JP6123921B2 - Zeolite membrane composite for gas separation and method for producing the same - Google Patents

Description

  The present invention relates to a zeolite membrane composite for gas separation. More specifically, the present invention relates to a zeolite membrane composite for gas separation that separates a specific gas component from a gas mixture composed of a plurality of gas components. The present invention relates to a zeolite membrane composite for gas separation that is formed on a ceramic support and includes the zeolite crystal phase, and a gas separation method that uses the zeolite membrane composite as a gas separation means.

  Gas separation / purification methods include membrane separation methods, adsorption separation methods, absorption separation methods, distillation separation methods, and cryogenic separation methods, but membrane separation methods involve little phase change during gas separation, This is a technique in which the pressure difference is used as driving energy to separate the gas by the difference in velocity of the gas passing through the membrane. The membrane separation method is easy to handle and relatively small in scale as compared with other gas separation / purification methods, so that the target gas can be separated and concentrated at low cost and energy saving.

As a gas separation method using a membrane, a method using a polymer membrane has been proposed since the 1970s. However, while the polymer film has the characteristics of excellent processability, it has been a problem that the performance deteriorates due to deterioration due to heat, chemicals, and pressure.
In recent years, various inorganic films having good chemical resistance, oxidation resistance, heat stability, and pressure resistance have been proposed in order to solve these problems. Among these, zeolite has regular sub-nanometer pores, and therefore functions as a molecular sieve, so that it can selectively pass specific molecules and is expected to exhibit high separation performance.

  Specific examples of membrane separation of mixed gas include carbon dioxide and nitrogen, carbon dioxide and methane, hydrogen and hydrocarbons, hydrogen and oxygen, hydrogen and gas separation from thermal power plants and petrochemical industries. There are carbon dioxide, nitrogen and oxygen, paraffin and olefin separation. Known zeolite membranes for gas separation include zeolite membranes such as A-type membranes, FAU membranes, MFI membranes, SAPO-34 membranes, and DDR membranes.

  The A-type zeolite membrane is easily affected by moisture, and it is difficult to form a membrane without crystal gaps, and the separation performance is not high. The FAU membrane has a zeolite pore size of 0.6 to 0.8 nm, and is a size that allows two gas molecules to enter the zeolite pores. This membrane is suitable for separation of molecules having adsorption characteristics into zeolite pores and molecules having no adsorption properties, for example, separation of carbon dioxide and nitrogen. However, non-adsorbing molecules are difficult to separate and have a narrow application range. The pore diameter of the MFI membrane is 0.55 nm, and the pores are somewhat large for separating gas molecules, and the separation performance is not high.

  In addition, separation of carbon dioxide and methane is desired in natural gas refining plants and plants that biogas are produced by methane fermentation of raw garbage. DDR (Patent Document 1), SAPO-34 (Non-Patent Document 1), and SSZ-13 (Non-Patent Document 2) using a molecular sieving function are known as high-performance films.

JP 2004-105942 A

Shiguang Li et al., "Improved SAPO-34 Membranes for CO2 / CH4 Separation", Adv. Mater. 2006, 18, 2601-2603 Halil Kalipcilar et al., "Synthesis and Separation Performance of SSZ-13 Zeolite Membranes on Tubular Supports", Chem. Mater. 2002, 14, 3458-3464

  However, DDR (Patent Document 1) has good separation performance, but has a low carbon dioxide permeance (also referred to as “permeance”) due to the two-dimensional structure of the zeolite. Further, SAPO-34 (Non-Patent Document 1), which is a CHA-type aluminophosphate having a three-dimensional structure, has good separation performance and permeance, but performance in the presence of water deteriorates.

  Moreover, in a chemical plant, the mixed gas often contains water, and the performance deteriorates in the presence of water, which may not be practical. Similarly, the CHA type aluminosilicate SSZ-13 (Non-patent Document 2), which is also a SUS support membrane, has insufficient separation ability due to the coexistence of non-zeolite pores (defects) in the zeolite membrane. The permeance was not enough. Thus, a separation membrane for a gas mixture that can withstand practical use has not been known.

  An object of the present invention is to provide a zeolite membrane composite for gas separation that has solved the problems of the prior art, has excellent water resistance, and has excellent characteristics for separating a gas mixture.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a zeolite membrane composite having certain physical properties becomes a zeolite membrane composite having both a practically sufficient processing amount and separation treatment performance. And previously proposed (Japanese Patent Application No. 2010-043366). As a result of further studies, the present inventors have found that these zeolite membrane composites have excellent characteristics for separation of gas mixtures, and have reached the present invention.

That is, the gist of the present invention resides in the following (1) to (6).
(1) A zeolite membrane composite having a zeolite membrane on a ceramic support, the air permeability when the zeolite membrane composite is placed under atmospheric pressure and the inside of the zeolite membrane composite is connected to a 5 kPa vacuum line Is 700 L / (m ² · h) or less, and the zeolite membrane contains a CHA-type aluminosilicate zeolite mainly composed of an oxide of Si and Al , and the SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite Is a zeolite membrane composite for gas separation, characterized by having a particle size of 12 to 100,000 and a particle size of 30 nm or more .
(2) The zeolite membrane composite for gas separation according to (1), wherein the permeance when carbon dioxide is permeated at a temperature of 50 ° C. and a differential pressure of 0.098 MPa is 1 × 10 ⁻⁹ or more.
(3) The zeolite membrane composite for gas separation according to (1) or (2), wherein the zeolite membrane has a thickness of 20 μm or less.
(4) A method for producing a zeolite membrane composite for gas separation according to any one of (1) to (3), wherein the ceramic support is used for hydrothermal synthesis including a Si element source and an Al element source. A method for producing a zeolite membrane composite for gas separation, which is put in a reaction mixture and crystallizes zeolite in a membrane form on the surface of the support by hydrothermal synthesis.
(5) The method for producing a zeolite membrane composite for gas separation according to (4), wherein the ratio of the Si element source and the Al element source is 5 to 100,000 in terms of a SiO ₂ / Al ₂ O ₃ molar ratio.
(6) The method for producing a zeolite membrane composite for gas separation according to (4) or (5), wherein the aqueous reaction mixture contains potassium or sodium as an alkali source.

According to the present invention, it has excellent chemical resistance, heat stability, oxidation resistance, pressure resistance, a large amount of gas permeation, high separation coefficient, high wet heat stability, and excellent characteristics for separation of gas mixtures. A zeolite membrane composite can be provided. Further, by using the zeolite membrane composite of the present invention as a gas separation means, gas separation can be performed with high performance with small scale equipment, energy saving and low cost.

  Further, according to the present invention, a gas having a high permeability is allowed to permeate from a gas mixture, and the gas having a low permeability is concentrated to separate the gas having a high permeability out of the system. The target gas can be separated from the gas mixture with high purity by concentrating and recovering.

It is a schematic diagram of the apparatus used for the permeation | transmission test of single component gas. It is a schematic diagram of the apparatus used for the permeation | transmission test of mixed gas. It is an XRD pattern (a in the figure) of the CHA-type zeolite membrane produced in Example 1 and an XRD pattern (b) in the figure of the powdered CHA-type zeolite.

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 zeolite membrane composite for gas separation of the present invention is a zeolite membrane composite for gas separation that permeates and separates a gas component having a high permeability from a gas mixture composed of a plurality of gas components, the zeolite membrane comprising: It includes a CHA-type aluminosilicate zeolite and is formed on a ceramic support. In the present specification, the “ceramic support” may be simply abbreviated as “support”.

(Zeolite membrane composite for gas separation)
In the present invention, the zeolite membrane composite is used as a membrane separation means for permeating and separating a highly permeable gas component from a gas mixture composed of a plurality of gas components as described above. The gas component, separation method, separation performance, and the like will be described in the section of gas separation and separation performance after the details of the zeolite membrane composite.

(Zeolite membrane)
In the present invention, as a component constituting the zeolite membrane, in addition to zeolite, an inorganic binder such as silica and alumina, an organic substance such as a polymer, a silylating agent for modifying the zeolite surface, and the like may be included as necessary.
The zeolite membrane may partially contain an amorphous component or the like, but is preferably a zeolite membrane composed substantially only of zeolite.

