WO2007077646A1

WO2007077646A1 - Process for producing composite membrane

Info

Publication number: WO2007077646A1
Application number: PCT/JP2006/316250
Authority: WO
Inventors: Hironobu Shirataki; Zhengbao Wang; Kensuke Aoki; Hiroyoshi Ohya
Original assignee: Asahi Kasei Chemicals Corporation
Priority date: 2005-12-28
Filing date: 2006-08-18
Publication date: 2007-07-12
Also published as: JP2009066462A

Abstract

A process for producing a composite membrane, comprising bringing a porous support provided on its surface with zeolite microparticles with the use of an organic polymer as a binder into contact with a synthetic solution containing a raw material of zeolite and carrying out a hydrothermal synthesis to thereby form a zeolite crystal membrane on the surface of the porous support.

Description

Specification

Method for producing composite membrane

Technical field

[0001] The present invention relates to a method for producing a composite membrane in which a layer composed of zeolite crystals having a molecular sieving function is formed on a hollow cylindrical porous support, a composite membrane obtained by the production method, The present invention also relates to a material separation method for separating a specific component from a liquid, gas, or a mixture thereof by a per-partition method or a per-permeation method using the composite membrane.

Background art

[0002] As a method for selectively separating water or organic substances from a solution in which water and organic substances are uniformly mixed, a distillation method is widely used. Ethanol, isopropanol, butanol, etc. become azeotropic at a certain concentration or higher by mixing with water, so they cannot be separated by the usual distillation method, and harmful entrainers such as benzene are not used. It is necessary to use the azeotropic distillation method used.

[0003] In addition to the need for such a harmful third component, the azeotropic distillation method also has high energy costs. Therefore, in recent years, as an alternative separation method, a pervaporation method or a single paper method is used. A separation method using a myelination has attracted attention, and it is known that a separation membrane using a zeolite membrane is high and exhibits separation performance.

In particular, in the case of dehydration by pervaporation using a hydrophilic A-type zeolite membrane formed on a porous support, the permeation flux Q = 2. 15 kgZm ² h in an aqueous solution at a temperature of 75 ° C and 90% by weight of ethanol. Thus, an extremely high separation performance with a separation coefficient a of 10,000 or more can be obtained (see Patent Document 1).

[0004] As a film forming method for forming a layer (membrane) composed of zeolite crystals on a porous support, a method is used in which a seed crystal of zeolite is applied to a porous support and the crystals are grown by hydrothermal synthesis. Method (for example, see Non-Patent Document 1), a method of growing crystals by direct hydrothermal synthesis (Patent Document 2), a gel as a raw material for zeolite is applied on a porous support, and then a film is formed by steam treatment. Examples include the dry gel method (Patent Document 3). Among these film forming methods The so-called seed crystal method, in which a seed crystal is applied to a support and is hydrothermally synthesized, is particularly effective in practical use as a method for forming a film of dense zeolite crystals without defects (Patent Document 1 and Four).

[0005] However, in the seed crystal method, it is an important factor that the seed crystal is uniformly applied in an appropriate amount on the support, and the seed crystal is not dispersed on the support surface. If it is uniform, a defect-free zeolite crystal film cannot be obtained, and high separation performance cannot be obtained. For this reason, there are many reports that do not reproduce the dewatering performance of Patent Document 1 even with A-type zeolite formed by a method using a similar seed crystal (for example, see Non-Patent Documents 2-4). .

[0006] Even in the case of a film formation method using a seed crystal that has been put to practical use in industry, it is not easy to control the state of application of the seed crystal to the surface of the support. For example, Patent Document 1 uses a method of rubbing seeds on a support, Patent Document 4 immerses the support in a seed dispersion aqueous solution, and Patent Document 5 brushes the seed dispersion aqueous solution on the surface of the porous support. By so doing, seed crystals are given to each. However, even if these methods are used, the control of the state of application of the seed to the support is not complete, and the seed crystal is fixed to the support surface by a cohesive force such as van der Waalska or zeta potential (Non Patents). Reference 5), it is difficult to completely suppress partial detachment due to vibration and contact. For this reason, defects such as the presence of defects in the membrane obtained by hydrothermal synthesis and the insufficient separation of the separation function due to the presence of non-crystalline components in the portion where the amount of seed crystals is excessive are caused. It is extremely difficult to keep it down enough.

[0007] In order to fix the seed crystal on the surface of the support, a method using bentonite as a binder as a method for supporting zeolite fine particles on the surface of a porous support using a binder (Patent Document 6), and water glass Alternatively, a method using silica sol as a binder is disclosed (Patent Document 7). However, in order for bentonite to function as a binder, it must be fired at 400 ° C or higher and hardened. At such high temperatures, the structure of the zeolite is destroyed and the crystal film is formed. It is not effective as a seed crystal loading method. In addition, since water glass or silica sol has low coating properties, it is not easy to uniformly and firmly support the zeolite fine particles on the surface of the porous support. Furthermore, since the solvent of bentonite, water glass or silica sol is limited to water or an organic solvent containing a large amount of water, A porous support capable of supporting zeolite fine particles as a binder is limited to a support having a high hydrophilic material force such as alumina.

In addition, the mechanism of the formation of the zeolite crystal film by the seed crystal is considered that the gap between the seed and the seed is filled with the gel of the synthesis solution used for hydrothermal synthesis, and the seed crystal becomes the nucleus and this gel grows into the crystal film. (Non-patent document 6). Therefore, the binder that fixes the seed crystal becomes an impurity that inhibits the seed from functioning as a nucleus of growth, and has not been used as a method for forming a zeolite crystal film.

As described above, it has been difficult to obtain a high-yield zeolite crystal film uniformly formed without defects and non-crystalline components on the surface of the support.

Patent Document 1: JP-A-7-185275

Patent Document 2: JP-A-6-99044

Patent Document 3: JP-A-7-89714

Patent Document 4: Japanese Unexamined Patent Application Publication No. 2004-82008

Patent Document 5: JP-A-8-318141

Patent Document 6: Japanese Patent Laid-Open No. 60-129119

Patent Document 7: JP-A-7-109116

Non-patent literature 1: Masakazu Kondo et al., Rubular-type pervaporation module with zeo lite NaA membrane "J. Memb. Sci., 1997, 133, 133

Non-Patent Document 2: M. P. Pina et al., "A semi-continuous mthod for the synthesis of NaA zeolite membranes on tubular supports" J. Memb. Sci., 2004, 244, 141

Patent Document 3: F.T.de Bruijn et al., "Influence of the support layer on the flux limitation in pervaporation J. Memb. Sci., 2003, 223, 141

Non-Patent Document 4: A. Huang et al., "Synthesis and properties of A-type zeolite membran es by secondary growth method with vacuum seeding" J. Memb. Sci., 2004, 245, 41 Non-Patent Document 5: M. Pera- Titus et al., "Preparation of zeolite NaA membrane on the in ner side of tubular support by means of a controlled seeding technique" Catalysis To day, 2005, 281, 104

Non-Patent Document 6: K. Okamoto et al., "Zeolite NaA membrane: Preparation, Single-Gas Permeation, and Pervaporation and Vapor Permeation of Water / organic Liquid "Ind. Eng. Chem. Res., 2001, 40, 163

Disclosure of the invention

Problems to be solved by the invention

[0009] The present invention relates to a separation membrane having a high separation factor and a high permeation flux, which is made of a zeolite crystal membrane, and in particular, from a azeotropic mixture by a pervaporation method or a perpermeation method. It is an object of the present invention to provide a composite membrane suitable for separating components and a method for producing it in high yield.

