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 20% by mass or less, preferably 10% by mass or less, more preferably as the concentration of the Si compound. Is 5% by mass or less. The concentration in the case of Si element is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and usually 10% by mass or less, preferably 5% by mass. % Or less, more preferably 2% by mass or less.

It is preferable that an acid or a base is present in the solution as a catalyst for the zeolite surface OH group and the Si compound, a dehydration condensation reaction between the Si compounds, and an alkoxy group hydrolysis reaction. Accordingly, the pH of the solution may be generally 0 to 12, preferably 0.5 to 10, more preferably about 1 to 8.
For example, by adding a basic substance such as NaOH, KOH, or amine in water, a trace amount of OH ⁻¹ ions may be actively present. In that case, the OH ⁻¹ ion concentration in the aqueous solution is usually 0. 0.01 mol / l or less, more preferably 0.005 mol / l or less, and usually 0.0001 mol / l or more, preferably 0.0005 mol / l or more, more preferably 0.001 mol / l or more. The presence of OH ^-1 ions in water makes it possible to obtain the same effect in a shorter time than when no OH ^-1 ions exist. If the OH ^-1 ion concentration in water is too high, the zeolite membrane is easily dissolved and broken, and strict control of the treatment time is required.

Examples of the acid present in the aqueous solution include organic acids such as carboxylic acid and sulfonic acid, and inorganic acids such as sulfuric acid and phosphoric acid. Among these, carboxylic acid and inorganic acid are particularly preferable.
As the carboxylic acid, for example, formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, maleic acid, phthalic acid, lactic acid, citric acid, acrylic acid and the like are preferable, formic acid, acetic acid and lactic acid are more preferable, and acetic acid is particularly preferable. . As the inorganic acid, for example, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid and the like are preferable, and sulfuric acid, nitric acid, and phosphoric acid are more preferable.

The concentration of the acidic substance in the aqueous solution is preferably 0.01 mol / l or more, more preferably 0.05 mol / l or more, further preferably 10 mol / l or less, and particularly preferably 1 mol / l or less.
The H ⁺ concentration is usually 1 × 10 ⁻¹⁰ mol / l or more, preferably 1 × 10 ⁻⁸ mol / l or more, more preferably 1 × 10 ⁻⁷ mol / l or more, and particularly preferably 1 × 10 ^{−5. 5} mol / l or more, usually 10 mol / l or less, preferably 5 mol / l or less, more preferably 1 mol / l or less.

A basic substance may coexist so that the H ⁺ concentration falls within the above range. Examples of the basic substance include NaOH, KOH, amine and the like.
Next, the immersion treatment using an organic solvent in the immersion treatment will be described.
In this case, the temperature of the solution is usually 20 ° C. or higher, preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and is usually 200 ° C. or lower, preferably 150 ° C. or lower, more preferably 110 ° C. or lower. If the temperature is too low, the progress of the dehydration condensation reaction and hydrolysis reaction performed between the Si compound and the membrane surface and the Si compound is insufficient, and the modification with the Si compound is not performed sufficiently, and the separation performance may not be sufficiently improved. . If the temperature is too high, the zeolite membrane may be broken.

  The immersion time is usually 0.5 hours or longer, preferably 1 hour or longer, more preferably 3 hours or longer, and usually 50 hours or shorter, preferably 24 hours or shorter, more preferably 10 hours or shorter. If the immersion time is too short, the change of the film surface does not proceed sufficiently and a sufficient effect may not be obtained. If the soaking time is too long, the zeolite may partially dissolve in water and break the zeolite.

The pressure during the surface treatment is not particularly limited, and atmospheric pressure can be performed under reflux conditions as necessary. Or you may process under the self-generated pressure which arises when the processing solution put into the airtight container was heated to the said temperature range as needed. Further, if necessary, an inert gas such as nitrogen may be added.
Examples of the organic solvent that can be used include nonpolar solvents such as toluene and hexane, alcohol solvents such as anisole and isopropyl alcohol, and polar solvents such as acetone. Of these, toluene and isopropyl alcohol are particularly preferable. These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

Further, when an organic solvent is used, water may be added into the system. The concentration of water that can be added is usually 0.001% by mass or more, preferably 0.05% by mass or more, more preferably 0.2% by mass or more, and usually 5% by mass or less, preferably 3% by mass or less, More preferably, it is 2 mass% or less.
The content of the Si compound in the solution is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and usually 10% by mass or less, as the Si element concentration. Preferably it is 5 mass% or less, More preferably, it is 2 mass% or less. The content of the Al compound is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and usually 10% by mass or less, preferably as Al element concentration. Is 5% by mass
Hereinafter, it is more preferably 1% by mass or less.

  In the surface treatment, the surface treatment can be performed by immersing in a liquid containing at least an Si compound, or dropping or spraying a liquid containing at least an Si compound, and then heating. In this case, it can also process without adding a solvent. In particular, when a silicate oligomer is used as the Si compound, it is not necessary to add a solvent. Even when the solvent is not further added, as another element source (compound), for example, an Al compound may be included.

  The immersion, dropping, or spraying temperature in this case is usually 1 ° C. or higher, preferably 5 ° C. or higher, more preferably 10 ° C. or higher, particularly preferably 15 ° C. or higher, and usually 200 ° C. or lower, preferably 150 ° C. or lower. More preferably, it is 130 degrees C or less, Most preferably, it is 100 degrees C or less, Most preferably, it is 80 degrees C or less. If the temperature is too low, the fluidity of the Si compound becomes low, and the Si compound does not uniformly adhere to the surface of the zeolite membrane composite, and the modification may become partial. If the temperature is too high, the reaction between the Si compounds proceeds quickly, and the adhesion to the surface of the zeolite membrane composite and the reaction may not proceed sufficiently.

The immersion time is usually 0.5 seconds or more, preferably 1 second or more, more preferably 2 seconds or more, particularly preferably 3 seconds or more, and usually 10 hours or less, preferably 7 hours or less, more preferably 5 hours or less. More preferably, it is 3 hours or less, particularly preferably 1 hour or less.
The pressure during the surface treatment is not particularly limited, and the atmospheric pressure or the self-generated pressure generated when the treatment solution placed in the sealed container is heated to the above temperature range is sufficient. Further, an inert gas such as nitrogen may be added as necessary.

  When the zeolite membrane composite is immersed in the liquid containing the Si compound after being immersed in the liquid containing the Si compound or when the liquid containing the Si compound is dropped or sprayed, the tubular zeolite membrane composite is immersed in the liquid containing the Si compound. In this case, it is desirable to prevent a large amount of Si compound from penetrating into the support by covering only the bottom or top and bottom with a silicon rubber stopper or Teflon (registered trademark) tape. By contacting the Si compound only on the surface of the zeolite membrane and preventing penetration into the support portion, the surface of the zeolite membrane can be efficiently surface-treated while maintaining a high permeation amount.

