JP2002058972A - Composite membrane of porous organic high polymer membrane and zeolite, and method of manufacturing for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inexpensively manufacture a separation membrane of high effi ciency and good workability. SOLUTION: The composite separation membrane is formed by using a porous organic high polymer membrane which is flexible and has the good workability as a blank membrane and depositing zeolite as a composite separation membrane thereon, by which the high-efficiency separation performance of the zeolite is induced without impairing the flexibility and reworkability of the porous organic high polymer membrane. The composite separating membrane is inexpensively manufactured by utilizing conventional equipment for the porous organic high polymer membrane without special remodeling thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a flexible and processable compound obtained by laminating and complexing a zeolite crystal having a molecular sieving effect (hereinafter referred to as "molecular sieving effect" as appropriate) with a porous organic polymer film. It relates to a high-performance separation membrane that can be mass-produced.

[0002]

BACKGROUND ART A reverse osmosis membrane for selectively permeating water from seawater to obtain fresh water, an ultrafiltration membrane for concentrating and separating proteins from cheese whey, a gas separation membrane for recovering hydrogen gas from off-gas of petroleum refining, Separation membranes such as pervaporation membranes that obtain pure alcohol by dehydration from a water azeotrope such as ethanol or isopropanol have been developed and widely applied as energy-saving separation techniques.

Incidentally, porous organic polymer membranes used for these separation membranes (hereinafter referred to as "organic polymer membranes, polymer membranes" as appropriate)
Also called. ) Is widely used as described above because the membrane itself is flexible and can be formed into various shapes such as a tube shape, a spiral shape, and a hollow fiber shape, and can be easily mass-produced. However, the separation mechanism is based on the affinity between the size of the micropores formed by casting the organic solvent solution in which the raw material polymer is dissolved in water, removing the organic solvent and separating the polymer into microphases, and the gas to be separated. Because of the statistical separation mechanism that depends on sex differences, in the above-mentioned separation membrane, even if the molecular size is different, complete separation of substances having similar chemical properties, for example, affinity, is in principle possible. Impossible.

On the other hand, zeolite crystals having a pore size of 3Å, 4Å, 5Å, or 9Å or the like have a molecular size sieving effect of a crystal having a strictly uniform pore size, so that gas separation by the adsorption method of O ₂ and N _{2 in} air can be performed. It is applied to the separation of para-xylene from meta-xylene by the adsorption method, and has been put into practical use as a highly efficient separation method. However, zeolite has poor workability and is difficult to form into a film.

[0005] In order to overcome such poor processability of zeolite, an attempt to form a zeolite having a pore size of a molecular size on the order of nanometers into a membrane and use it as a separation membrane has attracted attention and studied as a method for obtaining an ultimate separation membrane. Recently, there has been research on a membrane in which zeolite crystals are grown and laminated on alumina or a porous stainless steel plate, and it is reported that the membrane has extremely high separation performance. However, this method also has flexibility and
It is a separation membrane that uses a non-reworkable material membrane as a base material, and thus lacks reworkability and impact resistance. It also requires special manufacturing equipment and is expensive and is not practical. There are many.

[0006]

Accordingly, the present invention relates to a porous organic polymer, which comprises a flexible organic film having good processability as a raw material membrane and a zeolite membrane formed into a composite separation membrane. Utilize high-efficiency zeolite separation performance without impairing the flexibility and reworkability of the membrane, and use the conventional equipment for manufacturing porous organic polymer membranes without special modification do it,
It is an object to manufacture a composite separation membrane at low cost.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a porous organic polymer film was subjected to a coupling treatment to the substrate, and further subjected to a coupling treatment as necessary. By laminating them using zeolite, a high-performance flexible composite separation membrane has been completed.

According to the first and second aspects of the present invention, a zeolite seed crystal having a small diameter is arranged on a porous organic polymer membrane having micropores, and the same kind of crystal is used as the seed crystal. It is characterized in that a seed crystal is grown and laminated by a hydrothermal synthesis reaction in a raw material mixture to be produced to form a composite film of a porous organic polymer film and zeolite.