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. Moreover, it is the range of 100 micrometers or less normally, Preferably it is 60 micrometers or less, More preferably, it is 20 micrometers or less. If the film thickness is too large, the amount of permeation tends to decrease. If it is too small, the selectivity tends to decrease or the film strength tends to decrease.
The particle diameter of the zeolite forming the zeolite membrane is not particularly limited, but if it is too small, there is a tendency to decrease permeation selectivity and the like by increasing the grain boundary. 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, the case where the particle diameter of zeolite is the same as the thickness of the membrane is more preferable. 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 preferred because the zeolite particle size and membrane thickness may be the same.

The shape of the zeolite membrane 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 0.5 cm to 2 cm, and a thickness of 0.5 mm to 4 mm are practical and preferable.

(Zeolite)
In the present invention, the zeolite constituting the zeolite membrane is a CHA type aluminosilicate.
The aluminosilicate used in the present invention is mainly composed of Si and Al oxides, and may contain other elements as long as the effects of the present invention are not impaired.
The SiO ₂ / Al ₂ O ₃ molar ratio of the aluminosilicate used in the present invention is not particularly limited, but is usually 5 or more, preferably 8 or more, more preferably 10 or more, still more preferably 12 or more. is there. The upper limit is usually an amount of Al as an impurity, and the SiO ₂ / Al ₂ O ₃ molar ratio is 100,000 or less. When the SiO ₂ / Al ₂ O ₃ molar ratio is less than the lower limit, the denseness of the zeolite membrane may be lowered, and the durability tends to be lowered. The SiO ₂ / Al ₂ O ₃ molar ratio can be adjusted by the reaction conditions of hydrothermal synthesis described later.
_{Incidentally,} SiO 2 / _Al 2 _{O 3} molar ratio, a scanning electron microscope - is a value obtained by energy dispersive X-ray spectroscopy (SEM-EDX). In order to obtain information on only a film of several microns, the X-ray acceleration voltage is usually measured at 10 kV.

(CHA type zeolite)
In the present invention, the CHA-type zeolite is a code that defines the structure of zeolite defined by the International Zeolite Association (IZA) and indicates a CHA structure. It is a zeolite having a crystal structure equivalent to that of naturally occurring chabasite. The CHA-type zeolite has a structure characterized by having three-dimensional pores composed of oxygen 8-membered rings having a diameter of 0.38 × 0.38 nm, and the structure is characterized by X-ray diffraction data.

The framework density (T / nm ³ ) of the CHA-type zeolite is 14.5. The SiO ₂ / Al ₂ O ₃ molar ratio is the same as described above.
Here, the framework density (T / nm ³ ) means the number of elements (T element) other than oxygen constituting the skeleton per nm ³ (1000 ^{３ 3} ) of the zeolite, and this value is the structure of the zeolite. It is determined by. The relationship between framework density and zeolite structure is shown in ATLAS OF ZEOLITE FRAMEWORK TYPES Fifth Revised Edition 2001 ELSEVIER.

(Ceramic support)
The ceramic support may be any porous inorganic substance having chemical stability that can crystallize zeolite in the form of a film on the surface thereof. Specific examples include ceramic sintered bodies such as silica, α-alumina, γ-alumina, mullite, zirconia, titania, yttria, silicon nitride, and silicon carbide.

The ceramic support has an effect of enhancing the adhesion at the interface by partly converting into a zeolite during synthesis of the zeolite membrane.
Furthermore, since the ceramic support containing at least one of alumina, silica, and mullite is easy to partially zeolitize the support, the bond between the support and the zeolite becomes strong and the membrane is dense and has high separation performance. Is more preferable because it becomes easier to form.

The shape of the support is not particularly limited as long as it can effectively separate a gas mixture or a liquid mixture. Specifically, for example, a flat plate shape, a tubular shape, a cylindrical shape, a cylindrical shape, or a prismatic shape is used. There are honeycomb-shaped materials and monoliths with a large number of.
In the present invention, a zeolite membrane is formed on the surface of the ceramic support, preferably the zeolite is crystallized into a membrane.

  The average pore diameter of the support is not particularly limited, but those having a controlled pore diameter are preferred, 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 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 or a dense zeolite membrane tends to be difficult to form.

The surface of the support is preferably smooth, and the surface may be polished with a file or the like as necessary. The surface of the support means a surface portion of the support on which the zeolite membrane is formed, and may be any surface of each shape as long as it is a surface, or may be a plurality of surfaces. 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.
Further, the pore diameter of the support is not particularly limited and need not be particularly controlled, but the porosity is usually preferably 20% or more and 60% or less. The porosity affects the permeation flow rate when separating the gas or liquid, 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.

(Zeolite membrane composite)
A zeolite membrane composite is one in which zeolite is fixed in the form of a film on the surface of the support, and in some cases, a part of the zeolite is fixed to the inside of the support. preferable.
As the zeolite membrane composite, a zeolite membrane crystallized into a membrane by hydrothermal synthesis on the surface of the support is preferable.

  The position of the zeolite membrane on the support is not particularly limited, and when a tubular support is used, the zeolite membrane may be attached to the outer surface, the inner surface, or both sides depending on the system to be applied. Also good. Further, it may be laminated on the surface of the support, or crystallized so as to fill the pores of the surface layer of the support. In this case, it is important that there are no cracks or continuous micropores inside the crystallized film layer, and forming a so-called dense film improves the separability.

In the present invention, the zeolite membrane composite has an X-ray diffraction pattern in which the intensity of the peak near 2θ = 17.9 ° is not less than 0.5 times the intensity of the peak near 2θ = 20.8 °. Preferably there is.
Here, the peak intensity refers to a value obtained by subtracting the background value from the measured value. The peak intensity ratio represented by (the intensity of the peak around 2θ = 17.9 °) / (the intensity of the peak around 2θ = 20.8 °) (hereinafter this may be referred to as “peak intensity ratio A”). Speaking of
Usually 0.5 or more, preferably 0.8 or more. Although an upper limit is not specifically limited, Usually, it is 1000 or less.

In the present invention, the zeolite membrane composite has an X-ray diffraction pattern in which the intensity of the peak near 2θ = 9.6 ° is at least four times the intensity of the peak near 2θ = 20.8 °. It is preferable.
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 4 or more, preferably 6 or more, more preferably 8 or more, and particularly 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 X-rays on the surface of the membrane composite on which the zeolite is mainly attached. The body itself or the one cut into an appropriate size restricted by the apparatus is preferable.

The X-ray diffraction pattern here 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 subjected to variable → fixed slit correction.
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 peaks not derived from the substrate.
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 X-ray diffraction pattern, the peak near 2θ = 9.6 ° is a collection of SIMULATED XRD POWDER PATTERNS FOR ZEOLITE Third Revised Edition 1996 ELSEVIER

(No. 166), it is a peak derived from the plane having an index of (1, 0, 0) in the CHA structure.
In addition, the peak near 2θ = 17.9 ° in the X-ray diffraction pattern shows the space group in the rhombohedral setting according to COLLECTION OF SIMULATED XRD POWDER PATTERNS FOR ZEOLITE Third Revised Edition 1996 ELSEVIER.

(No. 166) is a peak derived from the (1,1,1) index in the CHA structure.
According to X-ray diffraction pattern, the peak near 2θ = 20.8 ° is a collection of SIMULATED XRD POWDER PATTERNS FOR ZEOLITE Third Revised Edition 1996 ELSEVIER

(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 (1, 0, 0) plane and the peak intensity derived from the (2, 0, -1) plane (peak intensity ratio B) is COLLECTION OF SIMULATED XRD POWDER PATTERNS FOR ZEOLITE According to Third Revised Edition 1996 ELSEVIER, it is 2.5.

  Therefore, when this ratio is 4 or more, for example, the zeolite crystal is oriented so that the (1,0,0) plane when the CHA structure is a rhombohedral setting is oriented almost parallel to the surface of the membrane composite. It is thought that it means growing in an oriented manner. 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 (peak intensity ratio A) is COLLECTION OF SIMULATED XRD POWDER PATTERNS FOR ZEOLITE According to Third Revised Edition 1996 ELSEVIER, it is 0.3.
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.
As described below, a dense zeolite membrane in which CHA-type zeolite crystals are grown in an orientated state is formed in an aqueous reaction mixture using, for example, a specific organic template when the zeolite membrane is formed by a hydrothermal synthesis method. This can be achieved by allowing a K ⁺ ion to coexist with.