  The heating temperature after dipping or dropping or spraying the liquid containing the Si compound is usually 30 ° C. or higher, preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower. More preferably, it is 200 degrees C or less, Most preferably, it is 150 degrees C or less. When the temperature is lower than this range, the modification with the Si compound on the surface of the zeolite membrane may not be sufficiently immobilized. When the temperature is higher than this range, although depending on the boiling point of the Si compound, the Si compound volatilizes from the surface and the modification may not be performed sufficiently.

  When heating after immersion or dropping or spraying the liquid containing the Si compound, the heating time is usually 30 minutes or longer, preferably 1 hour or longer, more preferably 1.5 hours or longer, more preferably 2 hours or longer. Usually, it is 30 hours or less, preferably 25 hours or less, more preferably 20 hours or less, and further preferably 15 hours or less. When the time is shorter than this range, the modification with the Si compound on the zeolite membrane surface may not be sufficiently immobilized. When the time is longer than this range, the modification with the Si compound is heated more than sufficiently fixed, which is disadvantageous in terms of energy.

When heating after immersion or dropping or spraying a liquid containing a Si compound, it is preferable that water be present in the heating system. By coexisting water, the hydrolysis of alkoxysilane contained in the silicate oligomer or the like is likely to proceed, and the surface of the zeolite membrane can be sufficiently modified.
Heating after dipping or dropping or spraying the liquid containing the Si compound can be performed with a normal drier or the like, or the film after dipping may be placed in a sealed container and heated. A small amount of water may be allowed to coexist so as not to come into contact with the film when immersed in a sealed container or when the film containing the Si compound is dropped or sprayed.
The zeolite membrane composite thus produced has excellent characteristics as described above, and can be suitably used as a membrane separation means in the separation or concentration method of the present invention.

<Separation or concentration method>
In the separation or concentration method of the present invention, a porous support-zeolite membrane composite obtained by the above production method is brought into contact with a gas or liquid mixture comprising a plurality of components, and the mixture is highly permeable. It is characterized by concentrating a low-permeability substance by permeating and separating the substance, or by permeating a high-permeability substance from the mixture.

  In the separation or concentration method of the present invention, a gas or liquid mixture composed of a plurality of components is brought into contact with one side of the support side or the zeolite membrane side through an inorganic porous support provided with a zeolite membrane, and the opposite side thereof. By setting the pressure at a lower pressure than the side in contact with the mixture, a substance having a high permeability to the zeolite membrane (a substance in the mixture having a relatively high permeability) is selectively selected from the mixture, that is, the main substance of the permeate. Permeate as a component. Thereby, a highly permeable substance can be separated from the mixture. As a result, the specific component can be separated and recovered or concentrated by increasing the concentration of the specific component (substance in the mixture having relatively low permeability) in the mixture.

The mixture to be separated or concentrated is not particularly limited as long as it is a gas or liquid mixture composed of a plurality of components that can be separated or concentrated by the porous support-zeolite membrane composite in the present invention. It may be a mixture.
When the mixture to be separated or concentrated is, for example, a mixture of an organic compound and water (hereinafter sometimes referred to as “hydrous organic compound”), water is usually highly permeable to the zeolite membrane. So water is separated from the mixture and the organic compound is concentrated in the original mixture. A separation or concentration method called a pervaporation method (permeation vaporization method) or a vapor permeation method (vapor permeation method) is one embodiment of the method of the present invention. The pervaporation method is a separation or concentration method in which a liquid mixture is directly introduced into a separation membrane, so that a process including separation or concentration can be simplified.

  The vapor permeation method is a separation / concentration method in which a liquid mixture is vaporized and then introduced into a separation membrane. Therefore, the vapor permeation method can be used in combination with a distillation apparatus or for separation at higher temperature and pressure. In addition, the vapor permeation method introduces the liquid mixture after vaporizing it into the separation membrane, reducing the effects of impurities contained in the supply liquid and substances that form aggregates and oligomers in the liquid state on the membrane. can do. The inorganic porous support-zeolite membrane composite obtained by the present invention can be suitably used for any method.

  In addition, when performing separation at a high temperature by the vapor permeation method, in general, the higher the temperature and the higher the concentration of the component having low permeability in the mixture, for example, in the case of a mixture of an organic compound and water, Although the separation performance decreases as the concentration of the compound increases, the inorganic porous support-zeolite membrane composite obtained by the present invention has high separation performance even at high temperatures and even when the concentration of the low-permeability component in the mixture is high. Can be expressed. In general, the vapor permeation method separates the liquid mixture after vaporizing it, and therefore usually the separation is performed under harsher conditions than the pervaporation method. Therefore, durability of the membrane composite is also required. The inorganic porous support-zeolite membrane composite obtained by the present invention is suitable for the vapor permeation method because it has durability capable of being separated even under high temperature conditions.

  The porous support-zeolite membrane composite has specific physicochemical properties, so that not only when the concentration of the low-permeability component in the mixture is high, but also when the concentration of the low-permeability component is low However, it exhibits high permeation performance, selectivity, and performance as a separation membrane with excellent durability. For example, a mixture of an organic compound and water exhibits high selectivity regardless of the concentration of water. That is, the zeolite membrane composite having specific physicochemical properties of the present invention is suitable for separation and concentration of a mixture in a wide concentration range.

The high permeation performance here indicates a sufficient throughput, for example, a permeation flux of a substance that permeates the membrane is, for example, a mixture of acetic acid and water having a water content of 10% by mass at 90 ° C. at 1 atm ( When permeated with a pressure difference of 1.01 × 10 ⁵ Pa), 0.5 kg / (m ² · h) or more, preferably 1 kg / (m ² · h) or more, more preferably 1.5 kg / (m ² · h) or more. The upper limit of the permeation flux is not particularly limited, and is usually 20 kg / (m ² · h) or less, preferably 15 kg / (m ² · h) or less.

Further, when a mixture of phenol and water having a water content of 10% by mass is permeated at 75 ° C. with a pressure difference of 1 atm (1.01 × 10 ⁵ Pa), the permeation flux of the substance that permeates the membrane is It means 0.5 kg / (m ² · h) or more, preferably 1 kg / (m ² · h) or more, more preferably 3 kg / (m ² · h) or more. The upper limit of the permeation flux is not particularly limited, and is usually 30 kg / (m ² · h) or less, preferably 20 kg / (m ² · h) or less.

In addition, when a mixture of 2-propanol or N-methyl-2-pyrrolidone having a water content of 30% by mass and water is permeated at 70 ° C. with a pressure difference of 1 atm (1.01 × 10 ⁵ Pa), 1 kg / (M ² · h) or more, preferably 3 kg / (m ² · h) or more, more preferably 5 kg / (m ² · h) or more. The upper limit of the permeation flux is not particularly limited, and is usually 20 kg / (m ² · h) or less, preferably 15 kg / (m ² · h) or less.