[0009] The invention described in claim 3 of the present application is to provide a method in which the surface and pores of the porous organic polymer membrane, or the seed crystal of zeolite, or the surface and pores of the porous organic polymer membrane and Both zeolite seed crystals are treated with a binder that has a functional group that is reactive and compatible with the functional group of the porous organic polymer membrane and that has a functional group that is reactive and compatible with zeolite. It is characterized by.

[0010] The invention described in claim 4 of the present application is directed to a method in which a zeolite seed crystal is formed on one or both sides of a porous organic polymer membrane in water or an organic solvent, or in a mixed solution of water and an organic solvent. It is characterized by being arranged by vibration.

The invention described in claim 5 of the present application is characterized in that the porous organic polymer film has heat resistance and chemical resistance having a glass transition point of 50 ° C. or higher. The shape of the porous organic polymer film is tubular, spiral, flat, or hollow fiber.

The invention described in claim 7 of the present application is one wherein the zeolite comprises at least one of A-type, X-type, Y-type, L-type, sodalites, and model nights, including seed crystals. And a composite separation membrane that is a crystal having a pore structure.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be specifically described below.

The outline of the manufacturing method is as follows. A coupling treatment is performed on a predetermined porous organic polymer film using a predetermined liquid. Separately, the finely divided zeolite is subjected to a coupling treatment as required, and the organic polymer film is immersed in the slurry of the zeolite, and the zeolite is brought into close contact with the organic polymer film as a seed crystal. Next, the organic polymer film is immersed in a slurry made of a material suitable for growing the zeolite, and a predetermined hydrothermal synthesis reaction is performed. The details will be specifically described below.

The porous organic polymer film usable in the present invention is mainly 0.0005 μm (nominal pore diameter, the same applies hereinafter).
The following reverse osmosis membrane, 0.005-0.001 μm nanofilter,
There is an ultrafiltration membrane of 0.001 to 0.2 μm and a microfilter of 0.2 to 1 μm, and if the porous structure has through-holes, the pore size distribution slopes in the film thickness direction even for a symmetric membrane whose pore size distribution is symmetrical on both sides of the membrane. May be used, but the asymmetric film is more preferable from the viewpoint of the retention of the seed crystal.

As the shape of the porous organic polymer membrane, a tubular, spiral, plate-and-frame, pleated or hollow fiber membrane or the like can be used. This has the advantage that the area can be increased.

The material of the porous organic polymer film is not particularly limited as long as it has heat resistance higher than the hydrothermal reaction temperature and chemical resistance. Particularly preferred materials include polyvinyl alcohol, crosslinked polyacrylonitrile, polyolefin, polyvinylidene halide, polysulfone, polyethersulfone, polyphenylene sulfone, polyamide, polyetheramide, polysulfonamide, polyimide, and block copolymers of these organic polymers. Coalescence and mixtures. The number average molecular weight of these polymers is desirably 10,000 or more and as large as possible.

In addition, coupling treatment is indispensable for firmly fixing the precipitated crystals of zeolite to the porous organic polymer membrane, and the silane coupling agent is extremely effective for the coupling treatment. It has been found that the silane coupling agent is a silane compound that has one or more functional groups that react with inorganic OH groups on one side and has an organic functional group on the other side, and binds an organic polymer membrane to zeolite. An organosilicon compound that may cause the organic compound to be used is used. Functional groups that react with inorganic OH groups include, for example, methoxysilane groups, ethoxysilane groups, and silicon halide groups, and organic functional groups that react with polymers having active hydrogen such as OH groups and NH groups. Epoxy group, CO group
There are an amino group that reacts with a polymer having a functional group such as a COOH group and a CN group, and a vinyl group that reacts with a polymer having a C radical. For the organic silicon compound, for example, for a silane coupling agent having an epoxy group, β- (3,4 epoxychlorohexyl) ethyltrimethoxysilane / γ-glycidoxypropyltrimethoxysilane / γ-glycidoxypropylmethyl There are diethoxysilane and γ-glycidoxypropyltriethoxysilane compounds, and silane coupling agents having an amino group include Ν-β (aminoethyl) γ-aminopropylmethyldimethoxysilane and Ν-β
(Aminoethyl) γ-aminopropyltrimethoxysilane ・ Ν-β (aminoethyl) γ-aminopropyltriethoxysilane ・ γ-aminopropyltrimethoxysilane ・
γ-aminopropyltriethoxysilane / Ν-phenyl γ
-Aminopropyltrimethoxysilane compound, and examples of the silane coupling agent having a vinyl group include vinyltrichlorosilane / vinyltrimethoxysilane / vinyltriethoxysilane / vinyltris (β-methoxyethoxy) silane compound.