Another object of the present invention is to provide a method for separating a desired component from a mixed liquid, particularly an azeotropic mixture, using the composite membrane.

Means for solving the problem

[0010] When a zeolite crystal film is formed on a support by a conventional seed crystal method, seeds are imparted to the surface of the support by a method such as rubbing or dipping, and then the zeolite crystal film is formed by hydrothermal synthesis. Form a film. At this time, if the seed application is uneven, the amount applied is inappropriate, or the seed is detached after the application, defects will occur immediately, resulting in a decrease in separation performance and membrane formation. It is thought that the rate will decrease.

On the other hand, the present inventors imparted zeolite fine particles serving as seed crystals to the surface of a hollow cylindrical porous support using an organic polymer as a binder, so that the seed crystals are uniformly and strongly supported. Then, hydrothermal synthesis is performed to produce a zeolite crystal film with high yield and high separation performance in a simple manner without hindering the seed crystal from functioning as a nucleus for crystal growth. The present inventors have found that a composite membrane having the above can be obtained, and have completed the present invention.

That is, the present invention is as follows.

[0011] (1) A porous support having an organic polymer as a binder and provided with zeolite fine particles on the surface is brought into contact with a synthesis solution containing a zeolite raw material and subjected to hydrothermal synthesis to thereby form the porous support. A method for producing a composite film, comprising forming a zeolite crystal film on a surface.

(2) The porous support is formed by using a dispersion solution in which zeolite fine particles are dispersed in a solution of an organic polymer to form a zeolite on at least one of the inner surface and the outer surface of the porous support. 2. The method according to claim 1, wherein the method is a cylindrical porous support obtained by applying yttrium fine particles.

(3) The method according to claim 1, wherein the organic polymer is selected from the group consisting of polybutyral, polyvinyl alcohol, polysulfone, polyethersulfone, polyvinylidene fluoride, and polyethylene glycol.

(4) The method according to claim 1, wherein the porous support also has an inorganic force selected from ceramics and metal forces.

(5) The method according to claim 1, wherein the porous support comprises an organic polymer.

(6) The method according to claim 1, wherein the porous support is a hollow fiber obtained by wet spinning, which also has a mixture force of organic polymer and zeolite fine particles.

(7) The zeolite crystal film is an A type, an X type, a Y type, a T type, an L type, a ZSM, a sodalite, a mordenite, and a silicalite. 1 method.

(8) A composite membrane obtained by the production method according to any one of claims 1 to 7.

(9) The porous support has a three-layer structure having a layer composed of an organic polymer and zeolite fine particles and further having a zeolite crystal film thereon. A composite membrane obtained by the method according to any one of the above.

(10) The composite film according to claim 8 or 9, wherein the zeolite crystal film is made of hydrophilic zeolite.

(11) The composite film according to claim 8 or 9, wherein the zeolite crystal film is made of hydrophobic zeolite.

(12) Using the composite membrane according to any one of claims 7 to 10, a mixed solution or a mixture comprising two or more components by a pervaporation method or a single permeation method. A material separation method comprising separating at least one component from a gas.

(13) The method according to claim 12, wherein at least one component is separated from the mixed solution composed of water and organic matter.

(14) The method according to claim 12, wherein at least one component is separated by a mixed solution force having two or more kinds of organic substances.

The invention's effect [0012] According to the method for producing a composite film of the present invention, a zeolite crystal film that is uniform and has very few defects and non-crystalline components can be produced in a high yield. In addition, the composite membrane obtained by the method for producing a composite membrane of the present invention has high permeation flux and separation coefficient, and is excellent in adhesion between the zeolite crystal membrane and the porous support. Using such a composite membrane, it is versatile and

In a wide range of applications, it is possible to produce a separation module with a high separation factor and permeation flux and a high throughput. As a result, it is possible to economically separate the resulting mixture as an alternative to the distillation method.

In particular, the composite membrane of the present invention is suitable for selectively separating a desired component by the pervaporation method using an azeotropic mixture force composed of water and an organic compound.

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] The present invention is described in detail below.

The composite membrane obtained by the production method of the present invention uses an organic polymer as a binder, and is provided on at least one of the inner surface and the outer surface of a cylindrical porous support provided with zeolite fine particles on the surface. It has a structure in which a zeolite crystal film is formed. Zeolite crystal film is formed by hydrothermal synthesis by contacting the surface of a porous support with fine particles of zeolite crystal using an organic polymer as a binder in contact with the synthesis solution used as the raw material for the zeolite crystal film. To do. Since the zeolite fine particles are uniformly and firmly supported on the surface of the porous support using an organic polymer as a binder, not only the formation of a defect-free zeolite crystal film can be easily performed at a high yield, The separation factor and the permeation flux when separation is performed using the obtained zeolite crystal film by the pervaporation method or the pervaporation method are also improved.

[0014] The size of the zeolite fine particles supported on the surface of the porous support is preferably 0.01 μm or more and 10 m or less from the viewpoint of uniform dispersibility and adhesive strength on the surface of the porous support. More preferably, it is 0.1 μm or more and 5 μm or less.

As the zeolite fine particles, A-type, X-type, Y-type, T-type, L-type, ZSMs, sodalites, mordenites, silicalites, etc. can be used, but the zeolite crystal film formed on the surface thereof. Select the same type of zeolite.

From the viewpoint of forming a zeolite crystal film without defects, a zeolite crystal film is formed. It is desirable that zeolite fine particles occupy a surface area of 1% or more of the surface of the porous support before the hydrothermal synthesis. There is no upper limit to the proportion of the area occupied by the zeolite fine particles.