Further, high transmission performance can be expressed by permeance (also referred to as “permeance”). Permeance refers to the pressure normalized flux, divided by the product of membrane area, time, and water partial pressure difference. When expressed in units of permeance, for example, a mixture of acetic acid and water having a water content of 10% by mass permeated at 90 ° C. with a pressure difference of 1 atm (1.01 × 10 ⁵ Pa). Usually, 3 × 10 ⁻⁷ mol / (m ² · s · Pa) or more, preferably 5 × 10 ⁻⁷ mol / (m ² · s · Pa) or more, more preferably 1 × 10 ⁻⁶ mol / (m ² · s · Pa) or more. The upper limit of permeance is not particularly limited, and is usually 1 × 10 ⁻⁴ mol / (m ² · s · Pa) or less, preferably 5 × 10 ⁻⁵ mol / (m ² · s · Pa) or less.

Further, when a mixture of phenol and water having a water content of 10% by mass is permeated at 75 ° C. with a pressure difference of 1 atm (1.01 × 10 ⁵ Pa), and 2-propanol having a water content of 30% by mass or When a mixture of N-methyl-2-pyrrolidone and water is permeated at 70 ° C. with a pressure difference of 1 atm (1.01 × 10 ⁵ Pa), the water permeance is usually 3 × 10 ⁻⁷ mol / mol. (M ² · s · Pa) or more, preferably 5 × 10 ⁻⁷ mol / (m ² · s · Pa) or more, more preferably 1 × 10 ⁻⁶ mol / (m ² · s · Pa) or more, in particular It is preferably 2 × 10 ⁻⁶ mol / (m ² · s · Pa) or more. The upper limit of permeance is not particularly limited, and is usually 1 × 10 ⁻⁴ mol / (m ² · s · Pa) or less, preferably 5 × 10 ⁻⁵ mol / (m ² · s · Pa) or less.

Selectivity is represented by a separation factor. The separation factor is the following index representing the selectivity generally used in membrane separation.
Separation factor = (P _α / P _β ) / (F _α / F _β )
[Where P _α is the mass percent concentration of the main component in the permeate, P _β is the mass percent concentration of the subcomponent in the permeate, and F _α is the mass of the component that is the main component in the permeate in the mixture to be separated. The percent concentration, _Fβ, is the mass percent concentration in the separated mixture of components that are subcomponents in the permeate. ]
The separation factor is, for example, when a mixture of acetic acid and water having a water content of 10% by mass is permeated at 90 ° C. with a pressure difference of 1 atm (1.01 × 10 ⁵ Pa), and for example having a water content of 10% by mass. When a mixture of phenol and water is permeated at 75 ° C. with a pressure difference of 1 atm (1.01 × 10 ⁵ Pa), and for example 2-propanol or N-methyl-2-pyrrolidone with a water content of 30% by weight When the mixture of water and water is permeated at 70 ° C. with a pressure difference of 1 atm (1.01 × 10 ⁵ Pa), it is usually 2000 or more, preferably 4000 or more, more preferably 10,000 or more, particularly preferably 20000 or more. It is. The upper limit of the separation factor is the case where only water is completely transmitted. In this case, the separation factor is infinite, but is preferably 10000000 or less, more preferably 1000000 or less.

As a water-containing organic compound, the water content may be adjusted in advance by an appropriate water adjustment method. Examples of the moisture adjustment method include methods known per se, such as distillation, pressure swing adsorption (PSA), temperature swing adsorption (TSA), and desiccant system.
Further, water may be further separated from the water-containing organic compound from which water has been separated by the zeolite membrane composite. Thereby, water can be separated to a higher degree and the water-containing organic compound can be further concentrated.

  Examples of organic compounds include carboxylic acids such as acetic acid, acrylic acid, propionic acid, formic acid, lactic acid, oxalic acid, tartaric acid, benzoic acid, sulfonic acid, sulfinic acid, habituric acid, uric acid, phenol, enol, and diketone type compounds. Organic acids such as thiophenol, imide, oxime, aromatic sulfonamide, primary and secondary nitro compounds; alcohols such as methanol, ethanol and isopropanol (2-propanol); ketones such as acetone and methyl isobutyl ketone Aldehydes such as acetaldehyde, ethers such as dioxane and tetrahydrofuran; organic compounds containing nitrogen such as amides such as dimethylformamide and N-methylpyrrolidone (N-containing organic compounds), esters such as acetates and acrylates Na And the like.

Among these, the effect of the inorganic porous support-zeolite membrane composite stands out when separating the organic acid from a mixture of organic acid and water that can take advantage of both the characteristics of molecular sieve and hydrophilicity. To express. A preferred example is a mixture of carboxylic acids and water, particularly preferably separation of acetic acid and water.
In addition, the organic substance in the case of separating the organic substance and water from the mixture of the organic substance other than the organic acid and water preferably has 2 or more carbon atoms, and more preferably 3 or more carbon atoms.

Among these organic substances other than organic acids, organic compounds containing at least one selected from alcohols, ethers, ketones, aldehydes, and amides are particularly desirable. Among these organic compounds, those having 2 to 10 carbon atoms are preferable, and those having 3 to 8 carbon atoms are more preferable.
Moreover, as an organic compound, the high molecular compound which can form a mixture (mixed solution) with water may be sufficient. Examples of such a polymer compound include those having a polar group in the molecule, for example, polyols such as polyethylene glycol and polyvinyl alcohol; polyamines; polysulfonic acids; polycarboxylic acids such as polyacrylic acid; Carboxylic acid esters; modified polymer compounds obtained by modifying polymers by graft polymerization, etc .; copolymerized polymer compounds obtained by copolymerization of nonpolar monomers such as olefins and polar monomers having polar groups such as carboxyl groups And the like.

  The water-containing organic compound may be a mixture that forms an azeotrope, such as a mixture of water and phenol. In the separation of a mixture that forms an azeotrope, water is selectively used rather than separation by distillation. It is preferable in terms of efficient separation. Specifically, a mixture of alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol and water; a mixture of esters and water such as ethyl acetate, ethyl acrylate and methyl methacrylate; A mixture of carboxylic acids such as formic acid, isobutyric acid, valeric acid and water; a mixture of aromatic organic substances such as phenol and aniline and water; a mixture of nitrogen-containing compounds such as acetonitrile and acrylonitrile and water, and the like.

  Further, the water-containing organic compound may be a mixture of water and a polymer emulsion. Here, the polymer emulsion is a mixture of a surfactant and a polymer, which is usually used for adhesives, paints, and the like. Examples of the polymer used in the polymer emulsion include polyvinyl acetate, polyvinyl alcohol, acrylic resin, polyolefin, olefin-polar monomer copolymer such as ethylene-vinyl alcohol copolymer, polystyrene, polyvinyl ether, polyamide, polyester, and cellulose. Thermoplastic resins such as derivatives; thermosetting resins such as urea resins, phenol resins, epoxy resins, polyurethanes; rubbers such as natural rubber, polyisoprene, polychloroprene, butadiene copolymers such as styrene-butadiene copolymers, etc. Can be mentioned. As the surfactant, a known one may be used.