(Method for producing zeolite membrane)
In the present invention, the method for producing a zeolite membrane is not particularly limited as long as it can form a membrane containing zeolite. For example, (1) a method for crystallizing zeolite in a film form on a support, (2) A method of fixing zeolite to the support with an inorganic binder or an organic binder, (3) a method of fixing a polymer in which zeolite is dispersed, and (4) impregnating the support with a zeolite slurry, and optionally sucking the support. Any method such as a method for fixing zeolite to a support by the above method can be used.

Among these, a method of crystallizing zeolite on a ceramic support in a film form is particularly preferable. There is no particular limitation on the method of crystallization, but the support is placed in a reaction mixture for hydrothermal synthesis used for zeolite production (hereinafter sometimes referred to as an “aqueous reaction mixture”) and directly hydrothermal synthesis is performed. Thus, a method of crystallizing zeolite on the surface of the support is preferred.
Specifically, for example, an aqueous reaction mixture that has been homogenized by adjusting the composition may be sealed in a heat and pressure resistant container such as an autoclave in which a support is gently fixed, and heated for a certain period of time.

The aqueous reaction mixture preferably contains an Si element source, an Al element source, an organic template (if necessary), and water, and further an alkali source 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 crystallinity is 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.
As the organic template, amines and quaternary ammonium salts are usually used. 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. 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.

  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.
In addition, 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 an 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 is usually Na, K, Li, Rb, Cs, Ca, Mg, Sr, Ba, preferably Na, K, more preferably K. Two or more kinds of alkalis may be used in combination, and specifically, Na and K or Li and K 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 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. Moreover, it is usually 100,000 or less.
When the SiO ₂ / Al ₂ O ₃ ratio is in this range, a CHA-type aluminosilicate zeolite capable of forming a dense film can be crystallized.

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 ratio) is usually 0.005 or higher, preferably at least 0.01, more preferably 0. 02 or more, usually 1 or less, preferably 0.4 or less, more preferably 0.2 or less. In addition to being able to produce a dense zeolite membrane when in this range, the produced zeolite is highly acid resistant and Al is not easily desorbed. Also, under this condition, a particularly dense and acid-resistant CHA-type aluminosilicate zeolite can be formed.

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.
When forming a CHA type aluminosilicate zeolite membrane, it is preferable that potassium (K) is contained in the alkali metal in terms of producing a denser and higher crystalline membrane. 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, preferably 0.1 or more, more preferably 0.3 or more, and the upper limit. Is usually 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 finer crystals are more likely to form and form a dense membrane when the amount of water is greater than that of the general powder synthesis method. is there.

Generally, the amount of water when synthesizing powdered CHA-type aluminosilicate zeolite is about 15 to 50 in terms of H ₂ O / SiO ₂ molar ratio. Separation in which a CHA-type aluminosilicate zeolite crystallizes into a dense membrane on the surface of the support, etc., under the condition that the H ₂ O / SiO ₂ molar ratio is high (50 to 1000), that is, a lot of water. A high performance zeolite membrane composite can be obtained.

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 a CHA type aluminosilicate zeolite membrane is formed, it is preferable to use a seed crystal of CHA type zeolite.
It is desirable that the seed crystal has a small particle size, and it may be used after pulverization if necessary. The particle size is usually 0.5 nm or more, preferably 1 nm or more, more preferably 2 nm or more, and is usually 5 μm or less, preferably 3 μm or less, more preferably 2 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 to the surface, For example, a method of applying a slurry obtained by mixing crystals with a solvent such as water onto a support can be used. 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 seed crystals to be dispersed is not particularly limited, and is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more with respect to the total weight of the dispersion. Moreover, it is 20 weight% or less normally, Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less, More preferably, it is 3 weight% 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 of the support surface where no zeolite is generated is formed during hydrothermal synthesis, resulting in a defective film. there is a possibility. If the amount of seed crystals in the dispersion is too large, the amount of seed crystals adhering to the support by the dipping method becomes almost constant, which is disadvantageous in terms of cost because the seed crystals are wasted.

It is desirable to deposit the seed crystal on the support by dipping or slurry coating, and after drying, form a zeolite membrane.
The weight of the seed crystal to be deposited in advance 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, 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. Also, if the amount of 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 surface, thereby inhibiting film growth on the support. May be. 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 zeolite in the present invention 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. If necessary, an inert gas such as nitrogen may be added.
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.

  In the case of drying, the temperature of the heat treatment is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, usually 200 ° C. or lower, preferably 150 ° C. or lower. The temperature of the heat treatment is usually 350 ° C. or higher, preferably 400 ° C. or higher, more preferably 430 ° C. or higher, more preferably 450 ° C. or higher, and usually 900 ° C. or lower, preferably 850 ° C. or lower, for the purpose of firing the template. More preferably, it is 800 ° C. or less, and particularly preferably 750 ° C. or less.

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.
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.

  If the calcination temperature is too low, the proportion of the remaining organic template tends to increase, and the pores of the zeolite are small, so that the amount of gas permeation during separation and concentration may decrease. If the calcination temperature is too high, the difference in the coefficient of thermal expansion between the support and the zeolite becomes large, so that the zeolite membrane may be easily cracked, and the denseness of the zeolite membrane may be lost and the separation performance may be lowered.

  The firing time varies depending on the temperature rising rate or the temperature falling rate, but is not particularly limited as long as the organic template is sufficiently removed, and is preferably 1 hour or longer, more preferably 5 hours or longer. The upper limit is not particularly limited, and is, for example, usually within 200 hours, preferably within 150 hours, more preferably within 100 hours, and particularly preferably within 24 hours. Firing may be performed in an air atmosphere, but may be performed in an atmosphere to which oxygen is added.

It is desirable that the rate of temperature increase during firing be 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. Examples of ions to be ion-exchanged include protons, alkali metal ions such as Na ⁺ , K ⁺ and Li ⁺ , alkaline earth metal ions such as Ca ²⁺ , Mg ²⁺ , Sr ²⁺ and Ba ²⁺ , Fe, Cu, Zn, Ag and the like. And transition metal ions. Among these, alkali metal ions such as proton, Na ⁺ , K ⁺ , and Li ⁺ 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 etc. after processing at the temperature of 100 degreeC. Furthermore, you may bake at 200 to 500 degreeC as needed.
The air permeation amount of the zeolite membrane composite after the heat treatment is usually 1400 L / (m ² · h) or less, preferably 1000 L / (m ² · h) or less, more preferably 700 L / (m ² · h) or less, More preferably 600 L / (m ² · h) or less, further preferably 500 L / (m ² · h) or less, particularly preferably 300 L / (m ² · h) or less, and most preferably 200 L / (m ² · h). It is. 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 amount of air permeation when the zeolite membrane composite is placed under atmospheric pressure and the inside of the zeolite membrane composite is connected to a 5 kPa vacuum line, as described in detail in the Examples section. [L / (m ² · h)].
The zeolite membrane composite thus produced has excellent characteristics and can be suitably used as a membrane separation means for gas separation in the present invention.

(Gas separation)
The gas separation method of the present invention is characterized in that a gas mixture composed of a plurality of gas components is brought into contact with the zeolite membrane composite, and a highly permeable gas component is permeated and separated from the gas mixture. It is.
One of the separation functions of the zeolite membrane in the present invention is separation as a molecular sieve, and gas molecules having a size larger than the effective pore diameter of the zeolite used can be suitably separated from gas molecules smaller than that. .

Therefore, the highly permeable gas component in the present invention is a gas component composed of gas molecules that easily pass through the pores of the zeolite crystal phase of CHA-type aluminosilicate, and a gas having a molecular diameter smaller than about 0.38 nm. A gaseous component consisting of molecules is preferred.
The effective pore size of zeolite can be controlled by the metal species to be introduced, ion exchange, acid treatment, silylation, and the like. It is also possible to improve the separation performance by controlling the effective pore diameter.