[0015] The porous support used in the present invention has a hollow cylindrical shape, that is, a hollow fiber shape and a tubular shape, and also includes a lotus root shape and a Hercam shape. The size of the porous support is not particularly limited. For example, in the case of hollow fibers and tubes, the outer diameter is preferably in the range of 0.5 mm to 10 cm, and the wall thickness is preferably in the range of 0.05 mm to 2 cm. preferable.

[0016] The porosity of the porous support used in the composite membrane of the present invention is 10% or more from the viewpoint of the permeation flux of the composite membrane. Depending on the material of the porous support, the porosity of the mechanical support is high. The viewpoint power is preferably 99% or less. More preferably, it is 30% or more and 95% or less, and most preferably 40% or more and 90% or less.

The pore size of the porous support needs to be large enough to prevent the permeation flux from decreasing because the movement of molecules separated by the pervaporation or the pervaporation is inhibited. Specifically, the average pore diameter is preferably lOnm or more from the viewpoint of permeation flux and 5 m or less from the viewpoint of the uniformity of the zeolite crystal film. More preferably, it is 50 nm or more and 2 μm or less.

[0017] The raw material of the porous support is made of alumina, mullite, silica, zirconia, bentonite, cordierite, silicon nitride, silicon carbide, ceramics such as glass, inorganic materials such as stainless steel and metals such as aluminum, polysulfone, Polyethersulfone, poly (vinylidene fluoride), polyethylene, polypropylene, polyacrylonitrile, polyamide, polyimide, polyester, polycarbonate, polyetherketone, silicone, cellulose and derivatives thereof, and copolymers containing these polymers. A molecule is used.

Among these, as raw materials that can form a cylindrical porous body and whose pore diameter and porosity are easy to control, ceramics such as alumina, mullite, bentonite, cordierite, polysulfone, polyethersulfone, polyfluoride Organic polymers such as vinylidene, polyethylene and polyacrylonitrile are preferred. A porous support obtained as a composite of an organic polymer and a ceramic can also be preferably used. Furthermore, the same kind of zeolite that forms the crystalline film A composite porous body obtained by mixing a kind of zeolite fine particles and an organic polymer can also be used as a preferred support.

[0019] When an inorganic material is used as the porous support, a wide range of materials can be selected as the organic polymer serving as a binder for supporting the zeolite fine particles on the surface. Typical examples include polyvinyl butyral, polyethylene glycol, polypropylene glycol, polystyrene, polyacrylate, polymethyl methacrylate, polybutyl alcohol, polysulfone, polyethersulfone, polyvinylidene fluoride, polyethylene, Polypropylene, polyamide, polyimide, polyester, polycarbonate, polyetherketone, polybutadiene, polyacrylonitrile, poly (butyl acetate), polyvinyl chloride, cellulose and derivatives thereof, and copolymers containing these polymers can be mentioned.

When an organic polymer is used as a binder, a solution obtained by dissolving the organic polymer in an appropriate solvent and dispersed with zeolite fine particles is applied to the porous support or applied. Is preferred. Further, even if the zeolite fine particles are applied by applying or immersing the porous support in a milky liquid such as latex and applying the zeolite fine particles, it does not matter as long as the polymer acts as a binder. .

Among these polymers, polyvinyl butyral, polyvinyl alcohol, polysulfone, polyether sulfone, polyvinylidene fluoride, and polyethylene glycol are preferable because they are particularly soluble in a common solvent and have good coating properties.

When an inorganic material is used as the porous support, since the inorganic substance is not dissolved by the organic solvent, the organic polymer used as the binder dissolves any of the above organic polymers, and the solvent dissolves the organic polymer. Any solvent can be selected.

[0020] On the other hand, when an organic polymer is used as the porous support, selection of the binder and its solvent is important unless latex is used as the binder. That is, it is necessary to select a support, a binder, and a solvent so that the organic polymer solvent that is the binder does not dissolve the organic polymer that is the support. Therefore, in the case where an organic polymer having a high molecular force such as polysulfone, polyethersulfone, polyvinylidene fluoride, polyethylene, or polyacrylonitrile is used as the porous support, the organic polymer that can be used as the binder is Bulbutyral, polybulal alcohol, and polyethylene glycol are preferred. These solvents include methanol, ethanol, 2-propanol, 1-butanol, methoxypropanol, ethylene glycol, 1,5-pentanediol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and diethylene glycol dimethylol. Ethenole, ethylene glycol dimethyl ether, 2-butoxyethanol, ethylenic glycolenomonoisobutinoleether, ethylene glycolenomonoisopropino ether, and ethylene glycol monohexyl ether are preferably used. Further, a combination of polyvinyl alcohol as the binder organic polymer and water or an alkaline aqueous solution as the solvent thereof can also be used as a combination without dissolving the organic polymer as the support.

[0021] As a method for supporting the zeolite fine particles on the surface of the porous support using the organic polymer, a dispersion solution in which the zeolite fine particles are dispersed in a solution of the organic polymer and its solvent is prepared, and the porous support is prepared. It is preferable that the quality support is lifted after being crushed and dried. Alternatively, the fine particles of zeolite can be supported on the surface of the support by applying the dispersion directly to the surface of the porous support with a brush or the like and drying.

[0022] By using an organic polymer as a binder, the zeolite fine particles are firmly fixed to the surface of the porous support, so that the seed crystals are supported as compared with the conventional supporting method in which the fine particles are fixed by cohesive force. It is extremely easy to handle the support from the start to the hydrothermal synthesis! That is, when the seeds are supported by cohesive force, the seeds partially peel off when touching the surface or applying an impact before hydrothermal synthesis, and the seeds are separated from the seeds immediately by convection in the synthesis solution. Since the zeolite fine particles may be detached from the support force, the denseness of the crystal film obtained after hydrothermal synthesis tends to decrease.

[0023] On the other hand, the use of an organic polymer as a binder suppresses the elimination of species before and during hydrothermal synthesis, thus facilitating the formation of a dense crystal film and separation. High performance zeolite crystal membranes can be obtained in high yield.

In contrast to the case where an inorganic binder such as water glass or silica sol is used as a binder, when the organic polymer of the present invention is used as a binder, an organic solvent can be used as a solvent for the binder. Polysulfone, polyvinylidene fluoride, only with a hydrophilic support, A seed can be easily and uniformly supported on a highly hydrophobic support such as polyethylene.

[0024] In the composite membrane of the present invention, a layer (membrane) made of zeolite crystals is formed on the surface of the porous support. Zeolite crystals form grain boundaries and are packed densely to form a layer (film) on the surface of a hollow cylindrical porous support.

As the zeolite, various hydrophilic zeolites and hydrophobic zeolites can be used. Examples of the hydrophilic zeolite include A type, X type, Y type, T type, and L type, and examples of the hydrophobic zeolite include ZSMs, sodalites, mordenites, and silicalites. Moreover, when these contain an alkali metal or an alkaline earth metal, various zeolites in which they are replaced with other metal ions can also be used.