In the method of the present invention, the mixture to be separated or concentrated may be a mixed gas, such as carbon dioxide, oxygen, nitrogen, methane, ethane, ethylene, propane, propylene, normal butane, isobutane, 1 Examples include those containing at least one component selected from -butene, 2-butene, isobutene, sulfur hexafluoride, helium, carbon monoxide, nitrogen monoxide, water and the like. Among these gas components, the gas component with high permeance passes through the zeolite membrane complex and is separated, and the gas component with low permeance is concentrated on the supply gas side.

  In particular, the mixed gas preferably contains at least one gas molecule having a kinetic diameter of 4 mm or less. According to the present invention, particularly in a gas containing at least one of components having a kinetic diameter of 4 mm or less as a component, a component having low permeability due to separation of a component having high permeability or permeation of a component having high permeability. Can be concentrated with high separation performance.

The mixed gas includes at least two components of the above components. In this case, the two components are preferably a combination of a component having a high permeance and a component having a low permeance.
Here, permeance (also referred to as “permeance”) is obtained by dividing the amount of the permeated substance by the product of the membrane area, time, and the partial pressure difference between the permeating substance supply side and the permeating side. [Mol · (m ² · s · Pa) ⁻¹ ].

  Specific examples of the mixed gas include a mixed gas containing oxygen, a mixed gas containing methane and helium, a mixed gas containing carbon dioxide and nitrogen, air, natural gas, combustion gas, coke oven gas, It can be used for separation or concentration of biogas such as land file gas generated from a landfill, and steam reformed gas of methane produced and discharged in the petrochemical industry.

When a mixed gas containing oxygen is used, it is preferably used to separate oxygen from the mixed gas or to allow oxygen to permeate from the mixed gas. Examples of the mixed gas containing oxygen include air.
When a mixed gas containing methane and helium is used, it is preferably used to separate helium from the mixed gas or to transmit helium from the mixed gas. Examples of the mixed gas containing methane and helium include natural gas.

When a mixed gas containing carbon dioxide and nitrogen is used, it is preferably used to separate carbon dioxide from the mixed gas or to allow carbon dioxide to permeate from the mixed gas. Examples of the mixed gas containing carbon dioxide and nitrogen include combustion gases.
Oxygen is highly permeable to the zeolite membrane used in the present invention. Therefore, by bringing the mixed gas containing oxygen into contact with the zeolite membrane and separating it, the oxygen-containing mixed gas, for example, the oxygen concentration in the air can be increased, and a high-oxygen-concentrated mixed gas can be produced. it can.

For example, when air is used as the mixed gas, the oxygen concentration can be 30% or more, and further 35% or more.
Moreover, helium has high permeability with respect to the zeolite membrane used in the present invention. Therefore, helium can be separated by contacting the zeolite membrane with, for example, natural gas containing helium or methane.

In addition, carbon dioxide has high permeability with respect to the zeolite membrane used in the present invention. Therefore, carbon dioxide can be separated by bringing the zeolite membrane into contact with, for example, a combustion gas containing carbon dioxide or nitrogen.
The conditions for separating and concentrating these mixed gases may be those known per se according to the target gas species, composition, and the like.

As a form of the separation membrane module having the zeolite membrane composite used for the separation of the mixed gas, a flat membrane type, a spiral type, a hollow fiber type, a cylindrical type, a honeycomb type, and the like can be considered, and an optimum form according to the application target is provided. To be elected.
One example is a cylindrical separation membrane module.
In FIG. 1, a cylindrical zeolite membrane composite 1 is installed in a thermostatic chamber (not shown) in a state of being stored in a pressure vessel 2 made of stainless steel. A temperature control device is attached to the thermostat so that the temperature of the sample gas can be adjusted.

  One end of the cylindrical zeolite membrane composite 1 is sealed with a cylindrical end pin 3. The other end is connected by a connecting portion 4, and the other end of the connecting portion 4 is connected to the pressure vessel 2. An inner side of the cylindrical zeolite membrane composite and a pipe 11 for discharging the permeated gas 8 are connected via the connection portion 4, and the pipe 11 extends to the outside of the pressure-resistant vessel 2. A pressure gauge 5 for measuring the pressure on the supply side of the sample gas is connected to the pressure vessel 2. Each connection part is connected with good airtightness.

In FIG. 1, a cylindrical zeolite membrane composite 1 is installed in a thermostatic chamber (not shown) in a state of being stored in a pressure vessel 2 made of stainless steel. A temperature control device is attached to the thermostat so that the temperature of the sample gas can be adjusted.
One end of the cylindrical zeolite membrane composite 1 is sealed with a circular end pin 3. The other end is connected by a connection portion 4, and the other end of the connection portion 4 is connected to the pressure vessel 2. A pipe 11 that discharges the permeate gas 8 and the inside of the cylindrical zeolite membrane composite 1 are connected via a connecting portion 4, and the pipe 11 extends to the outside of the pressure vessel 2. A pipe 12 for supplying the sweep gas 9 is inserted into the zeolite membrane composite 1 via the pipe 11. Furthermore, a pressure gauge 5 for measuring the pressure on the supply side of the sample gas (mixed gas) and a back pressure valve 6 for adjusting the pressure on the supply side are connected to any part that communicates with the pressure vessel 2. Each connection part is connected with good airtightness.

A sample gas (supply gas 7) is supplied between the pressure vessel 2 and the zeolite membrane composite 1 at a constant flow rate, and the pressure on the supply side is made constant by the back pressure valve 6. The gas passes through the membrane 1 according to the partial pressure difference between the inside and outside of the membrane 1 and is discharged through the pipe 11.
The gas separation temperature from the mixed gas is 0 to 500 ° C. Considering the separation characteristics of the membrane, the temperature is preferably within the range of room temperature to 100 ° C.

Hereinafter, the present invention will be described more specifically based on experimental examples (Examples and Comparative Examples). However, the present invention is not limited to the following experimental examples unless it exceeds the gist.
In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the value of the upper limit or the lower limit. It may be a range defined by a combination of values of the following examples or values of the examples.

Example 1
A membrane complex of an inorganic porous support and a CHA-type zeolite membrane was prepared as follows by directly hydrothermally synthesizing CHA-type zeolite on the inorganic porous support.
The following was prepared as a reaction mixture for hydrothermal synthesis.
Aluminum hydroxide (containing 53.5% by mass of Al ₂ O ₃ , manufactured by Aldrich) mixed with 0.29 g of lithium hydroxide monohydrate, 13.9 g of 1 mol / L-KOH aqueous solution, and 104.0 g of water 1 .32 g was added and stirred to dissolve to obtain a transparent solution. As an organic template, 2.35 g of an aqueous solution of N, N, N-trimethyl-1-adamantanammonium hydroxide (hereinafter referred to as “TMADAOH”) (containing 25% by mass of TMADAOH, manufactured by Seychem) was added, and colloidal. 10.4 g of silica (Snowtech-40 manufactured by Nissan Chemical Co., Ltd.) was added and stirred for 2 hours to obtain a reaction mixture.