The pore size is slightly affected by the atomic size of the metal species introduced into the zeolite framework. When a metal having a smaller atomic diameter than silicon, specifically boron (B), for example, is introduced, the pore diameter becomes smaller, and a metal having an atomic diameter larger than silicon, specifically tin (Sn), etc. When is introduced, the pore diameter becomes large.
Further, the pore diameter may be affected by removing the introduced metal from the skeleton by acid treatment.

  When exchanging with monovalent ions having a large ion radius by ion exchange, the effective pore diameter becomes smaller, whereas when exchanging with monovalent ions having a small ion radius, the effective pore diameter is CHA structure. It becomes a value close to the pore diameter of. Also in the case of divalent ions such as calcium, depending on the position of the exchange site, the effective pore size is close to the pore size of the CHA structure.

Silylation can also reduce the effective pore size of zeolite. By silylated the terminal silanol on the outer surface and further laminating the silylated layer, the effective pore diameter of the pores facing the outer surface of the zeolite is reduced.
Further, another separation function of the zeolite composite membrane of the present invention is to control the adsorptivity of gas molecules to the zeolite membrane by controlling the surface physical properties of the zeolite. That is, by controlling the polarity of the zeolite, it is possible to facilitate the passage of molecules having a high adsorptivity to the zeolite.

It is possible to increase the polarity by substituting Si of the zeolite skeleton with Al, and thereby, gas molecules having a large polarity can be actively adsorbed and permeated into the zeolite pores. Further, when the amount of Al substitution is reduced, a zeolite membrane having a small polarity is obtained, which is advantageous for allowing gas molecules having a small polarity to permeate.
It is also possible to control the polarity by putting Ga, Fe, B, Ti, Zr, Sn, Zn into another element source in addition to the Al element source.

In addition, the permeation performance can be controlled by controlling the adsorption performance of the molecules and the pore diameter of the zeolite by ion exchange.
In the present invention, preferred gas mixtures include carbon dioxide, hydrogen, oxygen, nitrogen, methane, ethane, ethylene, propane, propylene, normal butane, isobutane, 1-butene, 2-butene, isobutene, sulfur hexafluoride, helium. , Carbon monoxide, nitric oxide, water and the like, containing at least one component selected. Among the components of the gas mixture containing the gas, a gas component having a high permeance passes through the zeolite membrane composite and is separated, and a gas component having a low permeance is concentrated on the supply gas side.

Furthermore, as a gas mixture, what contains at least 2 types of component of the said component is more preferable. In this case, the two components are preferably a combination of a component having a high permeance and a component having a low permeance.
Although the conditions for gas separation vary depending on the target gas species and composition, and the performance of the membrane, the temperature is usually 0 to 300 ° C, preferably room temperature to 200 ° C, more preferably room temperature to 150 ° C.

The pressure of the supply gas may be the same as long as the gas to be separated is high, or may be used by adjusting the pressure appropriately to a desired pressure. When the gas to be separated is lower than the pressure used for separation, the pressure can be increased with a compressor or the like.
The pressure of the supply gas is not particularly limited, but is usually atmospheric pressure or larger than atmospheric pressure, preferably 0.1 MPa or more, more preferably 0.11 MPa or more. The upper limit is usually 20 MPa or less, preferably 10 MPa or less, more preferably 1 MPa or less.

The differential pressure between the gas on the supply side and the gas on the permeate side is not particularly limited, but is usually 20 MPa or less, preferably 10 MPa or less, more preferably 5 MPa or less, and even more preferably 1 MPa or less. Moreover, it is 0.001 MPa or more normally, Preferably it is 0.01 MPa or more, More preferably, it is 0.02 MPa or more.
Here, the differential pressure refers to the difference between the partial pressure on the gas supply side and the partial pressure on the permeation side. The pressure [Pa] in the present invention refers to an absolute pressure unless otherwise specified.

  The flow rate of the supply gas is a flow rate that can compensate for the decrease in the permeated gas, and the concentration in the vicinity of the membrane of the gas having a small permeability in the supply gas matches the concentration in the entire gas. However, it is usually 0.5 mm / sec or more, preferably 1 mm / sec or more, and the upper limit is not particularly limited. 1 m / sec or less, preferably 0.5 m / sec or less.

In the separation method of the present invention, a sweep gas may be used. In the method using the sweep gas, a gas different from the supply gas is allowed to flow on the permeate side, and the gas that has permeated the membrane is recovered.
The pressure of the sweep gas is usually atmospheric pressure, but is not particularly limited, preferably 20 MPa or less, more preferably 10 MPa or less, still more preferably 1 MPa or less, and the lower limit is preferably 0.09 MPa or more, more preferably, It is 0.1 MPa or more. In some cases, the pressure may be reduced.

The flow rate of the sweep gas is not particularly limited, but is usually 10 ⁻⁷ mol / (m ² · s) or more and 10 ⁴ mol / (m ² · s) or less.
Although the apparatus used for gas separation is not specifically limited, Usually, it uses as a module. The membrane module may be, for example, an apparatus as shown in FIGS. 1 and 2, or may be a membrane module exemplified in “Gas Separation / Purification Technology”, page 22 of the Toray Research Center 2007 issue. Good.

(Separation performance)
The zeolite membrane composite in the present invention is excellent in chemical resistance, oxidation resistance, heat stability, and pressure resistance, exhibits high permeation performance and separation performance, and has excellent performance. In particular, it exhibits excellent separation performance for separating inorganic gases and lower hydrocarbons.
The high permeation performance here indicates a sufficient throughput, for example, the permeance (Permeance) [mol · (m ² · s · Pa) ⁻¹ ] of the gas component that permeates the membrane, for example, carbon dioxide, When permeated at a temperature of 50 ° C. and a differential pressure of 0.098 MPa, it is usually 1 × 10 ⁻⁹ or more, preferably 5 × 10 ⁻⁸ or more, more preferably 1 × 10 ⁻⁷ or more, and the upper limit is not particularly limited. Usually, it is 1 × 10 ⁻⁴ or less.

Further, permeance [mol · (m ² · s · Pa) ⁻¹ ] is usually 1 × 10 ⁻⁷ or less, preferably 1 × 10 ⁻⁸ or less, more preferably when methane is permeated under the same conditions. Is 5 × 10 ⁻⁹ or less, and ideally the permeance is 0, but may be practically on the order of 10 ⁻¹⁰ to 10 ⁻¹⁴ or more.
Here, the permeance is obtained by dividing the amount of the permeating substance by the product of the membrane area, time, and the partial pressure difference between the permeating substance supply side and the permeating side, and the unit is [mol · (m ² · s · Pa) ⁻¹ ], which is a value calculated by the method described in the example section. Sometimes referred to as “transmittance”.

The selectivity of the zeolite membrane is expressed by a separation factor. The separation coefficient is an index representing selectivity generally used in membrane separation, and is a value calculated by the method described in the section of the examples.
The separation factor is, for example, usually 2 or more, preferably 10 or more, more preferably 30 or more when a mixed gas of carbon dioxide and methane in a volume ratio of 1: 1 is permeated at a temperature of 50 ° C. and a differential pressure of 0.098 MPa. Especially preferably, it is 50 or more. The upper limit of the separation factor is a case where only carbon dioxide permeates. In that case, the separation factor is infinite, but in practice, the separation factor may be about 100,000 or less.

As described above, the zeolite membrane composite for gas separation of the present invention is excellent in chemical resistance, oxidation resistance, heat stability, pressure resistance, exhibits high permeation performance, separation performance, and is excellent in durability. For example, it can be particularly suitably used as the following gas separation technique.
Carbon dioxide separation technology includes the removal of carbon dioxide from natural gas and landfill gas (approximately 60% methane, 40% carbon dioxide, trace amounts of nitrogen and water vapor) generated by landfilling organic matter such as domestic waste. Removal of carbon dioxide and the like.

Hydrogen separation technologies include hydrogen recovery in the petroleum refining industry, hydrogen recovery and purification in various reaction processes in the chemical industry (mixtures of hydrogen, carbon monoxide, carbon dioxide, hydrocarbons, etc.), and production of high-purity hydrogen for fuel cells. and so on. Hydrogen production for fuel cells is obtained by a steam reforming reaction of methane, and it is necessary to separate hydrogen from a mixed gas of H ₂ , CO, CH ₄ , and H ₂ O.