[0025] The size of the crystals forming the zeolite crystal film is preferably in the range of 0.01 μm force to 10 μm in order to prevent both separation performance and permeation flux from deteriorating. Preferably 0.1 μm force or 5 μm.

The thickness of the zeolite layer is preferably 0.1 μm or more from the viewpoint of separation performance and 50 μm or less from the viewpoint of the permeation flux, more preferably 0.5 μm force or 30 μm. is there.

The zeolite crystal film in the composite film of the present invention is formed by bringing the porous support of the present invention into contact with a synthesis solution containing a zeolite raw material and performing hydrothermal synthesis under appropriate conditions.

[0026] As the silica component used as a raw material for zeolite, sodium silicate, water glass, colloidal silica, silicon dioxide, alkoxysilane hydrolyzate, and the like can be used. Examples of the alumina component that is a raw material for zeolite include sodium aluminate, aluminum hydroxide, aluminum nitrate, aluminum salt, boehmite, and the like. Further, sodium hydroxide is used as a raw material of sodium that exhibits alkalinity during hydrothermal synthesis and forms zeolite. If necessary, calcium hydroxide, calcium hydroxide, calcium carbonate, calcium nitrate, calcium chloride, etc., magnesium oxide, magnesium hydroxide, magnesium oxide, magnesium nitrate, salt匕 Barium nitrate, barium chloride, barium hydroxide, etc. are used as barium oxide components such as magnesium. [0027] In hydrothermal synthesis, a synthetic support containing the above-mentioned zeolite raw material is placed in a sealable container such as an autoclave, and a porous support provided with zeolite fine particles using an organic polymer as a binder is provided here. The zeolite crystal film is formed on the surface of the porous support by immersing and allowing the synthesis reaction to proceed at an appropriate temperature for an appropriate time. At this time, when the zeolite crystal film is formed only on the outer surface of the porous support, the synthetic solution comes into contact with the inner surface by sealing the openings at both ends of the cylindrical porous support. After so doing, immerse in the synthesis solution. In addition, when forming a zeolite crystal film only on the inner surface of the porous support, the outer surface is covered with a Teflon (registered trademark) seal or the like to block the contact of the synthetic solution with the outer surface, thereby forming a cylindrical shape. The inside of the porous support is filled with the synthesis solution, and the support is immersed in the synthesis solution and the synthesis reaction is allowed to proceed at an appropriate temperature for an appropriate time, or the temperature inside the porous support is increased. A zeolite crystal film is formed by a method such as circulating a synthetic solution in which the temperature is controlled.

[0028] By using the composite membrane of the present invention, a mixed solution force of two or more liquids can be separated by a pervaporation method.

As the mixed solution, a mixed solution of water and an organic material or a mixed solution of two or more organic materials is preferably used.

In the case of selectively separating water or organic matter by the pervaporation method, for example, mixed solution force containing ethanol and water obtained by fermentation To selectively separate ethanol or water Conventionally, distillation has been a common separation method. However, since the mixture of ethanol and water obtained by fermentation contains a large amount of water, a large amount of energy is required to separate and concentrate by distillation. In such a case, when the composite membrane of the present invention is used, by selectively selecting the type of zeolite, the pervaporation method can be used to selectively select only the target product from the mixture of water and organic matter and to reduce the force. It becomes possible to separate by energy consumption.

[0029] When only water is selectively separated, hydrophilic zeolite such as A-type, X-type and T-type is used as the type of zeolite. On the other hand, when ethanol is selectively separated, hydrophobic zeolite such as ZSMs and silicalites is used. In the case of a mixture other than the above, the optimum zeolite may be selected depending on the type and purpose. Examples of separating a mixed solution of two or more organic substances include ketones such as acetone and methyl ethyl ketone, halogenated hydrocarbons such as carbon tetrachloride and trichloroethylene, and aromatics such as benzene and cyclohexane. Examples include extracting alcohols from a mixed solution with alcohols such as methanol, ethanol and propanol.

Example

Hereinafter, the present invention will be specifically described with reference to examples.

In the present invention, the average pore diameter and porosity of the porous support were measured by a mercury intrusion method using a pore sizer 9320 porosimeter (trade name) manufactured by Micromeritics. In the measurement, mercury was injected by using a cell having a cell volume of about 6 cm ³ and a stem volume of 0.4 cm ^{3 in} a pressure range of 0 MPa to 206.8 MPa. The porous support used for the measurement was kept in an oven at 150 ° C. for 4 hours before drying, dried, cooled to room temperature in a desiccator, and then used for the measurement. The amount of sample to be filled in the measurement cell was adjusted so that the total mercury intrusion volume was in the range of 0.1 ml to 0.3 ml, and a sample of 0.1 lg to 0.5 g was used in this measurement.

[0031] (1) Average pore diameter of porous support

In the mercury intrusion method, the relationship between the pressure at the time of intrusion and the pore diameter at which mercury intrudes at that pressure is expressed by the following Washburn equation (1).

[0032] [Equation 1]

In the above formula (1), each character represents:

D: Pore diameter of porous support

P: Pressure when injecting mercury y: Surface tension of mercury (480dyneZcm)

0: Contact angle between mercury and pore wall (130 ° in this case)

[0033] From the above equation, the relationship between the press-fit pressure P and the pore diameter D is obtained. Since the intrusion pressure P and the amount of mercury injected so far can be obtained by measurement, the average pore diameter based on the volume average of the porous support can be obtained from the above relational expression.

[0034] (2) Porosity of porous support

The volume of the porous support sample in the measurement cell is the sum of the volume of the sample and mercury in the cell before applying pressure when the sample and mercury are injected into the measurement cell, and the volume difference of the injected mercury. As required. The porosity of the porous support is determined as the ratio of the volume of the porous support sample used for the measurement to the volume corresponding to the total mercury intrusion when mercury is injected to the maximum pressure in the measurement pressure range. It is done.

[0035] (3) Energy dispersive X-ray spectroscopy (EDS)

The distribution of organic binder in the composite membrane before and after hydrothermal synthesis was determined by mapping by energy dispersive X-ray spectroscopy (EDS) using EMAX-7000 manufactured by Horiba. In the measurement, the electron beam acceleration voltage was 15kV, the working distance was 12mm, the beam current was 0.4nA, and the mapping was performed by detecting the characteristic X-rays of carbon atoms by irradiating the electron beam.