The composition (molar ratio) of this reaction mixture was SiO ₂ / Al ₂ O ₃ / LiOH / KOH / H ₂
O / TMADAOH = 1 / 0.1 / 0.1 / 0.2 / 100 / 0.04 and SiO ₂ / Al ₂ O ₃ = 10.
As the inorganic porous support, a mullite tube (outer diameter 12 mm, inner diameter 9 mm) was cut to a length of 80 mm, washed with an ultrasonic cleaner and dried.

As a seed crystal, the gel composition (molar ratio) of SiO ₂ / Al ₂ O ₃ / NaOH / KOH / H ₂ O / TMADAOH = 1 / 0.033 / 0.1 / 0.06 / 40 / 0.07 is 160. A CHA-type zeolite crystallized by hydrothermal synthesis at 2 ° C. for 2 days was used. The support was immersed in a dispersion obtained by dispersing the seed crystal in 1% by mass of water for a predetermined time, and then dried at 100 ° C. for 5 hours to adhere the seed crystal. The mass of the attached seed crystal was 1.9 g / m ² .

  A total of three of the support to which the seed crystal was attached in this way and two supports to which the seed crystal was similarly attached was perpendicular to the Teflon (registered trademark) inner cylinder (200 ml) containing the reaction mixture. The autoclave was sealed by dipping in the direction, and was heated in a stationary state at 160 ° C. for 48 hours under an autogenous pressure. After the elapse of a predetermined time, the support-zeolite membrane complex was taken out of the reaction mixture after being allowed to cool, and dried at 100 ° C. for 2 hours or more after washing.

The zeolite membrane composite before template firing was fired in an electric furnace at 500 ° C. for 5 hours. The mass of the CHA-type zeolite crystallized on the support, which was determined from the difference between the mass of the membrane composite after firing and the mass of the support, was 146 g / m ² .
The zeolite membrane composite thus obtained was surface treated as follows. A solution in which methyl silicate oligomer (MKC (registered trademark) silicate, MS-51, manufactured by Mitsubishi Chemical Corporation) is mixed at 30% by mass with isopropyl alcohol is capped with an air hole on the upper end surface, and the lower end surface The zeolite membrane composite with plugs without holes was soaked at room temperature for about 5 seconds and pulled up. Then air-dried, and a Teflon (registered trademark) inner cylinder filled with about 1 g of water at the bottom, standing vertically using a jig, sealing the autoclave, heating at 100 ° C. for 6 hours, and after a predetermined time, After allowing to cool, the zeolite membrane composite was taken out and further heat-treated at 150 ° C. for 1 h.

This zeolite membrane composite, _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane itself was measured by SEM-EDX is 33.6, _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane surface as measured by XPS 200 It can be seen that the ratio of Si on the surface is high.
Using the obtained inorganic porous support-CHA type zeolite membrane composite, single component gas permeation evaluation was performed at 50 ° C. by the following method. The obtained CO ₂ / N ₂ , He / CH ₄ permeance ratio, and He permeance are shown in Table 1. The CO ₂ / N ₂ permeance ratio was 35 and the He / CH ₄ permeance ratio was 145, indicating that the membrane had high separation performance.

Using the obtained inorganic porous support-CHA type zeolite membrane composite, air separation was evaluated at 50 ° C. using the apparatus shown in FIG. The obtained separation results are shown in Table 1. The oxygen concentration after separation was 44%, and it was found that a high concentration of oxygen could be obtained with high separation performance.
In the above examples, the physical properties and separation performance were measured as follows.

<Measurement of physical properties and separation performance>
(1) SEM-EDX measurement SEM-EDX measurement of the zeolite membrane was performed under the following conditions.
-Device name: SEM: FE-SEM Hitachi: S-4800
EDX: EDAX Genesis
・ Acceleration voltage: 10 kV
The entire field of view (25 μm × 18 μm) at a magnification of 5000 was scanned, and X-ray quantitative analysis was performed.
By this SEM-EDX measurement, the SiO2 / Al2O3 molar ratio of the produced zeolite membrane itself was determined. In the SEM-EDX measurement, information on only the zeolite membrane of several microns can be obtained by setting the X-ray irradiation energy to about 10 kV.

(2) XPS measurement XPS (X-ray photoelectron spectroscopy) measurement of the zeolite membrane surface was performed under the following conditions.
・ Device name: Quantum2000 manufactured by PHI
-X-ray source: Monochromatic Al-Kα, output 16 kV-34 W (X-ray generation area 170 μmφ)
・ Charge neutralization: Combined use of electron gun (5μA) and ion gun (2V) ・ Spectroscopic system: Pulse energy 187.85 eV @ Wide spectrum
117.40 eV @ narrow spectrum (Al2p)
29.35 eV @ narrow spectrum (C1s, O1s, Si
2p)
Measurement area: Spot irradiation (irradiation area <340 μmφ)
・ Extraction angle: 45 ° (from the surface)
By this XPS measurement, the SiO ₂ / Al ₂ O ₃ molar ratio on the surface of the produced zeolite membrane was determined.

(3) Single component gas permeation evaluation The single component gas permeation test was performed as follows using the apparatus schematically shown in FIG. The sample gases used were carbon dioxide (purity 99.9%, manufactured by High Pressure Gas Industries), methane (purity 99.999%, manufactured by Japan Fine Products), nitrogen (purity 99.99%, manufactured by Toho Oxygen Industries), Helium (purity 99.99, manufactured by Japan Helium Center).

In FIG. 1, a cylindrical zeolite membrane composite 1 is installed in a thermostatic chamber (not shown) in a state of being stored in a pressure vessel 2 made of stainless steel. A temperature control device is attached to the thermostat so that the temperature of the sample gas can be adjusted.
One end of the cylindrical zeolite membrane composite 1 is sealed with a cylindrical end pin 3. The other end is connected by a connecting portion 4, and the other end of the connecting portion 4 is connected to the pressure vessel 2. An inner side of the cylindrical zeolite membrane composite and a pipe 11 for discharging the permeated gas 8 are connected via the connection portion 4, and the pipe 11 extends to the outside of the pressure-resistant vessel 2. A pressure gauge 5 for measuring the pressure on the supply side of the sample gas is connected to the pressure vessel 2. Each connection part is connected with good airtightness.
In FIG. 1, a cylindrical zeolite membrane composite 1 is installed in a thermostatic chamber (not shown) in a state of being stored in a pressure vessel 2 made of stainless steel. A temperature control device is attached to the thermostat so that the temperature of the sample gas can be adjusted.