  In addition, as oxygen separation technology, production of oxygen-enriched gas from air (medical and combustion oxygen-enriched air, etc.), as nitrogen separation technology, production of nitrogen-rich gas from air (explosion-proof, antioxidant, etc.) ), Water vapor separation (dehumidification of precision machinery, etc.), dissolved gas separation (deaeration from water and organic liquids), organic gas separation (organic gas separation in the oil refining industry and petrochemical industry, separation of olefins and paraffins), etc. Is mentioned.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, the physical properties and separation performance of the zeolite membrane were measured by the following methods. Hereinafter, “CHA-type silicate zeolite” is simply referred to as “CHA-type zeolite”.

(1) X-ray diffraction (XRD)
XRD measurement was performed based on 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 Slit)
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, the X-ray is not a line in contact with the surface of the sample table out of two lines where the cylindrical tubular membrane composite placed on the sample table and a surface parallel to the surface of the sample table are in contact with each other so that noise is not required as much as possible. The main line was placed on the other line above the surface of the sample table.

In addition, the irradiation width is fixed to 1 mm with an automatic variable slit and measured, and then XRD analysis software JADE 7.5.2 (Japanese version) of Materials Data, Inc. is used to perform variable slit → fixed slit conversion to XRD. Got a pattern.
(2) SEM-EDX
-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.

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

(4) Air permeation amount At atmospheric pressure, one end of the zeolite membrane composite is sealed, and the other end is connected to a 5 kPa vacuum line while maintaining airtightness. The flow rate of air that permeated the zeolite membrane composite was measured with a mass flow meter installed in between, and the air permeation amount [L / (
m ² · h)]. As the mass flow meter, 8300 manufactured by KOFLOC, for N ₂ gas, maximum flow rate 500 ml / min (20 ° C., converted to 1 atm) was used. 8 made by KOFLOC
In 300, when the mass flow meter display is 10 ml / min or less (20 ° C., converted to 1 atm), Lintec MM-2100M, for Air gas, maximum flow rate 20 ml / min
It measured using min (0 degreeC, 1 atmosphere conversion).

(5) Single-component gas permeation test The single-component gas permeation test was performed as follows using the apparatus schematically shown in FIG. 1 or 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), hydrogen (purity 99.99% or higher, HORIBA STEC hydrogen generation) Generated from the reactor OPGU-2200), nitrogen (purity 99.99%, manufactured by Toho Oxygen Industry), helium (purity 99.99, manufactured by Japan Helium Center)
It is.

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 permeate gas 8 are connected via the connecting portion 4, and the pipe 11 extends to the outside of the pressure 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. 2, a cylindrical zeolite membrane composite 1 is installed in a thermostat (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 are connected via the 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. 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, when performing a single component gas permeation test, a sample gas (supply gas 7) is supplied between the pressure vessel 2 and the zeolite membrane composite 1 at a constant pressure, and passes through the zeolite membrane composite. The permeated gas 8 is measured with a flow meter (not shown) connected to the pipe 11.
In the apparatus shown in FIG. 2, when a single component gas permeation test is performed, 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 back pressure valve 6 is used to supply the sample gas. Keep pressure constant. The flow rate of the exhaust gas 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 removed 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, the 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} Indicates the pressure [Pa] of the highly permeable gas and the low permeable gas, respectively. ]

(6) 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 gases used were carbon dioxide (purity 99.9%, manufactured by High Pressure Gas Industries), methane (purity 99.999%, manufactured by Japan Fine Products), hydrogen (purity 99.99% or higher, HORIBA STEC hydrogen generation) Generated from OPGU-2200), nitrogen (9
9.99%, manufactured by Toho Oxygen Industry). A gas mixed at a predetermined ratio was supplied using a flow rate control device.

The specific configuration of the apparatus of FIG. 2 used for the mixed gas permeation test is as described above.
In the apparatus of FIG. 2, the sample gas (supply gas 7) is supplied between the pressure-resistant 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 flow rate of the exhaust gas discharged from the pipe 11 is measured, and the exhaust gas is collected and component analysis is performed by a gas chromatograph. When the sweep gas is used, the flow rate of the exhaust gas (the exhaust gas of the sweep gas 9 and the accompanying permeate gas 8) discharged from the pipe 11 by flowing the sweep gas 9 from the pipe 12 to the inside of the zeolite membrane composite 1. In addition, the exhaust gas is collected and the components are analyzed by gas chromatography.

At this time, the flow velocity of each component gas that has permeated 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)
[In the formula (2), Q ′ ₁ and Q ′ ₂ represent the permeation amount [mol · (m ² · s) ⁻¹ ] of a highly permeable gas and a low permeable gas, respectively, and 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. ]

In addition, a permeance ratio may be used as an index representing separation performance. The permeance ratio is a ratio of gas permeance with high permeability to gas permeance with low permeability, and is calculated by the following equation (3).
Permeance ratio = Permeance ₁ / Permeance ₂ (3)
[In formula (3), permeance ₁ and permeance ₂ show the permeance [mol · (m ² · s · Pa) ⁻¹ ] of a gas with high permeability and a gas with low permeability, respectively. ]

The permeance in the mixed gas permeation test is the difference between the partial pressure of each component of the gas on the supply side and the partial pressure of each component of the gas on the permeation side, and the permeation amount per hour per area of each gas. Calculated by dividing by pressure difference. Specifically, it can be calculated by the following formula (4). Permeance = Q / (P (supply)-P (transmission))
[In Formula (4), Q indicates the permeation amount [mol · (m ² · s) ⁻¹ ] of the gas component to be calculated, and P (supply) and P (permeation) are calculated in the supplied gas, respectively. The partial pressure [Pa] of the gas to be calculated and the partial pressure [Pa] of the gas to be calculated in the permeated gas are shown. ]
The permeation amount of each gas component in the mixed gas permeation test was calculated from the total permeation amount and composition by measuring the total permeation amount with a flow meter and measuring the gas composition of the permeated gas with gas chromatography.

Example 1
(1) Preparation of CHA-type aluminosilicate zeolite membrane composite A ceramic support-CHA-type zeolite membrane composite was prepared by hydrothermal synthesis of CHA-type aluminosilicate zeolite directly on a ceramic support.
A reaction mixture for hydrothermal synthesis was prepared as follows.

A mixture of 10.5 g of 1 mol / L-NaOH aqueous solution and 7.0 g of 1 mol / L-KOH aqueous solution and 100.6 g of water was mixed with aluminum hydroxide (containing 53.5% by mass of Al ₂ O ₃ , manufactured by Aldrich). 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 Corp.) is added, and further colloidal. 10.5 g of silica (Snowtech-40 manufactured by Nissan Chemical Industries, Ltd.) was added and stirred for 2 hours to obtain an aqueous 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 ceramic support, a mullite tube PM (outer diameter: 12 mm, inner diameter: 9 mm) manufactured by Nikkato Co., Ltd. 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, A CHA-type zeolite obtained by hydrothermal synthesis at 160 ° C. for 2 days and crystallizing was filtered, washed with water and dried. The seed crystal grain size was about 0.3 to 3 μm.
The support was immersed in a dispersion of the seed crystal in about 1% by mass of water for a predetermined time, and then dried at 100 ° C. for 5 hours or more to attach the seed crystal. The mass of the attached seed crystal was about 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 aqueous reaction mixture in the vertical direction, and the autoclave was sealed, and allowed to stand at 160 ° C. for 48 hours. And heated under autogenous pressure. After the elapse of a predetermined time, the support-zeolite membrane composite was taken out of the reaction mixture after being allowed to cool, washed, and then dried at 100 ° C. for 5 hours or more.
This membrane composite was baked in an electric furnace at 550 ° C. for 10 hours in air. At this time, the rate of temperature increase and the rate of temperature decrease were both 0.5 ° C./min. The mass of the CHA-type zeolite crystallized on the support, which was obtained from the difference between the mass of the membrane composite after firing and the mass of the support, was 154 g / m ² .

The film thickness obtained from SEM measurement was about 15 μm. Moreover, the air permeation amount after firing was 50 L / (m ² · h).
The XRD pattern of the produced zeolite membrane is shown in FIG. * In the figure is a peak derived from the support. From XRD measurement, it was found that CHA-type zeolite was produced.
FIG. 3 b) shows the XRD pattern of powdered CHA-type zeolite (zeolite generally referred to as SSZ-13 in US Pat. No. 4,544,538, hereinafter referred to as “SSZ-13”).