[Example 1]

(Preparation of zeolite fine particle dispersion)

As a binder, 3 g of polysulfone (manufactured by Aldrich, Mn = 16000) 25.5 g of dimethylacetamide was added and stirred until it was uniformly dissolved. Here, 1.5 g of polyethylene glycol 400 (manufactured by Wako Pure Chemical Industries, Ltd.) was added and further stirred until a uniform transparent polymer solution was obtained. To this high molecular solution, 6 g of A-type zeolite fine particles (manufactured by Sigma-Aldrich, Molecular Sieve 4A, particle size: 5 μm) were added and stirred for 2 hours to prepare a uniform zeolite fine particle dispersion.

[0037] (Support of zeolite fine particles on porous support)

As the porous support, an alumina porous support with an outer diameter of 1.6 mm, a film thickness of 0.4 mm, a porosity determined by the mercury intrusion method of 37%, and an average pore diameter of 0 is prepared. did.

The alumina porous support was immersed in a 50% aqueous solution of polyethylene glycol # 2000 (manufactured by Kanto Yigaku) for 1 minute and then dried in an oven at 60 ° C. for 2 hours. This alumina porous support was immersed in the above zeolite fine particle dispersion for 10 seconds, dried in an oven at 60 ° C. for 1 minute, and then immersed in water for 3 minutes to solidify polysulfone. After extracting polyethylene glycol by immersing in water at 60 ° C for 3 hours, the surface of the mullite tube is porous with about 5 m thick polysulfone and zeolite fine particles by scanning electron microscopic observation. A layer was formed. In this way, the zeolite fine particles supported on the support using the organic polymer as a binder did not separate even when impacted on the support and did not separate even when rubbed with a finger.

Figure 1 shows the cross-sectional electron microscope (SEM) image of the support carrying the resulting zeolite fine particles and the distribution of silicon and carbon in the cross section observed by energy dispersive X-ray spectroscopy (EDS). . The SEM image shows that zeolite fine particles are applied to the surface of the porous support. Also, the EDS image shows brightly the part where the silicon (Si) atoms that make up the zeolite fine particles and the carbon (C) atoms that make up the binder are present, and from the image obtained by this EDS method. This indicates that carbon is unevenly distributed around the zeolite fine particles, and the zeolite fine particles are bound to the support surface by the organic polymer.

(Formation of zeolite crystal film)

The above porous support having a length of 10 cm was prepared, and a layer made of A-type zeolite crystals was formed on the surface of the porous support by a hydrothermal synthesis method. The synthesis solution is water, sodium silicate, sodium aluminate and sodium hydroxide, Na 0: SiO: AI O: H 0 = 2: 2: 1: 125

2 2 2 3 2

Using a slurry blended in a molar ratio, immerse the above porous support in a Teflon (registered trademark) container containing the slurry, and place the container in an autoclave at 100 ° C for 3 hours. Hydrothermal synthesis reaction was performed for 15 minutes.

After the reaction, the porous support was taken out, washed thoroughly with water, and dried at 60 ° C. for 3 hours. When the cross section of the porous support after drying was observed with an electron microscope, there was a porous layer of organic polymer and zeolite fine particles on the porous support, and the surface on the side in contact with the synthesis solution was observed. It was confirmed that a crystal film with a thickness of about 5 m was formed on the surface. Figure 2 shows this SEM image. In FIG. 2, I is a zeolite crystal layer (film), II is a zeolite particle Z organic polymer binder layer, and ΙΠ is an alumina porous support layer. As a result of analyzing this by wide-angle X-ray diffraction, it was confirmed that a dense layer of A-type zeolite crystals was formed.

Figure 3 shows the cross-sectional SEM image of the dense zeolite film on the obtained support and the carbon distribution in the cross-section observed by the EDS method. From the image obtained by the EDS method, it is shown that carbon (C) is dispersed and present on the surface of the zeolite crystal film and in the porous layer composed of the zeolite fine particles and the organic polymer binder. Note that the binder present on the surface of the zeolite crystal membrane may flow out during the dehydration test by the pervaporation described below, but does not affect the separation performance.

(Dehydration test with pervaporation)

Twenty composite membranes thus obtained were prepared, both ends were fixed with silicone resin, and one side was sealed to produce a module. Using this module, an ethanol aqueous solution was selectively separated by the pervaporation method. Figure 4 shows a schematic diagram of the separation device using the modules used in this test. A 90% by weight aqueous solution of ethanol is supplied inside module 5 by circulating it at a temperature of 75 ° C., and the inside of the porous support in module 5 is depressurized by vacuum pump 1 to Water in an ethanol aqueous solution was allowed to permeate from the outer surface to the interior of the air. Water separated through the composite membrane passed through vacuum line 2 and was collected in trap 3 cooled by liquid nitrogen. Between the vacuum line 2 and the trap 3, a vacuum gauge 4 is installed. In the figure, trap 6 was installed to trap the vacuum pump force when oil flows backward.

The weight of water in the cooling trap 3 was measured, and the permeation flux (Q) was determined by determining the permeation amount per unit area and unit time of the membrane. By measuring the concentration of ethanol contained in the trapped water using gas chromatography, the separation factor was determined. Specifically, the weight concentrations of ethanol and water on the supply side are

1% by weight and X

The separation factor (H) is calculated by the following equation (2), assuming that the concentration of ethanol and water on the permeate side in the trap is Y wt% and Y wt%, respectively.

2

α = (Χ / Χ) / (Υ / Υ) · '· (2) Separation experiment was conducted to selectively extract water from an aqueous solution of 90% by weight of ethanol using a pervaporation method at a temperature of 75 ° C. The permeation flux (Q) of water was 5.3 kgZm ² h, and the separation factor was 130000.

After the evaluation, the module was disassembled and individual separation experiments were performed on the composite membrane. One of the 20 samples had a force of 000, but the remaining 19 samples all had a separation factor of 10000 or more. In addition, the permeation flux of the composite membrane with a separation factor of 10000 or more was 5. Okg / m or more.

[0040] (Example 2)

(Preparation of zeolite fine particle dispersion)

As a binder, polyvinyl butyral 300 (manufactured by Wako Pure Chemical Industries, average polymerization degree 200-400) 0.4 g and methoxypropanol 19.8 g were mixed, and after the binder was completely dissolved, A type zeolite fine particles (Mizusawa A zeolite fine particle dispersion was prepared by adding 0.4 g of Shilton-B, particle size 0.8;

[0041] (Support of zeolite fine particles on porous support)

After sealing both ends of an alumina porous support obtained by sintering alumina particles having an outer diameter of 1.2 mm, a film thickness of 0.2 mm, an average pore diameter of 0.25 m, and a porosity of 48%, zeolite It was soaked in the fine particle dispersion for 10 seconds. After pulling up, drying was performed in an air atmosphere at 60 ° C. for 1 hour, whereby zeolite fine particles were supported on the surface of the porous alumina support by a binder. The supported zeolite fine particles were not detached even when an impact was applied to the support, and they did not desorb even when rubbed with a finger.