  One end of the cylindrical zeolite membrane composite 1 is sealed with a circular end pin 3. The other end is connected by a connection portion 4, and the other end of the connection portion 4 is connected to the pressure vessel 2. A pipe 11 that discharges the permeate gas 8 and the inside of the cylindrical zeolite membrane composite 1 are connected via a connecting portion 4, and the pipe 11 extends to the outside of the pressure vessel 2. Further, a pipe (sweep gas introduction pipe) 12 for supplying the sweep gas 9 is inserted into the zeolite membrane composite 1 via the pipe 11. Furthermore, a pressure gauge 5 for measuring the pressure on the supply side of the sample gas and a back pressure valve 6 for adjusting the pressure on the supply side are connected to any part that communicates with the pressure vessel 2. Each connection part is connected with good airtightness.

In the apparatus of FIG. 1, when performing a single component gas permeation test, a sample gas (supply gas 7) is supplied between the pressure-resistant container 2 and the zeolite membrane complex 1 at a constant flow rate, and is supplied by a back pressure valve 6. The pressure of is constant. The flow rate of the exhaust gas 10 discharged from the pipe 11 is measured.
More specifically, in order to remove components such as moisture and air, the sample temperature and the supply gas of the zeolite membrane composite 1 are supplied after drying at a temperature higher than the measurement temperature and purging with a supply gas to be exhausted or used. The flow rate of the sample gas (permeate gas 8) permeated through the zeolite membrane composite 1 was measured after the permeate gas flow rate was stabilized with the differential pressure between the 7 side and the permeate gas 8 side constant, and the gas permeance [mol · (M ² · s · Pa) ⁻¹ ] is calculated. As the pressure for calculating the permeance, a pressure difference (differential pressure) between the supply side and the permeation side of the supply gas is used.

Based on the measurement result, the ideal separation coefficient α is calculated by the following equation (1).
α = (Q ₁ / Q ₂ ) / (P ₁ / P ₂ ) (1)
Wherein (1), _{Q 1} and _{Q 2,} respectively, the amount of transmission of high permeability gas and low permeability gas indicates ^{[mol · (m 2 · s} ) -1], P 1 and _{P 2} Respectively show the pressure [Pa] of the highly permeable gas and the low permeable gas that are the supply gas. ]

(4) Mixed gas permeation test The mixed gas permeation test of the zeolite membrane composite was performed as follows using the apparatus schematically shown in FIG. The sample gas used is compressed air.
In FIG. 1, a cylindrical zeolite membrane composite 1 is installed in a thermostatic chamber (not shown) in a state of being stored in a pressure vessel 2 made of stainless steel. A temperature control device is attached to the high-temperature bath so that the temperature of the sample gas can be adjusted.
One end of the cylindrical zeolite membrane composite 1 is sealed with a circular end pin 3. The other end is connected by a connection portion 4, and the other end of the connection portion 4 is connected to the pressure vessel 2. A pipe 11 that discharges the permeate gas 8 and the inside of the cylindrical zeolite membrane composite are connected via the connection portion 4, and the pipe 11 extends to the outside of the pressure vessel 2. A pipe 12 for supplying the sweep gas 9 is inserted into the zeolite membrane composite 1 via the pipe 11. Further, a pressure gauge 5 for measuring the pressure on the supply side of the sample gas and a back pressure valve 6 for adjusting the pressure on the supply side are connected to the pressure vessel 2. Each connection part is connected with good airtightness.

  In the apparatus of FIG. 1, the sample gas (supply gas 7) is supplied between the pressure-resistant container 2 and the zeolite membrane composite 1 at a constant flow rate, and the pressure on the supply side is made constant by the back pressure valve 6. On the other hand, the sweep gas 9 is caused to flow from the pipe 12 to the inside of the zeolite membrane complex 1, and the flow rate of the exhaust gas discharged from the pipe 11 (the exhaust gas of the sweep gas 9 and the accompanying permeated gas 8) is measured. The exhaust gas is collected and component analysis is performed by gas chromatography.

At this time, the flow velocity of each component gas that has passed through the zeolite membrane composite 1 is measured as described above, and the gas permeation [mol · (m ² · s) ⁻¹ ] is calculated.
Based on the measurement result, the separation coefficient α ′ is calculated by the following formula (2).
α ′ = (Q ′ ₁ / Q ′ ₂ ) / (P ′ ₁ / P ′ ₂ ) (2)
Wherein (2), Q _'1 and Q' _2, respectively, represents the permeability of the high permeability gas and low permeability gas ^{[mol · (m 2 · s} ) -1], P '1 And P ′ ₂ indicate the partial pressure [Pa] of the highly permeable gas and the low permeable gas in the supply gas, respectively. ]

(Comparative Example 1)
In the same manner as in Example 1, an inorganic porous support-CHA type zeolite membrane composite was prepared. The mass of the attached seed crystal is 0.7 g / m ² , and the mass of the CHA-type zeolite crystallized on the support determined from the difference between the mass of the membrane composite after firing and the mass of the support is 140 g / m ^2. It was m ^2. The zeolite membrane composite thus obtained was surface treated as follows. Tetraethoxysilane was plugged with a plug having an air hole on the upper end face and a plug having no hole on the lower end face, soaked at room temperature for about 5 seconds and pulled up. Then air-dried, and a Teflon (registered trademark) inner cylinder filled with about 1 g of water at the bottom, standing vertically using a jig, sealing the autoclave, heating at 100 ° C. for 6 hours, and after a predetermined time, After allowing to cool, the zeolite membrane composite was taken out and further heat-treated at 150 ° C. for 1 h.

For this zeolite membrane composite, the SiO ₂ / Al ₂ O ₃ molar ratio on the zeolite membrane surface measured by XPS was 23.0, and treatment with tetraethoxysilane increased the proportion of Si on the surface, increasing the value. It is thought that.
Using the obtained inorganic porous support-CHA-type zeolite membrane composite, single component gas permeation evaluation was performed at 50 ° C. in the same manner as in Example 1. The obtained CO ₂ / N ₂ , He / CH ₄ permeance ratio, and He permeance are shown in Table 1. The CO ₂ / N ₂ permeance ratio was 17, and the He / CH ₄ permeance ratio was 17.

  Using the obtained inorganic porous support-CHA type zeolite membrane composite, air separation was evaluated at 50 ° C. using the apparatus shown in FIG. The obtained separation results are shown in Table 1. The oxygen concentration after separation was 27%, and the concentration was not sufficient.