As a method for imparting a coupling action to the organic polymer film, a method of mixing a silane coupling agent having a coupling action with a solution of the organic polymer film and embedding it at the time of forming the organic polymer film. And a method of reacting an organic polymer film with a silane coupling agent.

In the method of embedding at the time of forming an organic polymer film, a silane coupling agent having an amino group such as Ν-β (aminoethyl) γ-aminopropyltrimethoxysilane is used as the silane coupling agent. .

As a method of reacting the silane coupling agent to the organic polymer film, a method of reacting the silane coupling agent in an inert organic solvent in which the functional group of the silane coupling agent is not deactivated or in a solution in which the organic solvent and water are dissolved is used. Using a solution containing a silane coupling agent, the module film is immersed in the solvent or solution, or the solution is applied to the module film, and heated at a temperature lower than the boiling point of the solvent to cause a reaction. When the organic solvent is used as it is, cyclohexane
There are hydrocarbons such as hexane, heptane and xylene, and the organic solvent used as a solution in water is dioxane, tetrahydrofuran, tetrahydropyran,
There are ether compounds such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether.

As a material for the zeolite, A-type, X-type, Y-type, L-type, sodalites, model nights and their alkali metals or alkaline earth metals including seed crystals are ionized with other metal ions. One or more of the various exchanged zeolites are used.

As a result of various experiments, the existence of a zeolite seed crystal is indispensable for laminating zeolite on an organic polymer membrane by hydrothermal synthesis. It has been found that a zeolite seed crystal of the same type is most suitable for growing and laminating a zeolite. That is, if there is no seed crystal, a crystal of a different type from the target type zeolite crystal is often precipitated, and even if the target type zeolite can be precipitated, the precipitated crystal adheres to the polymer film. It turned out that it was easily dropped off due to the extremely weak degree, and was not suitable for practical use.

For the production of the composite film, a zeolite seed crystal subjected to a coupling treatment can be used. To make the silane coupling agent react with the zeolite seed crystal, a solution prepared by dissolving the silane coupling agent in an organic solvent is used. Alternatively, the seed crystal powder is added to a solution obtained by dissolving the silane coupling agent in a mixed solution of an organic solvent and water that does not impair the dispersibility, and a slurry is formed.

As a result of the experiment, in order to obtain a membrane in which zeolite crystals are firmly fixed to the porous organic polymer membrane, it is necessary to reduce the size of the porous organic polymer membrane to such a degree that it can be in close contact with the pores of the porous organic polymer membrane. It has been found that it is important to use the zeolite seed crystal thus prepared and to make the zeolite seed crystal contact and deposit more closely on the surface and in the pores of the membrane.

As for the effect of grain refinement, it has been found that when the grain size of the seed crystal is 1 μm or less, the adhesion and contact properties can be improved by the anchor effect on the film. However, even in the ordinary synthesized zeolite, the particle size is large and generally several μm to several tens of m.
Since crystals having a diameter of 1 μm or less and having a diameter of 1 μm or less are usually as small as several percent or less, it is necessary to prepare fine grains for use as seed crystals. As a method of grain refinement, a wet milling method using a ball mill with a ball diameter of 0.2 mm to 5 mm was adopted.
0.40.412 μm (measured value by the microtrack method).