Figure 5 shows the cross-sectional electron microscope (SEM) image of the support on which the obtained zeolite fine particles are supported, and the carbon distribution in the cross section observed by energy dispersive X-ray spectroscopy (EDS). The SEM image shows that zeolite fine particles are applied to the surface of the porous support. In the EDS image, the part where the carbon atoms constituting the binder are present is shown in white. From the image obtained by this EDS method, carbon is unevenly distributed around the zeolite fine particles. Are bound to the surface of the support by the organic polymer. An A-type zeolite crystal film (layer) was formed on the surface of the porous support supporting the zeolite fine particles by hydrothermal synthesis in the same manner as in Example 1. After the reaction, the porous support was taken out, thoroughly washed with water, and dried at 60 ° C for 3 hours. When the cross section of the porous support after drying was observed with an electron microscope, a crystal film with a thickness of about 5 m was formed on the surface in contact with the synthesis solution, which was analyzed by wide-angle X-ray diffraction. As a result, it was confirmed that a dense film (layer) of A-type zeolite crystals was formed.

Figure 6 shows the cross-sectional SEM image of the dense zeolite film on the obtained support and the carbon distribution in the cross-section observed by the EDS method. From the image obtained by the EDS method, carbon is present in a dispersed state on the surface of the dense zeolite membrane, and after hydrothermal synthesis, the organic polymer used as a binder is mainly distributed on the surface of the dense zeolite membrane. Is shown. Note that the binder present on the surface of the zeolite fine membrane may not flow out during the dehydration test by pervaporation described below, but does not affect the separation performance.

[0042] (Dehydration test with pervaporation)

Thus obtained composite membrane was prepared twenty obtained by, to prepare a module in the same manner as in Example 1, from an aqueous solution of ethanol 90 weight ^_0/0, the par base Palais Chillon method at a temperature of 75 ° C, water In a separation experiment, the water permeation flux (Q) was 3.6 kg / m 2 and the separation factor (s) was 14000.

After the evaluation, the module was disassembled and individual separation experiments were performed on the composite membrane. One of the 20 samples had a force of 000, but the remaining 19 samples all had a separation factor of 10000 or more. In addition, the permeation flux of the composite membrane with a separation factor of 10,000 or more was 3.3 kg / m ² h or more.

[0043] (Comparative Example 1)

Except for the method of supporting the zeolite fine particles on the porous support used in Example 2, and without adding polyvinylpropylal as a binder to the dispersion, the same method as in Example 2 was used. An A-type zeolite crystal film was formed on the support.

This for twenty to prepare a module in the same manner as in Example 1 Te, by similarly Etano Lumpur 90 weight ^_0/0 aqueous force per base Palais Chillon method as in Example 1 were carried out separation experiments Toko The water permeation rate (Q) was 1.8 kg / m ² h, and the separation factor (H) was 1900. After the evaluation, the module was disassembled and a separate separation experiment was performed on the composite membrane. As a result, 5 out of 20 clear leaks were observed, and one separation factor was 50 or less. 300 force to 500, 3 separation factors ί 1000 force to 2000, and only the remaining 12 had a separation factor of 10000 or more. This indicates that about half of the 20 composite films obtained by hydrothermal synthesis contain defects in the zeolite crystal film. The permeation flux of the composite membrane with a separation factor of 10000 or more was 2. Okg / m or less.

[0044] (Example 3)

Polybur alcohol (Poval RS-117 (trade name) made by Kuraray) as a binder was mixed with 0.4 g and 19.6 g of water, and after the binder was completely dissolved, A-type zeolite fine particles (manufactured by Mizusawa igakusha) A zeolite fine particle dispersion solution was prepared by adding 0.6 g of Silton I B (trade name), particle size 0.8 m) and stirring sufficiently. The porous support used in Example 1 was immersed in water for 10 seconds to impregnate the pores of the support with water, and then placed in an air atmosphere at 60 ° C. for 30 seconds to obtain a surface portion of the support. Only dried. Subsequently, the zeolite was immersed in a zeolite fine particle dispersion for 10 seconds, dried and then dried in an air atmosphere at 60 ° C. for 1 hour, whereby the zeolite fine particles were supported on the surface of the porous support by a binder. The supported zeolite fine particles did not detach even when an impact was applied to the support, and did not detach when rubbed with a finger.

Using 20 of these, hydrothermal synthesis was performed in the same manner as in Example 1, and then a module was prepared. Similar to Example 1, a 90% ethanol aqueous solution power pervaporation method was used to perform a separation experiment. As a result, the permeation flux (Q) of water was 4.3 kgZm ² h, and the separation factor was 130000.

After the evaluation, the module was disassembled and individual separation experiments were performed on the composite membrane. One of the 20 samples had a force of 000, but the remaining 19 samples all had a separation factor of 10000 or more. In addition, the permeation flux of the composite membrane with a separation factor of 10,000 or more was 4.0 kg / m ² h or more.

[0045] (Example 4) As a binder, 2 g of poly (vinylidene fluoride) (ARKEMAi ^ KYNAR—720 (trade name)) and 18 g of dimethylacetamide were mixed and stirred until a uniform transparent polymer solution was obtained. To this polymer solution, 2 g of A-type zeolite fine particles (manufactured by Sigma-Aldrich, Molecular Sieve 4A, particle size: 5 m) was added and stirred for 2 hours to prepare a uniform zeolite fine particle dispersion. The porous support used in Example 1 was dipped in this zeolite fine particle dispersion for 10 seconds, and after lifting, dried in an air atmosphere at 60 ° C. for 1 hour, so that the zeolite fine particles were bonded to the surface of the porous support by a binder. Was supported. The supported zeolite fine particles were not detached even when impact was applied to the support, and they were not detached even when rubbed with a finger.

Using 20 of these, hydrothermal synthesis was performed in the same manner as in Example 1, and then a module was prepared. Similarly to Example 1, a 90% ethanol aqueous solution force pervaporation method was used to perform a separation experiment. However, the water permeation flux (Q) was 3.7 kgZm, and the separation factor was 1200.000.

After the evaluation, the module was disassembled and individual separation experiments were performed on the composite membrane. One of the 20 samples had an a force of ¾000, but the remaining 19 samples all had a separation factor of 10,000 or more. In addition, the permeation flux of the composite membrane with a separation factor of 10000 or more was 3.6 kg / m or more.