(Example 2)
The inorganic porous support CHA-type zeolite membrane composite was prepared as follows by directly hydrothermally synthesizing CHA-type zeolite on the inorganic porous support.
The following was prepared as a reaction mixture for hydrothermal synthesis.
Aluminum hydroxide (containing 53.5% by mass of Al ₂ O ₃ , manufactured by Aldrich) mixed with 10.5 g of 1 mol / L-NaOH aqueous solution, 7.0 g of 1 mol / L-KOH aqueous solution and 100.5 g of water 88 g was added, stirred and dissolved to obtain a transparent solution. As an organic template, 2.36 g of an aqueous solution of N, N, N-trimethyl-1-adamantanammonium hydroxide (hereinafter referred to as “TMADAOH”) (containing 25% by mass of TMADAOH, manufactured by Seychem) was added, and colloidal. 10.5 g of silica (Snowtech-40, manufactured by Nissan Chemical Industries, Ltd.) was added and stirred for 2 hours to obtain a reaction mixture.

The composition (molar ratio) of this reaction mixture was SiO ₂ / Al ₂ O ₃ / NaOH / KOH / H ₂ O / TMADAOH = 1 / 0.066 / 0.15 / 0.1 / 100 / 0.04, SiO 2 ₂ / Al ₂ O ₃ = 15.
As the inorganic porous support, a porous alumina tube (outer diameter 12 mm, inner diameter 9 mm) was cut to a length of 80 mm, washed with an ultrasonic cleaner and dried.

As a seed crystal, the gel composition (molar ratio) of SiO ₂ / Al ₂ O ₃ / NaOH / KOH / H ₂ O / TMADAOH = 1 / 0.033 / 0.1 / 0.06 / 40 / 0.07 is 160. A CHA-type zeolite crystallized by hydrothermal synthesis at 2 ° C. for 2 days was used. The seed crystal grain size was about 1 μm.
The support was immersed in a dispersion obtained by dispersing the seed crystal in 1% by mass of water for a predetermined time, and then dried at 100 ° C. for 5 hours to adhere the seed crystal. The mass of the attached seed crystal was 0.9 g / m ² .

The support to which the seed crystal was attached was immersed in a Teflon (registered trademark) inner cylinder (200 ml) containing the above reaction mixture in the vertical direction to seal the autoclave, and left standing at 160 ° C. for 48 hours. Heated under autogenous pressure. After the elapse of a predetermined time, after cooling, the support-zeolite membrane complex was taken out of the reaction mixture, washed and dried at 100 ° C. for 5 hours or more.
The zeolite membrane composite before template firing was fired in an electric furnace at 500 ° C. for 5 hours. The mass of the CHA-type zeolite crystallized on the support, which was determined from the difference between the mass of the membrane composite after firing and the mass of the support, was 130 g / m ² .

The air permeation amount of the zeolite membrane composite after calcination was 60 L / (m ² · h).
When XRD of the produced membrane was measured, it was found that CHA-type zeolite was produced.
From the XRD pattern, (the intensity of the peak near 2θ = 17.9 °) / (the intensity of the peak near 2θ = 20.8 °) = 3.5, and the XRD of the CHA-type zeolite of the powder used for the seed crystal The peak intensity around 2θ = 17.9 ° was remarkably larger than that in FIG. 2, and the orientation to the (1,1,1) plane in the rhombohedral setting was estimated.

As a result of observing the inorganic porous support-CHA type zeolite membrane composite with SEM, crystals were densely formed on the surface.
After the top and bottom of the zeolite membrane composite were plugged with silicon rubber plugs, methyl silicate oligomer (MKC (registered trademark) silicate MS51, manufactured by Mitsubishi Chemical Corporation, number of Si (4 to 11), SiO ₂ content of 52. (0 ± 1.0%) so that the entire zeolite membrane composite is immersed, and after holding for 5 seconds, the zeolite membrane composite is pulled up and left to stand for 1 hour in a dryer in which water coexists. A surface treatment was performed by heating at 100 ° C. for 4 hours.

For zeolite membrane composite surface-treated, _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane itself was measured by SEM-EDX is 17, _SiO 2 / _Al 2 _{O 3} molar ratio of the measured zeolite membrane surface by XPS Was 626.4. _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane surface is larger than in the _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane itself, the zeolite membrane surface is estimated to have been modified with Si compound.

Using the obtained inorganic porous support-CHA-type zeolite membrane composite, separation by selectively allowing water to permeate from a water / isopropanol (IPA) mixed solution (10/90% by mass) by a vapor permeation method. went. The inorganic porous support-CHA-type zeolite membrane composite is placed in a constant temperature bath at 120 ° C., and the water / IPA mixed solution is sent to the vaporizer at a flow rate of 1.2 cm ³ / min to vaporize the entire amount. The inorganic porous support-CHA type zeolite membrane composite was supplied.

The permeation results after 4 hours were a permeation flux: 1.9 kg / (m ² · h), a separation factor: 198800, and a water concentration in the permeate: 99.99% by weight. The water permeance was 1.2 × 10 ⁻⁶ mol / (m ² · s · Pa). The evaluation results are shown in Table 2.
In the above examples, the physical properties and separation performance were measured as follows.

<Measurement of physical properties and separation performance>
(1) X-ray diffraction (XRD) measurement XRD measurement of the zeolite membrane was performed under the following conditions.
-Device name: X'PertPro MPD manufactured by PANalytical, the Netherlands
Optical system specifications Incident side: Enclosed X-ray tube (CuKα)
Soller Slit (0.04 rad)
Divergence Slit (Variable Sli
t)
Sample stage: XYZ stage
Light receiving side: Semiconductor array detector (X 'Celerator)
Ni-filter
Soller Slit (0.04 rad)
Goniometer radius: 240mm
Measurement conditions X-ray output (CuKα): 45 kV, 40 mA
Scanning axis: θ / 2θ
Scanning range (2θ): 5.0-70.0 °
Measurement mode: Continuous
Reading width: 0.05 °
Counting time: 99.7 sec
Automatic variable slit (Automatic-DS): 1 mm (irradiation width)
Lateral divergence mask: 10 mm (irradiation width)

X-rays were irradiated in a direction perpendicular to the axial direction of the cylindrical tube. Also, X-rays are not the sample table surface, but the sample table surface, out of two lines where the cylindrical tubular membrane complex placed on the sample table and the surface parallel to the sample table surface are in contact with each other so that noise and the like do not enter as much as possible. It was made to hit mainly on the other line above the surface.
In addition, the irradiation width was fixed to 1 mm by an automatic variable slit and measured, and Materials Data, Inc. XRD analysis software JADE 7.5.2 (Japanese version) was used to perform variable slit → fixed slit conversion to obtain an XRD pattern.

(2) Air permeation amount One end of the zeolite membrane composite was sealed, the other end was sealed and connected to a 5 kPa vacuum line, and the air flow was measured with a mass flow meter installed between the vacuum line and the zeolite membrane composite. The flow rate was measured and the air permeation amount [L / (m ² · h)] was obtained. KOF as a mass flow meter
LOC 8300, N ₂ gas, maximum flow rate 500 ml / min (20 ° C., 1 atm conversion) was used. When the mass flow meter display on the KOFLOC 8300 is 10 ml / min (20 ° C, converted to 1 atm) or less, Lintec MM-2100M, for Air gas, maximum flow rate 20 ml / min (converted to 0 ° C, 1 atm) It measured using.

(3) SEM measurement SEM measurement was performed based on the following conditions.
Device name: SEM: FE-SEM Hitachi: S-4100
・ Acceleration voltage: 10 kV

(4) SEM-EDX measurement SEM-EDX measurement of the zeolite membrane was performed under the following conditions.
-Device name: SEM: FE-SEM Hitachi: S-4800
EDX: EDAX Genesis
・ Acceleration voltage: 10 kV
The entire field of view (25 μm × 18 μm) at a magnification of 5000 was scanned, and X-ray quantitative analysis was performed.

By this SEM-EDX measurement, the SiO ₂ / Al ₂ O ₃ molar ratio of the produced zeolite membrane itself was determined. In the SEM-EDX measurement, information on only the zeolite membrane of several microns can be obtained by setting the X-ray irradiation energy to about 10 kV.

(5) XPS measurement XPS (X-ray photoelectron spectroscopy) measurement of the zeolite membrane surface was performed under the following conditions.
・ Device name: Quantum2000 manufactured by PHI
-X-ray source: Monochromatic Al-Kα, output 16 kV-34 W (X-ray generation area 170 μmφ)
・ Charge neutralization: Combined use of electron gun (5μA) and ion gun (10V) ・ Spectroscopy system: Pulse energy 187.85 eV @ Wide spectrum
58.70 eV @ narrow spectrum (Na1s, Al2
p, Si2p, K2p, S2p)
29.35 eV @ wide spectrum (C1s, O1s, S
i2p)
Measurement area: Spot irradiation (irradiation area <340 μmφ)
・ Extraction angle: 45 ° (from the surface)
By this XPS measurement, the SiO ₂ / Al ₂ O ₃ molar ratio on the surface of the produced zeolite membrane was determined.

(6) Vapor Permeation Method FIG. 2 shows a schematic diagram of an apparatus used for the vapor permeation method. In FIG. 2, the liquid 19 to be separated is sent to the vaporizer 21 at a predetermined flow rate by the liquid feed pump 20, and the entire amount is vaporized by heating in the vaporizer 21 to become a gas to be separated. The gas to be separated is introduced into the zeolite membrane composite module 14 in the thermostatic chamber 13 and supplied to the outside of the zeolite membrane composite. The zeolite membrane composite module 14 is obtained by housing a zeolite membrane composite in a housing. The inside of the zeolite membrane composite is depressurized by the vacuum pump 18, and the pressure difference with the gas to be separated is about 1 atm. Although not shown, the inner pressure can be measured with a Pirani gauge. Due to this pressure difference, the permeate water in the gas to be separated permeates the zeolite membrane composite. The permeated substance is collected by the permeate collecting trap 16. On the other hand, components that have not permeated in the gas to be separated are liquefied and collected by the liquid collecting trap 15.

At regular intervals, mass measurement and composition analysis of the permeate collected in the permeate collection trap 16 are performed, and using these values, the separation factor, permeation flux, water permeance, etc. for each time are described above. Calculated as follows. The composition analysis was performed by gas chromatography.

(Comparative Example 2)
An inorganic porous support-CHA type zeolite membrane composite was produced under the same conditions as in Example 2. This zeolite membrane composite was immersed vertically in a Teflon (registered trademark) inner cylinder containing 121.5 g of demineralized water, 2.5 g of tetraethoxysilane (TEOS), and 13.5 g of a 1 mol / l nitric acid aqueous solution. Was sealed, heated at 100 ° C. for 20 hours under an autogenous pressure, allowed to cool after a predetermined time, and then the zeolite membrane composite was taken out and washed with demineralized water. The pH of the treatment liquid used for the surface treatment was 1.3, the H ⁺ concentration was 0.05 mol / l, and the Si content was 0.24% by mass.

For zeolite membrane composite surface-treated, _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane itself was measured by SEM-EDX is 17, _SiO 2 / _Al 2 _{O 3} molar ratio of the measured zeolite membrane surface by XPS Was 95.0. _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane surface is larger than in the _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane itself, the zeolite membrane surface is estimated to have been modified with Si compound.

Using the surface-treated inorganic porous support-CHA type zeolite membrane composite, from the water / isopropanol (IPA) mixed solution (10/90 mass%) by the vapor permeation method in the same manner as in Example 1. Separation with selective permeation of water was performed.
The permeation results after 4 hours were a permeation flux: 1.7 kg / (m ² · h), a separation factor: 74500, and a water concentration in the permeate: 99.99% by weight. In terms of water permeance, it was 9.9 × 10 ⁻⁷ mol / (m ² · s · Pa). The evaluation results are shown in Table 2.

  From the results of Example 2 and Comparative Example 2, it was found that the porous support-zeolite membrane composite obtained by the production method of the present invention was excellent in permeation flux, separation coefficient, and permeance.

  The porous support-zeolite membrane composite obtained by the present invention is, for example, separated from water-containing organic compounds such as chemical plants, fermentation plants, precision electronic component factories, battery manufacturing factories, etc., recovered organic compounds, etc. Can be particularly suitably used in the field where is required. Also, for example, separation or concentration of air, natural gas, combustion gas, coke oven gas, biogas such as land file gas generated from landfill, and steam reformed gas of methane produced and discharged in petrochemical industry It can also be suitably used in fields where oxygen-enriched gas with high oxygen concentration is required, such as chemical plants, garbage disposal plants, and automobiles.

1. 1. Zeolite membrane composite 2. Pressure vessel End pin 4. Connection part 5. Pressure gauge 6. Back pressure valve 7. Supply gas 8. Permeated gas 9. Sweep gas10. Exhaust gas 11. Piping 12. Piping 13. Constant temperature bath 14. Zeolite membrane composite module 15. Separation liquid collecting trap 16. Permeate collection trap 17. Cold trap 18. Vacuum pump 19. Liquid to be separated20. Liquid feed pump 21. Vaporizer

Claims (4)

A method for producing a porous support-zeolite membrane composite having a zeolite membrane formed on a porous support , used for separation or concentration of a gas or liquid mixture comprising:
After forming the zeolite membrane on the porous support,
Treating the zeolite membrane with a material having two or more Si atoms in the molecule,
A method for producing a porous support-zeolite membrane composite. The method for producing a porous support-zeolite membrane composite according to claim 1, wherein the treatment is an immersion treatment, a dropping treatment or a spraying treatment. The method for producing a porous support-zeolite membrane composite according to claim 1 or 2, wherein the zeolite membrane after the treatment is heated at a temperature of 30 ° C or higher. The method for producing a porous support-zeolite membrane composite according to any one of claims 1 to 3, wherein the material having two or more Si atoms in the molecule is selected from alkoxysilanes, organosilicon compounds, and silicate oligomers. .

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