As a method of contacting and depositing the finely divided zeolite seed crystals more closely on the surface and in the pores of the organic polymer film, a method in which the finely divided seed crystals are mixed with an organic solvent or a mixed solvent of water and an organic solvent is used. The present inventor has found that it is extremely effective to prepare a slurry dispersed in a polymer, put a module in the slurry, and apply a positive or negative pressure to the organic polymer film constituting the module. As a method of applying a positive or negative pressure, there is a method of applying pressure to the membrane surface or sucking from the opposite side of the membrane surface to reduce the pressure, and in this case, a method using ultrasonic waves is used for the zeolite grain boundary after hydrothermal synthesis. It was also found to be extremely excellent in suppressing the leak of water. The thickness of the deposited layer is preferably 10 μm or less.
It turned out that it was easy to fall off.

In order to grow and stack zeolite crystals on a porous organic polymer membrane in the presence of these seed crystals,
It is necessary to hydrothermally synthesize the zeolite using a raw material suitable for obtaining the desired zeolite, but the following is used as the raw material. The raw materials and the compounding ratio thereof are appropriately selected in order to precipitate the same type of zeolite as the seed crystal. The silica component is at least one of colloidal silica, water glass, sodium silicate, sodium orthosilicate, and tetraethylsiloxane.
Use one or more of organic acid salts such as aluminum hydroxide, aluminum nitrate, aluminum chloride, sodium aluminosilicate, boehmite, and acetic acid. If necessary, the calcium oxide component may be at least one of calcium hydroxide, calcium oxide, calcium nitrate, calcium chloride, etc., and the magnesium oxide component may be magnesium hydroxide, magnesium oxide, magnesium nitrate, magnesium chloride, etc. Among the barium oxide components, at least one of barium nitrate, barium chloride, barium hydroxide, etc., and the strontium oxide component, at least one of strontium nitrate, strontium chloride, strontium hydroxide, etc. As the alkali component, one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, carbonate, bicarbonate, ammonia, amines and the like are used. As a mineralizer that promotes crystallization,
Salt, potassium chloride, barium chloride, potassium sulfate, organic trialkylamine, tetraalkylammonium halide,
It is desirable to use one or more alcohols.

The raw materials having the compounding ratio selected for growing and laminating the desired zeolite crystals are mixed or dissolved in water, and the liquid is placed in a Teflon (registered trademark) sealable container. Then, the organic polymer membrane module provided with the seed crystal is immersed in this container, and the pressure is reduced to a predetermined pressure to degas. Thereafter, the container is placed in an autoclave, which is then hermetically sealed, and while being pressurized as necessary, kept at a predetermined temperature for a predetermined time to react. After the reaction, the module is taken out and sufficiently washed with clear water and ion-exchanged water to obtain a composite separation membrane of an organic polymer membrane and zeolite.

[0030]

Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

Embodiment 1 Nominal hole diameter 0.35 with a hollow fiber membrane diameter of about 0.9 mm and a length of about 80 mm, one end of which is sealed with epoxy resin
One or a plurality of μm polyvinyl alcohol hollow fiber membranes are used, and the other end is inserted into a suction or pressure tube (hereinafter referred to as an “adapter tube”) having an inner diameter of about 6 mm and a length of about 80 mm to suck or add the hollow fiber membrane. The module was manufactured by fixing both with an epoxy resin so that pressure could be applied. The module is immersed in a 5% solution of γ-glycidoxypropyltrimethoxysilane in dioxane, heated at 80 ° C for 1 hour in a closed container, taken out, and dried in a hot air dryer at the same temperature. The ring was processed. Next, A-type zeolite (hereinafter, also referred to as “zeolite A” as appropriate, also referred to as “other zeolite A” as appropriate) similarly wet-ground with a ball mill to an average particle size of 0.412 μm is 5w.
The module is immersed in a water slurry dispersed at a concentration of t%, suctioned and depressurized with an aspirator connected to the open end of the adapter tube while applying ultrasonic vibration, and seed crystals of A-type zeolite fine particles were formed on the outer wall of the hollow fiber membrane. As adsorbed. Next, water glass, caustic soda, sodium aluminate,
Na ₂ O / SiO ₂ = 5, Al ₂ O ₃ / SiO ₂ = 1/2, NaCl / SiO
_The module was immersed in a Teflon container containing a slurry mixed at a molar ratio of ₂ = 2, H ₂ O / SiO ₂ = 150, and was immersed in a 50 mmHg
It was degassed under reduced pressure as follows. Next, place the Teflon container containing the slurry and the module in an autoclave at 70 ° C.
For 86 hours. After the reaction, the module was taken out, washed sufficiently with water, and vacuum-dried at 70 ° C. to produce a composite membrane of polyvinyl alcohol and A-type zeolite. X-ray analysis of the membrane confirmed that A-type zeolite was synthesized. Using this composite membrane, a water-ethanol azeotrope is formed by pervaporation of water and ethanol at 75 ° C.
As a result of analysis by gas chromatography using a FFAP column, the permeation amount was 0.075 kg / m ² h, and the separation coefficient αH ₂ O / EtOH = 1.
7600 were obtained.

Examples 2 to 7 performed in the same manner as in Experimental Example 1
Table 1 shows Comparative Examples 1 to 3, including Example 1.

Embodiment 2 FIG. Using a module of a polyvinyl alcohol hollow fiber membrane with a nominal pore size of 0.10 μm, using a Y-type zeolite having an average particle size of 0.136 μm as a seed crystal, aqueous colloidal silica dispersion, caustic potassium, aluminum nitrate and potassium chloride aqueous solution were K ₂ O / SiO ₂ = 3.0, Al ₂ O ₃ / SiO ₂ = 1/8, KCl / Si
A hydrothermal reaction was carried out at 70 ° C. for 62 hours using a slurry having a molar ratio of O ₂ = 1 and H ₂ O / SiO ₂ = 150. Further, X-ray analysis of the membrane confirmed that Y-type zeolite was synthesized.

Embodiment 3 FIG. Use a polysulfone hollow fiber membrane with a nominal pore size of 0.30 μm. To make a module. The same seed crystal as in Example 1 was used, and Na ₂ O / SiO ₂ = 4 and Al ₂ O ₃ / SiO ₂ =
A hydrothermal treatment was carried out at 70 ° C. for 68 hours using a slurry having a molar ratio of 1, NaCl / SiO ₂ = 2 and H ₂ O / SiO ₂ = 170.
The result of the X-ray analysis of the produced membrane was confirmed to be A-type zeolite. The permeation rates of various pure gases were measured.

Embodiment 4 FIG. Using a module of a polysulfone hollow fiber membrane having a nominal pore size of 0.45 μm, the same silane coupling agent treatment as in Example 3 was performed, and the seed crystals had an average particle size of 0.41 μm.
Using a 2 μm type A zeolite and a slurry having the same composition as in Example 1, a hydrothermal reaction was performed at 70 ° C. for 86 hours. X-ray analysis of the membrane confirmed that A-type zeolite was synthesized. A separation test of the methanol / methyl tertiary butyl ether azeotrope at 55 ° C. by pervaporation was performed.

Embodiment 5 FIG. Using a module prepared in the same manner as in Example 1 and a seed crystal of A-type zeolite having an average particle size of 0.099 μm, Na ₂ O / SiO ₂ = 7, Al ₂ O ₃ / SiO ₂ = 1, NaCl / SiO ₂ =
2. A hydrothermal reaction was performed at 70 ° C. for 75 hours using a slurry mixed at a molar ratio of H ₂ O / SiO ₂ = 150. X-ray analysis of the membrane confirmed that A-type zeolite was synthesized.
A water / cyclohexane separation test was conducted by a vapor permeation method at 70 ° C. of a water / cyclohexane azeotrope.