(Example 5)

As binders, 4 g of polyethersulfone (RADEL A-100 from Solvay) and 16 g of dimethylacetamide were mixed and stirred until a uniform transparent polymer solution was obtained. To this polymer solution, 2 g of A-type zeolite fine particles (manufactured by Sigma-Aldrich, Molecular Sieve 4A, particle size: 5 m) were added and stirred for 2 hours to prepare a uniform zeolite fine particle dispersion. The porous support used in Example 1 was dipped in this zeolite fine particle dispersion for 10 seconds, and then pulled up and dried in an air atmosphere at 60 ° C. for 1 hour, so that the surface of the porous support was filled with zeolite. Fine particles were supported. The supported zeolite fine particles were not detached even when an impact was applied to the support, and they did not desorb even when rubbed with a finger.

Using 20 of these, hydrothermal synthesis was carried out in the same manner as in Example 1, and then a module was prepared. As in Example 1, a 90% ethanol aqueous solution power pervaporation method was used. In the separation experiment, the permeation flux (Q) of water was 4.3 kgZm ² h, and the separation factor was 1400.

After the evaluation, the module was disassembled and individual separation experiments were conducted on the composite membrane. As a result, all 20 αs had separation factors of 10000 or more, and all permeation fluxes were 4.0 kgZm ² h or more.

[Example 6]

As a binder, 4 g of polyethylene glycol (Type 2000P manufactured by Clariant) and 17 g of water were mixed and stirred until a uniform transparent polymer solution was obtained. To this polymer solution was added 2 g of type A zeolite fine particles (manufactured by Sigma-Aldrich, Molecular Sieve 4A, particle size 5 m) and stirred for 2 hours to prepare a uniform zeolite fine particle dispersion. The porous support used in Example 1 was dipped in this zeolite fine particle dispersion for 10 seconds, and after being pulled up and dried in an air atmosphere at 60 ° C. for 1 hour, the surface of the porous support was coated with a binder. Thus, zeolite fine particles were supported. The supported zeolite fine particles were not detached even when an impact was applied to the support, and they were not detached even when rubbed with a finger.

Using 20 of these, hydrothermal synthesis was performed in the same manner as in Example 1, and then a module was prepared. Similarly to Example 1, a 90% ethanol aqueous solution force pervaporation method was used to perform a separation experiment. However, the permeation flux (Q) of water was 3.6 kgZm and the separation factor was 1100.

After the evaluation, the module was disassembled and a separation experiment was performed individually on the composite membrane. As a result, 2 of 20 α forces were 3,000, but the remaining 18 all had a separation factor of 10000 or more. In addition, the permeation flux of the composite membrane with a separation factor of 10,000 or more was 3.5 kg / m ² h or more.

[0048] (Example 7)

An organic hollow fiber (PVDF—TP manufactured by Asahi Kasei Chemicals, outer diameter 2 mm, film thickness 0.3 mm, average pore diameter 0.45 m) made of polyvinylidene fluoride as a porous support was used in Example 2. Zeolite microparticles as seeds were supported using the same dispersion liquid. The supported zeolite fine particles were not detached even when an impact was applied to the support, and they were not detached even when rubbed with a finger. Figure 7 shows an SEM image of an organic hollow fiber carrying zeolite fine particles. Figure 7 shows that the zeolite fine particles are uniformly applied to the surface of the porous support. The porous support carrying the zeolite fine particles was hydrothermally synthesized under the same conditions as in Example 1 to form an A-type zeolite crystal membrane. The obtained composite membrane was brought into contact with a 90% by weight ethanol aqueous solution maintained at 75 ° C, and the inside of the hollow fiber was depressurized, and a separation experiment was conducted by the pervaporation method. Water permeation flux (Q) Was 4.2 kg / m ² h and the separation factor (α) was 10,000.

After the evaluation, the module was disassembled and the composite membrane was individually separated. As a result, 3 out of 20 at forces S3000 force and the force that was in the range of 5000 The remaining 17 were all separated by 10000 or more. there were. The permeation flux of the composite membrane with a separation factor of 10,000 or more was 4. Okg / m or more.

[0049] (Example 8)

Polysulfone (Aldrich, Mn = 22000) 20g, A-type zeolite fine particles (Suilton-B (trade name), particle size 0.8 μm) 65g, and dimethylacetamide 250g This was wet-spun using a double annular nozzle with an inner diameter of 0.5 mm and an outer diameter of 1.5 mm. At this time, water was used as the core solution and the gelling bath solution, and spinning was performed at a core solution flow rate of 5 mlZ, a stock solution flow rate of 20 mlZ, a gelling bath temperature of 10 ° C, and a winding speed of 17 mZ. By spinning after spinning by the above method, a hollow fiber having an outer diameter of 1.8 mm and an inner diameter of 1. Omm was obtained and used as a porous support. The average pore diameter of this porous support determined by mercury porosimetry was 0.4 / ζ πι, and the porosity was 47%. This porous support is loaded with zeolite fine particles as seeds using the same dispersion as used in Example 2, and hydrothermal synthesis is performed under the same conditions as in Example 1 to form a cage zeolite crystal film. O The obtained composite membrane was brought into contact with a 90% by weight aqueous ethanol solution maintained at 75 ° C, and the inner side of the hollow fiber was depressurized to conduct a separation experiment by the pervaporation method. The flux (Q) was 4.5 kgZm ² h, and the separation factor was 10,000.

[0050] (Example 9)

(Dehydration test with vapor permeation)

Using the composite membrane prepared in Example 1, water was selectively separated from a mixed gas composed of ethanol and water vapor by the vapor permeation method. Figure 8 The schematic diagram of the separation apparatus used for this test is shown.

Is entering the internal aqueous solution 200g of ethanol 90 weight ^_0/0 of the volume one liter autoclave 7, by heating the whole up to the closed to 130 ° C, mixed with internal autoclave with steam of ethanol and water gas And the atmosphere. The inside of the composite membrane 8 installed inside the autoclave was depressurized by the vacuum pump 1, and water in the ethanol aqueous solution was permeated from the outer surface of the composite membrane 8 into the hollow interior. The water separated through the composite membrane 8 passed through the vacuum line 2 and collected in the trap 3 cooled by liquid nitrogen. A vacuum gauge 4 is installed between the vacuum line 2 and the trap 3. In the figure, trap 6 was installed to capture the oil backflow from the vacuum pump. Similar to the pervaporation method, the permeation flux and separation factor by the vapor permeation method were determined from the weight of water in the cooling trap 3 and the ethanol concentration in the trapped water. The permeation flux (Q) was 16.2 kgZm ² h, and the separation factor was 16000.