FIG. 3 shows that the XRD pattern of the produced zeolite membrane has a significantly higher peak intensity around 2θ = 17.9 ° than the XRD pattern of SSZ-13, which is a powdered CHA-type zeolite.
For the powdered CHA-type zeolite SSZ-13 (peak intensity around 2θ = 17.9 °) / (peak intensity around 2θ = 20.8 °) = 0.2, (Intensity of peak near 2θ = 17.9 °) / (Intensity of peak near 2θ = 20.8 °)
= 3.5, and orientation to the (1,1,1) plane in rhombohedral setting was estimated.
Moreover, as a result of observing the zeolite membrane composite cut into strips by SEM, crystals were densely formed on the surface.
Was also measured by _{SEM-EDX, SiO 2 / Al} 2 O 3 molar ratio of the zeolite membrane was 17.

(2) Single-component gas permeability test The single-component gas permeability of the CHA-type zeolite membrane composite produced above was examined using the apparatus shown in FIG. The evaluated gases are carbon dioxide and methane.
The zeolite membrane composite 1 was pretreated at 140 ° C. and 200 Pa in advance for vacuum drying, and then the temperature was set to 50 ° C. Subsequently, the supply gas 7 is introduced between the cylinders of the pressure vessel 2 and the zeolite membrane composite 1 to keep the pressure at 0.1994 MPa, and the inside of the cylinder of the zeolite membrane composite 1 is set to 0.1013 MPa (atmospheric pressure). ) For 40 minutes or more, and the temperature, the pressure on the supply gas side, and the permeating gas velocity were set to a steady state.

At this time, the differential pressure between the supply gas 7 side and the permeate gas 8 side of the zeolite membrane composite 1 was 0.098 MPa.
As a result, the permeance when carbon dioxide was used as the supply gas was 3.47 × 10 ⁻⁷ mol · (m ² · s · Pa) ⁻¹ , and the permeance when methane was used was 3.9 × 10 ^{− 9} mol · (m ² · s · Pa) ⁻¹ . The ideal separation factor α of carbon dioxide and methane was 89.

(3) Mixed gas permeation test The mixed gas permeability of the CHA-type zeolite membrane composite produced above was examined using the apparatus shown in FIG.
As the supply gas, a mixed gas adjusted to 49% by volume of carbon dioxide and 51% by volume of methane with a flow rate adjusting device was used. The mixed gas is used as the supply gas 7 and introduced at a flow rate of 12 mmol / min between the cylinders of the pressure vessel 2 and the zeolite membrane composite 1 to maintain the supply gas pressure at 0.1994 MPa, and a sweep gas (nitrogen gas) 4.5 mmol / min (0.05 mol / (
m ² · s). In this state, the zeolite membrane composite 1 was dried (pretreated) at 140 ° C. and then allowed to stand at 50 ° C. for 40 minutes or longer, so that the temperature, the pressure on the supply gas side, and the permeated gas velocity were in a steady state.

The inside of the cylinder of the zeolite membrane composite 1 is 0.107 MPa, and the partial pressures of carbon dioxide and methane on the supply gas 7 side are 0.0977 MPa and 0.102 MPa, respectively.
The permeation amount of carbon dioxide was 14.4 mmol · (m ² · s) ⁻¹ , and the permeation amount of methane was 0.205 mmol · (m ² · s) ⁻¹ . The separation factor α ′ of carbon dioxide and methane was 73.

(Example 2)
(1) Production of CHA-type zeolite membrane composite A ceramic support-CHA-type zeolite membrane composite was produced by directly hydrothermally synthesizing CHA-type zeolite on a ceramic support.
A reaction mixture for hydrothermal synthesis was prepared as follows.

To a mixture of 3.5 g of 1 mol / L-NaOH aqueous solution, 7 g of 1 mol / L-KOH aqueous solution and 107.4 g of water, 0.44 g of aluminum hydroxide (containing 53.5% by mass of Al ₂ O ₃ , manufactured by Aldrich) was added. In addition, the mixture was stirred and dissolved to obtain a transparent solution. To this, 2.37 g of TMADAOH aqueous solution (containing 25% by mass of TMADAOH, manufactured by Seychem) was added as an organic template, and 10.5 g of colloidal silica (Snowtech-40 manufactured by Nissan Chemical Co., Ltd.) was further added, followed by stirring for 2 hours. A mixture was obtained.

The composition (molar ratio) of this reaction mixture was SiO ₂ / Al ₂ O ₃ / NaOH / KOH / H ₂ O / TMADAOH = 1 / 0.033 / 0.05 / 0.1 / 100 / 0.04, SiO ₂ / Al ₂ O ₃ = 30.
A CHA-type zeolite membrane composite was prepared in the same manner as in Example 1 except that the reaction mixture was used and the calcination temperature was 450 ° C.

The mass of the CHA type zeolite crystallized on the support was 154 g / m ² . Further, the permeation amount of air after firing was 50 L / (m ² · h).
From XRD measurement, it was found that CHA-type zeolite was produced. Further, (the intensity of the peak near 2θ = 17.9 °) / (the intensity of the peak near 2θ = 20.8 °) = 1.2, and the orientation to the (1,1,1) plane in the rhombohedral setting Was guessed.

Moreover, as a result of observing the CHA-type zeolite membrane composite cut into strips with an SEM, crystals were densely formed on the surface.
Was also measured by _{SEM-EDX, SiO 2 / Al} 2 O 3 molar ratio of the zeolite membrane was 22.

(2) Single component gas permeation test A single component gas permeation test was conducted in the same manner as in Example 1 except that the CHA-type zeolite membrane composite prepared above was used. The evaluated gases are carbon dioxide and methane.
The permeance of carbon dioxide is 3.50 × 10 ⁻⁷ mol · (m ² · s · Pa) ⁻¹ , the permeance of methane is 2.46 × 10 ⁻⁹ mol · (m ² · s · Pa) ⁻¹ , dioxide The ideal separation factor α between carbon and methane was 142.

(3) Mixed gas permeation test A mixed gas permeation test was conducted in the same manner as in Example 1 except that the CHA-type zeolite membrane composite produced above was used.
The permeation amount of carbon dioxide was 16.5 mmol · (m ² · s) ⁻¹ , the permeation amount of methane was 0.132 mmol · (m ² · s) ⁻¹ , and the separation factor α ′ of carbon dioxide and methane was 130. It was.

(Example 3)
Except that the firing temperature was 500 ° C., using the CHA-type zeolite membrane composite produced in the same manner as in Example 2, except that the pressure of the supply gas was 0.2975 MPa, the same as in Example 2, A mixed gas permeation test was performed. The evaluated gases are carbon dioxide and methane.
The permeation amount of carbon dioxide was 25.0 mmol · (m ² · s) ⁻¹ , the permeation amount of methane was 0.191 mmol · (m ² · s) ⁻¹ , and the separation factor α ′ of carbon dioxide and methane was 136. It was.

Example 4
(1) Single-component gas permeation test The single-gas component permeability of the CHA-type zeolite membrane composite prepared in the same manner as in Example 2 was evaluated using the apparatus shown in FIG. . The gases evaluated are carbon dioxide, methane, hydrogen, nitrogen and helium.

The zeolite membrane composite was introduced at 140 ° C. and He as the supply gas 7 between the pressure vessel 2 and the zeolite membrane composite 1 cylinder, and the pressure was kept at 0.400 MPa. The inside of the cylinder was set to 0.100 MPa (atmospheric pressure), dried for 120 minutes, and pretreated.
Thereafter, the pressure on the supply side was set to 0.200 MPa, and the supply gas was changed to each evaluation gas. At this time, the differential pressure between the supply gas 7 side and the permeate gas 8 side of the zeolite membrane composite 1 was 0.100 MPa.

Thereafter, the temperature was set to 50 ° C., and after the temperature was stabilized, the supply gas was changed to each evaluation gas. At this time, the differential pressure between the supply gas 7 side and the permeate gas 8 side of the zeolite membrane composite 1 was 0.100 MPa.
Table 1 shows the permeance of each gas thus obtained. The ideal separation factor α between carbon dioxide and methane at 50 ° C is 783, the ideal separation factor α between hydrogen and methane is 264, the ideal separation factor α between nitrogen and methane is 48, and the ideal separation factor α between nitrogen and methane is 48 ° C. The ideal separation factor α was 171, the ideal separation factor α for hydrogen and methane was 94, and the ideal separation factor α for nitrogen and methane was 12.