Embodiment 6 FIG. The module manufactured in the same manner as in Example 1 was used. For the seed crystal, a slurry in which A-type zeolite was dispersed in dioxane at 5% by weight was wet-pulverized with beads of 5 mmφ to obtain a slurry having an average particle size of 0.452 μm.
10% by weight of the same silane coupling agent as in Example 1 was used, and the mixture was subjected to a heating reaction at 80 ° C. for 1 hour in a closed vessel. Then, the module was immersed in the seed crystal slurry subjected to the coupling treatment, and the seed crystal was adsorbed on the module film. Then, the same hydrothermal reaction was performed using the same slurry as in Example 5. X-ray analysis of the membrane confirmed that A-type zeolite was synthesized. The water-ethanol azeotrope was subjected to a separation test of water and ethanol by pervaporation at 75 ° C.

Embodiment 7 FIG. The module manufactured in the same manner as in Example 1 was used. As the seed crystal, a slurry obtained by using Y-type zeolite and having an average particle diameter of 0.368 μm in the same manner as in Example 6 and further performing the same coupling treatment as in Example 6 was used. Then, the module was immersed in the seed crystal slurry subjected to the coupling treatment, and the seed crystal was adsorbed on the module film. Then, Na ₂ O / SiO ₂ = 3.0, Al ₂ O ₃ / S
A hydrothermal reaction was performed at 70 ° C. for 68 hours using a slurry having a molar ratio of iO ₂ = 1/7, NaCl / SiO ₂ = 1.0, and H ₂ O / SiO ₂ = 120. X-ray analysis of the membrane confirmed that it was a Y-type zeolite. A separation test was performed in the same manner as in Example 6.

Comparative Example 1 is the same as Example 1, except that the process of adsorbing seed crystals was not performed. Note that the synthesized grown crystal was almost amorphous, which is different from A-type zeolite.

Comparative Example 2 is the same as in Example 2, except that the organic polymer film was not treated with a silane coupling agent. The synthesized growth crystal was a Y-type zeolite.

Comparative Example 3 is the same as Example 3 except that the treatment of the silane coupling agent and the treatment of adsorbing seed crystals were not performed. No growth of zeolite crystals on the organic polymer film was observed.

The following can be seen from Table 1. Comparing Example 1 with Comparative Example 1, the permeation amount was reduced to about 1/65, but the separation coefficient was significantly improved to about 15,000 times.
It can be seen that the azeotropic mixture of ethanol and water can be easily dehydrated. Comparing Example 2 with Comparative Example 2, the permeation amount is reduced to about 1/17, but the separation coefficient is remarkably improved to about 4600 times. This is considered to be the effect of applying the coupling agent to the polymer film. Example 3 and Comparative Example 3
Compared to the above, the gas separation in gas separation decreased to about 1/5 to 1/320 due to the size of the molecule, but the separation coefficient increased to about 11 to 2 times, and gas separation became possible. Is shown. In particular, the possibility that normal butane and isobutane having the same molecular weight and the same molecular weight can be separated from each other depending on the molecular size is considered to be due to the effect of expressing the molecular sieve separation function of zeolite by the seed crystal and the coupling agent. Example 4 is an example of separation of an azeotrope of methanol as a raw material and methyl tertiary butyl ether as a product in an organic synthesis by pervaporation, and shows that separation by permeation of a small molecule such as methanol is possible. ing. This also expresses the molecular sieve characteristics of zeolite due to the effects of the seed crystal and the coupling agent. Example 5 is an application example for removing water by removing water generated by condensation reaction in various organic syntheses together with inert cyclohexane as a vapor. The vapor state of a water / cyclohexane azeotrope Very high separation performance was obtained for the separation with. This is also considered to be the effect of the seed crystal and the coupling agent. Example 6 and Example 7 are examples in which the treatment of the coupling agent was not performed on the polymer film but only on the seed crystal, and Examples 1 and 2 in which the treatment of the coupling agent was performed on the polymer film. High molecular sieve separation functionality is obtained in the same manner as described above.