[0051] (Comparative Example 2)

Water glass as a binder (Wako Pure Chemical Industries, SiO / Na 0 = 2. 06-2.31 (molar ratio)) 2.0

twenty two

g, water 18. Og was mixed and the binder was completely dissolved, then added A type zeolite fine particles (Silton B (trade name) manufactured by Mizusawa i 匕 gakusha, particle size 0.8 m) 0.4 g By stirring the mixture, a zeolite fine particle dispersion was prepared. The same organic hollow fiber as used in Example 2 was used as the porous support, both ends were sealed, immersed in a zeolite fine particle dispersion for 10 seconds, and then pulled up for 1 hour in an air atmosphere at 60 ° C. By drying, a treatment for supporting zeolite fine particles with a water glass binder was performed. Figure 9 shows an SEM image of the organic hollow fiber that has been loaded with zeolite fine particles as described above. FIG. 9 shows that when water glass is used as the binder, almost no zeolite fine particles are supported on the surface of the organic hollow fiber. This porous support was subjected to hydrothermal synthesis under the same conditions as in Example 1, and then subjected to a separation experiment by the pervaporation method. As a result, the separation performance was completely different with no difference in the composition of the feed liquid and the permeate. It ’s nasty.

After the evaluation, the module was disassembled and separate experiments were conducted on the composite membranes. As a result, clear leakage was observed in all of the 20 membranes, and there was a single product that showed separation performance.

[0052] (Comparative Example 3) Water glass as a binder (Wako Pure Chemical Industries, SiO / Na 0 = 2. 06-2.31 (molar ratio)) 10.

twenty two

After mixing 0 g and 10.0 g of water and completely dissolving the binder, add 0.5 g of A-type zeolite fine particles (Shilton I (Mizusawa Igaku Co., Ltd., trade name), particle size 0.8 m)) By stirring the mixture, a zeolite fine particle dispersion was prepared. The same alumina porous support as used in Example 1 was used as the porous support, both ends were sealed, and then immersed in a zeolite fine particle dispersion for 1 minute according to the method disclosed in Patent Document 6. The zeolite fine particles adhering to the surface by water flow after washing are washed and washed, and then dried in a 60 ° C air atmosphere for 1 hour to support the zeolite fine particles with the water glass binder. Processed. This porous support was subjected to hydrothermal synthesis under the same conditions as in Example 1 and then subjected to a separation experiment by the single-partition method. The water permeation flux (Q) was 1.9 kg.

/ m, separation factor) was 1500.

After the evaluation, the module was disassembled and the separation experiment was performed individually on the composite membrane. As a result, 6 out of 20 clear leaks were observed, and the separation factor for 6 was 100 forces and 2000, and the separation factor was over 10,000. Only the remaining eight were shown. This indicates that more than half of the 20 composite films obtained by hydrothermal synthesis contain defects in the zeolite crystal film. Further, all the permeation fluxes of the composite membrane having a separation factor of 10,000 or more were 2.0 kgZm ² h or less.

From these results, it is clear that when the composite membrane of the present invention is used as a method for economically separating the target product from the mixture, a higher processing capacity can be obtained than in the prior art. Industrial applicability

[0053] The composite membrane of the present invention can be suitably used as a separation membrane for extracting only a specific component of liquid, gas, or a mixture force thereof. In particular, because of the azeotropic state, the composite membrane of the present invention can be used in a system such as ethanol and water that could not be separated by a conventional distillation method.

Brief Description of Drawings

[0054] [Fig. 1] SEM and EDS images of a cross section in which a seed crystal is supported on the surface of an inorganic porous support by an organic binder.

[Fig.2] Hydrothermal synthesis after seed crystal is supported on the surface of inorganic porous support by organic binder A SEM image of the zeolite crystal film and the cross section of the support obtained by.

[Fig. 3] SEM and EDS images of zeolite crystal film and support cross section obtained by hydrothermal synthesis after supporting seed crystal on the surface of inorganic porous support with organic binder.

[4] A schematic diagram of a separation apparatus using a module using the composite membrane of the present invention.

[5] SEM and EDS images of a cross-section with a seed crystal supported on the surface of an inorganic porous support by an organic binder.

[Fig. 6] SEM and EDS images of zeolite crystal film and cross section of support obtained by hydrothermal synthesis after seed crystal is supported on the surface of inorganic porous support by organic binder.

[7] Surface SEM image of a porous support with a seed crystal supported on the surface of an organic porous support using an organic binder.

8] Schematic diagram of a separation apparatus using modules using the composite membrane of the present invention.

[9] Surface SEM image of a porous support with a seed crystal supported on the surface of the organic porous support using an inorganic binder (water glass).

Claims

The scope of the claims

[I] A porous support having an organic polymer as a binder and having zeolite fine particles applied to the surface is brought into contact with a synthesis solution containing a zeolite raw material, and hydrothermal synthesis is performed on the surface of the porous support. A method for producing a composite film comprising forming a zeolite crystal film.

[2] The porous support is provided with a zeolite fine particle on at least one of the inner surface and the outer surface of the porous support using a dispersion solution in which zeolite fine particles are dispersed in an organic polymer solution. The method according to claim 1, which is a cylindrical porous support obtained as described above.

[3] The method according to claim 1, wherein the organic polymer is selected from the group consisting of polybutyral, polybulualcohol, polysulfone, polyethersulfone, polyvinylidene fluoride, and polyethylene glycol.

[4] The method according to claim 1, wherein the porous support also has a ceramic or metal force that can be selected.

5. The method according to claim 1, wherein the porous support is made of an organic polymer.

6. The method according to claim 1, wherein the porous support is a hollow fiber obtained by wet spinning, which also has a mixture force of an organic polymer and zeolite fine particles.

[7] The zeolite crystal film is an A-type, X-type, Y-type, T-type, L-type, ZSMs, sodalites, mordenites, and silicalites. The method according to Item 1.

[8] A composite membrane obtained by the production method according to any one of claims 1 to 7.

[9] The three-layer structure according to [1] to [7], wherein the porous support has a layer having an organic polymer and a zeolite fine particle force, and further has a zeolite crystal film thereon. A composite membrane obtained by the method according to any one of the above.

10. The composite film according to claim 8 or 9, wherein the zeolite crystal film is made of hydrophilic zeolite.

[II] The composite film according to claim 8 or 9, wherein the zeolite crystal film is made of hydrophobic zeolite.

[12] Using the composite membrane according to any one of claims 7 to 10, from a mixed solution or a mixed gas composed of two or more components by a pervaporation method or a single permeation method. A material separation method comprising separating at least one component.

13. The method according to claim 12, wherein at least one component is separated from the mixed solution composed of water and organic matter. the method of.

The method according to claim 12, wherein at least one component is separated from a mixed solution composed of two or more organic substances.