The mixed gas permeability of the CHA-type zeolite membrane composite prepared above was examined using the apparatus shown in FIG. Specifically, the following mixed gas permeation tests 1 to 4 were performed. Drying (pretreatment) was performed in the same manner as the single gas permeation test.
(2) Mixed gas permeation test 1
A mixed gas adjusted to 75% by volume of carbon dioxide and 25% by volume of methane with a flow rate adjusting device was used as the supply gas. Introduced between the pressure vessel of FIG. 2 and the cylinder of the zeolite membrane composite 1 at a flow rate of 40, 24, and 8 mmol / min, the supply gas pressure was 0.300 MPa. The partial pressures of carbon dioxide and methane are 0.225 MPa and 0.0750 MPa, respectively. The inside of the cylinder of the zeolite membrane composite 1 is 0.100 MPa.

  Table 2 shows the permeation amount of carbon dioxide and methane, and the separation factor of carbon dioxide and methane. The separation factor was smaller under conditions where the total flow rate was low. This is probably because when the flow rate is small, the supply gas is not sufficiently mixed and the concentration of methane in the vicinity of the outside of the membrane is high.

(3) Mixed gas permeation test 2
As the supply gas, a mixed gas adjusted to 28% by volume of hydrogen and 72% by volume of methane by a flow rate adjusting device was used. The temperature chamber was set to 50 ° C., and the gas was introduced at a flow rate of 45, 27, and 9 mmol / min between the cylinder of the pressure-resistant vessel and the zeolite membrane composite 1 shown in FIG. The partial pressures on the supply gas 7 side of hydrogen and methane are 0.112 MPa and 0.288 MPa, respectively. The inside of the cylinder of the zeolite membrane composite 1 is 0.100 MPa.

  Table 3 shows the permeation amount of hydrogen and methane, and the separation factor of hydrogen and methane. The separation factor was smaller under conditions where the total flow rate was low. This is probably because when the flow rate is small, the supply gas is not sufficiently mixed and the concentration of methane in the vicinity of the outside of the membrane is high.

(4) Mixed gas permeation test 3
The feed gas was a standard gas of 55% nitrogen, 30% carbon monoxide, and 15% hydrogen. The temperature chamber was set to 50 ° C., and the pressure was supplied between the pressure vessel of FIG. 2 and the zeolite membrane composite 1 at a flow rate of 27 mmol / min, and the supply gas pressure was set to 0.300 MPa.
The partial pressures on the supply gas 7 side of nitrogen, carbon monoxide, and methane are 0.166 MPa, 0.0900 MPa, and 0.0440 MPa, respectively. The inside of the cylinder of the zeolite membrane composite 1 is 0.100 MPa.

Nitrogen, carbon monoxide, permeation amount of hydrogen is respectively ^{2.1mmol · (m 2 · s)} -1, 3.8mmol · (m 2 · s) -1, 2.9mmol · (m 2 · s) -1 The carbon monoxide and nitrogen and hydrogen and nitrogen separation coefficients α ′ were 1.4 and 2.1, respectively, and the permeance ratio was 1.6 and 3.4.

(5) Mixed gas permeation test 4
Air was used as the supply gas. The constant temperature bath was set to 50 ° C., and the gas was introduced between the pressure vessel of FIG. 2 and the zeolite membrane composite 1 at a flow rate of 27 mmol / min, so that the supply gas pressure was 0.300 MPa.
The permeation amounts of nitrogen and oxygen are 5.2 mmol · (m ² · s) ⁻¹ , 1.9 mmol · (m ² · s) ⁻¹ , respectively, and the separation coefficient α ′ of oxygen and nitrogen is 1.4, The permeance ratio was 1.6. The results are shown in Table 5.

(Example 5)
(1) Production of CHA-type zeolite membrane composite As the reaction mixture for hydrothermal synthesis, the following was prepared, and the inorganic porous support-CHA type was the same as in Example 1 except that the firing temperature was 500 ° C. A zeolite membrane composite was prepared.
The reaction mixture for hydrothermal synthesis was a mixture of 14.0 g of 1 mol / L-KOH aqueous solution and 104.0 g of water, 0.29 g of lithium hydroxide monohydrate and aluminum hydroxide (Al ₂ O ₃ 53.5 wt. 1.33 g (manufactured by Aldrich Co., Ltd.) was added and stirred to dissolve to obtain a transparent solution. To this was added 2.37 g of a TMADAOH aqueous solution (containing 25% by weight of TMADAOH, manufactured by Sechem Co.), and further 10.5 g of colloidal silica (Snowtech-40 manufactured by Nissan Chemical Co., Ltd.) was added and stirred for 2 hours to prepare.

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, SiO ₂ / Al ₂ O ₃ = 10.
The weight of the CHA-type zeolite crystallized on the support, determined from the difference between the weight of the calcined zeolite membrane composite and the weight of the support, was 120 g / m ² .
The air permeation amount of the zeolite membrane composite after calcination was 147 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, (peak intensity around 2θ = 17.9 °) / (2θ = 20.8 °)
The intensity of the peak in the vicinity of 2θ = 17.9 ° is significantly higher than the XRD of the powdered CHA-type zeolite used for the seed crystal, which is (1,1) in the rhombohedral setting. 1) Orientation to the plane was estimated.
As a result of observing the inorganic porous support-CHA-type zeolite membrane composite cut into strips by SEM, crystals were densely formed on the surface.
Further, the SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite membrane measured by SEM-EDX was 19.

(2) Single component gas permeation test A single component gas permeation test was conducted in the same manner as in Example 1 except that the CHA-type zeolite membrane composite prepared above was used. The evaluated gases are carbon dioxide and methane.
The permeance of carbon dioxide is 7.13 × 10 ⁻⁷ mol · (m ² · s · Pa) ⁻¹ , the permeance of methane is 6.07 × 10 ⁻⁹ mol · (m ² · s · Pa) ⁻¹ , dioxide The ideal separation factor α between carbon and methane was 117.

(Example 6)
(1) Production of CHA-type zeolite membrane composite As the reaction mixture for hydrothermal synthesis, the following was prepared, the standing time at 160 ° C., the heating time under autogenous pressure was 5 days, and the firing temperature was 500 ° C. An inorganic porous support-CHA type zeolite membrane composite was produced in the same manner as in Example 1 except that.

The reaction mixture for hydrothermal synthesis is a mixture of 15.0 g of 1 mol / L-NaOH aqueous solution and 75.0 g of water, and 0.71 g of aluminum hydroxide (containing 53.5% by weight of Al ₂ O ₃ , manufactured by Aldrich). In addition, it was stirred and dissolved to obtain a transparent solution. To this was added 25.3 g of a TMADAOH aqueous solution (containing 25% by weight of TMADAOH, manufactured by Sechem Co.), and a mixture of 9.0 g of fumed silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) and 10.0 g of water was added and stirred for 2 hours. Prepared.

The composition (molar ratio) of this reaction mixture was SiO ₂ / Al ₂ O ₃ / NaOH / H ₂ O / TMADAOH = 1 / 0.025 / 0.1 / 44 / 0.2, SiO ₂ / Al ₂ O ₃ = 40.
The weight of the CHA-type zeolite crystallized on the support, determined from the difference between the weight of the zeolite membrane composite after calcination and the weight of the support, was 330 g / m ² .

The air permeation amount of the zeolite membrane composite after calcination was 67 L / (m ² · h).
When XRD of the produced membrane was measured, it was found that CHA-type zeolite was produced. In the XRD pattern, (peak intensity around 2θ = 9.6 °) / (peak intensity around 2θ = 20.8 °) = 1.5, peak intensity around 2θ = 17.9 °) / ( 2θ
= Intensity of peak around 20.8 °) = 0.3. Thus, the XRD of the produced film
None of the peaks showed a specific intensity. From this, for example, it is presumed that the generated film is not oriented in any of the (1, 0, 0) plane and the (1, 1, 1) plane in rhombohedral setting.

(2) Single component gas permeation test A single component gas permeation test was conducted in the same manner as in Example 1 except that the CHA-type zeolite membrane composite prepared above was used.
The permeance of carbon dioxide is 9.29 × 10 ⁻⁷ mol · (m ² · s · Pa) ⁻¹ , and the permeance of methane is 1.27 × 10 ⁻⁹ mol · (m ² · s · Pa) ⁻¹ , dioxide The ideal separation factor α between carbon and methane was 7.3.

(Example 7)
Inorganic porous support-CHA-type zeolite as in Example 2 except that a 80 mm long porous alumina tube (outer diameter 12 mm, inner diameter 9 mm) was used as the ceramic support, and the firing temperature was 500 ° C. A membrane complex was prepared.
The weight of the CHA-type zeolite crystallized on the support, determined from the difference between the weight of the zeolite membrane composite after calcination and the weight of the support, was 157 g / m ² .

The air permeation amount of the zeolite membrane composite after calcination was 81.7 L / (m ² · min).
When XRD of the produced membrane was measured, it was found that CHA-type zeolite was produced. In the XRD pattern, from the XRD pattern, (the intensity of the peak near 2θ = 17.9 °) / (the intensity of the peak near 2θ = 20.8 °) = 2.0, and the CHA of the powder used for the seed crystal Compared with XRD of type zeolite, the intensity of the peak in the vicinity of 2θ = 17.9 ° was remarkably large, and the orientation to the (1,1,1) plane in the rhombohedral setting was estimated.

(2) Single-component gas permeation test A single-component gas permeation test was conducted using the CHA-type zeolite membrane composite produced above. As a pretreatment, the zeolite membrane composite is introduced at 140 ° C. and CO 2 as the supply gas 7 is introduced between the cylinders of the pressure vessel 2 and the zeolite membrane composite 1 to keep the pressure at 0.200 MPa, and the zeolite membrane The inside of the cylinder of the composite 1 was set to 0.098 MPa (atmospheric pressure) and dried for 70 minutes. Otherwise, the single component gas permeation test was conducted in the same manner as in Example 4. The gases evaluated are carbon dioxide, methane, hydrogen, nitrogen and helium.

  Table 6 shows the permeance of each gas thus obtained. The ideal separation factor α of carbon dioxide and methane at 50 ° C is 368, the ideal separation factor α of hydrogen and methane is 130, the ideal separation factor α of nitrogen and methane is 21, and the ideal separation factor α of carbon dioxide and methane at 140 ° C The ideal separation factor α was 54, the ideal separation factor α between hydrogen and methane was 41, and the ideal separation factor α between nitrogen and methane was 5.

(Comparative Example 1)
A ceramic support-MFI type zeolite membrane composite was produced by hydrothermal synthesis of MFI type zeolite directly on the ceramic support.
A reaction mixture for hydrothermal synthesis was prepared as follows.
To 118 g of water, 4.1 g of an aqueous solution of tetrapropylammonium hydroxide (hereinafter referred to as “TPAOH”) (containing 40% by mass of TPAOH, manufactured by Sechem Co.) was added as an organic template, and tetraethoxysilane (hereinafter referred to as “ 9.9 g) was added and stirred for 2 hours to give an aqueous reaction mixture.

The composition (molar ratio) of this reaction mixture is TEOS / TPAOH / H ₂ O = 1 / 0.17 / 140.
As the ceramic support, a porous alumina tube (outer diameter 12 mm, inner diameter 9 mm) was cut into a length of 80 mm, washed with an ultrasonic cleaner and dried.
As seed crystals, SiO ₂ / NaOH / TPAOH / H ₂ O = 1 / 0.1 / 0.1 / 40
The MFI-type zeolite obtained by hydrothermal synthesis at 160 ° C. for 1 day and crystallizing with a gel composition (molar ratio) was filtered, washed with water and dried.

The support was immersed in a dispersion of the seed crystal in about 1% by mass of water for a predetermined time, and then dried at 100 ° C. for 5 hours or more to attach the seed crystal. The mass of the attached seed crystal was about 1.6 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 aqueous reaction mixture in the vertical direction, and the autoclave was sealed, and allowed to stand at 160 ° C. for 48 hours. And heated under autogenous pressure. After the elapse of a predetermined time, the support-zeolite membrane composite was taken out of the reaction mixture after being allowed to cool, washed, and then dried at 100 ° C. for 5 hours or more.
This membrane composite was baked in an electric furnace at 450 ° C. for 32 hours in air. At this time, the rate of temperature increase and the rate of temperature decrease were both 0.5 ° C./min. The mass of the MFI 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 85 g / m ² .
From XRD measurement, it was found that MFI type zeolite was produced.

(2) Single component gas permeation test A single component gas permeation test was conducted in the same manner as in Example 7 except that the MFI type zeolite membrane composite produced above was used. The gases evaluated are carbon dioxide, methane, hydrogen, nitrogen and helium.

  Table 7 shows the permeance of each gas thus obtained. The ideal separation factor α of carbon dioxide and methane at 50 ° C is 1.2, the ideal separation factor α of hydrogen and methane is 1.0, the ideal separation factor α of nitrogen and methane is 0.5, and at 140 ° C The ideal separation factor α of carbon dioxide and methane was 0.7, the ideal separation factor α of hydrogen and methane was 1.2, and the ideal separation factor α of nitrogen and methane was 0.5.

  As in Examples 1 to 7, when a gas permeability evaluation is performed using a zeolite membrane containing a CHA-type aluminosilicate zeolite and formed on a ceramic support, the permeability may differ depending on the gas. Recognize. When mixed gas is used, highly permeable gas permeates the membrane, and less permeable gas concentrates without passing through the membrane, separating highly permeable gas out of the system, and having low permeable gas. The target gas could be separated from the gas mixture with high purity by concentrating and recovering the gas.

  On the other hand, when the gas permeability was evaluated using a zeolite membrane containing MFI type aluminosilicate and formed on a ceramic support, the gas permeability was almost uniform regardless of the gas. became. In the MFI membrane, it is considered that shape-selective separation is impossible because the molecular diameter of the gas evaluated is smaller than the pore diameter.

  The present invention can be used in any industrial field. For example, separation of a gas mixture in a chemical industrial plant that requires gas separation, a natural gas refining plant, a plant that generates biogas from raw garbage, and the like. It can be particularly preferably used.

1: Zeolite membrane composite 2: Pressure-resistant container 3: End pin 4: Connection part 5: Pressure gauge 6: Back pressure valve 7: Supply gas 8: Permeate gas 9: Sweep gas 10: Exhaust gas 11: Permeate gas exhaust pipe 12: Sweep gas introduction piping

Claims (6)

A zeolite membrane composite having a zeolite membrane on a ceramic support, the air permeability when the zeolite membrane composite is placed under atmospheric pressure and the inside of the zeolite membrane composite is connected to a vacuum line of 5 kPa is 700 L / (M ² · h) or less,
The zeolite membrane includes a CHA-type aluminosilicate zeolite mainly composed of oxides of Si and Al ,
A zeolite membrane composite for gas separation, wherein the zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 12 or more and 100,000 or less and a particle diameter of 30 nm or more . Permeance when carbon dioxide permeates at a temperature of 50 ° C. and a differential pressure of 0.098 MPa is 1 × 10 ^-9 The zeolite membrane composite for gas separation according to claim 1, which is as described above. The zeolite membrane composite for gas separation according to claim 1 or 2, wherein the zeolite membrane has a thickness of 20 µm or less. It is a manufacturing method of the zeolite membrane composite for gas separation as described in any one of Claims 1-3, Comprising: A ceramic support body in the reaction mixture for hydrothermal synthesis containing Si element source and Al element source And producing a zeolite membrane composite for gas separation, wherein the zeolite is crystallized into a membrane on the surface of the support by hydrothermal synthesis. 5. The method for producing a zeolite membrane composite for gas separation according to claim 4, wherein the ratio of the Si element source and the Al element source is 5 to 100,000 in terms of SiO ₂ / Al ₂ O ₃ molar ratio. The method for producing a zeolite membrane composite for gas separation according to claim 4 or 5, wherein the aqueous reaction mixture contains potassium or sodium as an alkali source.

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