[0043]

According to the present invention, since a zeolite having a molecular sieve effect can be firmly fixed and densely laminated on a porous organic polymer membrane to form a composite membrane, the following remarkable effects can be obtained. Effect.

In the present invention, by forming a composite separation membrane, the highest separation performance superior to any previously reported results was obtained. Also in the gas separation, the possibility of separation was found for the same type and the same molecular weight which cannot be separated by a normal organic polymer membrane, and it was found that the separation factor was high. It should be noted that a remarkable separation effect was particularly observed in the dehydration of organic liquid, vapor and gas.

Commercially available organic polymer membranes include those having hydrophilicity / hydrophobicity, those capable of introducing polar groups, and those capable of changing the pore size, pore shape, and pore size distribution in the permeation cross-sectional direction.
According to the present invention, a zeolite having a molecular sieve effect of various molecular sizes can be densely laminated in layers to form a composite membrane using these various organic polymer membranes.
With respect to the separation of the molecular size of a gas mixture, it has become possible to produce a module / separation apparatus that meets the actual conditions of use in a wide range of fields.

Further, since the manufacturing equipment of the porous organic polymer membrane which has been conventionally used as the manufacturing apparatus can be diverted without special modification, it is possible to provide a high-performance separation membrane at low cost. became.

[Table 1]

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Tetsuo Yazawa 1-81-3 Midorioka, Ikeda-shi, Osaka Prefecture Inside the Industrial Technology Research Institute, Osaka Institute of Technology (72) Inventor Tetsuro God 1--8-3 Midorioka, Ikeda-shi, Osaka No. 31 Inside the Osaka Institute of Technology (72) Inventor Kaoru Furukawa No. 1 Park City 3-1406 F-term (reference) 6-2, Minatojima Nakamachi, Chuo-ku, Kobe City, Hyogo Prefecture 4D006 GA03 GA06 LA06 MA01 MA02 MA03 MA04 MA06 MA22 MB11 MB15 MC03X MC33 NA45 4G073 CZ02 CZ04 CZ05 CZ07 CZ10 CZ16 FA30 FC12 FD07 FD21 GA11 UA06 UB40

Claims (7)

[Claims] 1. A method in which a zeolite seed crystal having a small diameter is arranged on a porous organic polymer membrane having micropores is placed in a raw material mixture that produces the same kind of crystal as the seed crystal. A composite film manufacturing method characterized by forming a composite film by growing and laminating by a thermal synthesis reaction. 2. The composite membrane according to claim 1, wherein the composite membrane is produced using a porous organic polymer membrane having a maximum pore diameter of 1 μm or less and a zeolite having a particle diameter of 0.01 to 1.0 μm. Manufacturing method of membrane 3. A binder having a functional group having reactivity and affinity with the functional group of the porous organic polymer membrane and having a functional group having reactivity and affinity with zeolite is prepared in advance by the porous organic polymer membrane. 3. The method for producing a composite membrane according to claim 1, wherein the composite membrane is treated on the surface or in the pores of the polymer membrane or on a zeolite seed crystal. 4. A zeolite seed crystal is disposed on one or both sides of a porous organic polymer membrane by ultrasonic vibration in water, an organic solvent, or a mixed solvent of water and an organic solvent. 4. A method for producing a composite membrane according to claim 1 5. A composite produced by the production method according to claim 1, wherein a porous organic polymer film having heat resistance and chemical resistance having a glass transition point of 50 ° C. or more is used. Separation membrane 6. The composite separation membrane according to claim 5, wherein a porous organic polymer membrane having a tubular, spiral, flat membrane or hollow fiber shape is used. 7. A zeolite comprising at least one of A-type, X-type, Y-type, L-type, sodalites and model nights, including seed crystals, and having a pore structure. 7. The composite separation membrane according to claim 5, wherein: