WO2007077646A1 - Procede de production d’une membrane composite - Google Patents

Procede de production d’une membrane composite Download PDF

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Publication number
WO2007077646A1
WO2007077646A1 PCT/JP2006/316250 JP2006316250W WO2007077646A1 WO 2007077646 A1 WO2007077646 A1 WO 2007077646A1 JP 2006316250 W JP2006316250 W JP 2006316250W WO 2007077646 A1 WO2007077646 A1 WO 2007077646A1
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Prior art keywords
zeolite
porous support
fine particles
organic polymer
composite membrane
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PCT/JP2006/316250
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English (en)
Japanese (ja)
Inventor
Hironobu Shirataki
Zhengbao Wang
Kensuke Aoki
Hiroyoshi Ohya
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Asahi Kasei Chemicals Corporation
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Publication of WO2007077646A1 publication Critical patent/WO2007077646A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B01D71/0281—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation
    • B01D61/3621—Pervaporation comprising multiple pervaporation steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range

Definitions

  • 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.
  • the azeotropic distillation method 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.
  • 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.
  • a separation coefficient a of 10,000 or more can be obtained (see Patent Document 1).
  • 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
  • Patent Document 2 a method of growing crystals by direct hydrothermal synthesis
  • Patent Document 3 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).
  • 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).
  • Patent Document 1 uses a method of rubbing seeds on a support
  • Patent Document 4 immerses the support in a seed dispersion aqueous solution
  • Patent Document 5 brushes the seed dispersion aqueous solution on the surface of the porous support.
  • Patent Document 6 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 7 a method using silica sol as a binder is disclosed.
  • bentonite 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.
  • water glass or silica sol 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • the zeolite crystal film is formed by hydrothermal synthesis.
  • 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.
  • 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.
  • the present invention is as follows.
  • 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.
  • 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.
  • the method according to claim 1, wherein the method is a cylindrical porous support obtained by applying yttrium fine particles.
  • organic polymer is selected from the group consisting of polybutyral, polyvinyl alcohol, polysulfone, polyethersulfone, polyvinylidene fluoride, and polyethylene glycol.
  • porous support also has an inorganic force selected from ceramics and metal forces.
  • porous support comprises an organic polymer.
  • porous support is a hollow fiber obtained by wet spinning, which also has a mixture force of organic polymer and zeolite fine particles.
  • 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.
  • 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.
  • a material separation method comprising separating at least one component from a gas.
  • the invention's effect 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.
  • 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
  • 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.
  • 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.
  • 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.
  • the size of the zeolite fine particles supported on the surface of the porous support is preferably 0.01 ⁇ m 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 ⁇ m or more and 5 ⁇ m or less.
  • 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.
  • 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.
  • 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.
  • the outer diameter is preferably in the range of 0.5 mm to 10 cm
  • the wall thickness is preferably in the range of 0.05 mm to 2 cm. preferable.
  • 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.
  • 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 ⁇ m or less.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. .
  • 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.
  • 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.
  • the binder 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • an organic solvent can be used as a solvent for the binder.
  • 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.
  • hydrophilic zeolites and hydrophobic zeolites can be used as the zeolite.
  • hydrophilic zeolite examples include A type, X type, Y type, T type, and L type
  • examples of the hydrophobic zeolite include ZSMs, sodalites, mordenites, and silicalites.
  • various zeolites in which they are replaced with other metal ions can also be used.
  • the size of the crystals forming the zeolite crystal film is preferably in the range of 0.01 ⁇ m force to 10 ⁇ m in order to prevent both separation performance and permeation flux from deteriorating. Preferably 0.1 ⁇ m force or 5 ⁇ m.
  • the thickness of the zeolite layer is preferably 0.1 ⁇ m or more from the viewpoint of separation performance and 50 ⁇ m or less from the viewpoint of the permeation flux, more preferably 0.5 ⁇ m force or 30 ⁇ m. 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.
  • 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.
  • alumina component that is a raw material for zeolite include sodium aluminate, aluminum hydroxide, aluminum nitrate, aluminum salt, boehmite, and the like.
  • sodium hydroxide is used as a raw material of sodium that exhibits alkalinity during hydrothermal synthesis and forms zeolite.
  • calcium hydroxide, calcium hydroxide, calcium carbonate, calcium nitrate, calcium chloride, etc., magnesium oxide, magnesium hydroxide, magnesium oxide, magnesium nitrate, salt ⁇ Barium nitrate, barium chloride, barium hydroxide, etc. are used as barium oxide components such as magnesium.
  • 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.
  • 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.
  • 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.
  • a mixed solution force of two or more liquids can be separated by a pervaporation method.
  • 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.
  • hydrophilic zeolite such as A-type, X-type and T-type is used as the type of zeolite.
  • hydrophobic zeolite such as ZSMs and silicalites is used.
  • 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.
  • 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.
  • 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.
  • each character represents:
  • 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.
  • 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.
  • 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.
  • EDS energy dispersive X-ray spectroscopy
  • EMAX-7000 manufactured by Horiba.
  • the electron beam acceleration voltage was 15kV
  • the working distance was 12mm
  • the beam current was 0.4nA
  • the mapping was performed by detecting the characteristic X-rays of carbon atoms by irradiating the electron beam.
  • polyethylene glycol 400 manufactured by Wako Pure Chemical Industries, Ltd.
  • 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.
  • 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.
  • 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). .
  • SEM image shows that zeolite fine particles are applied to the surface of the porous support.
  • 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.
  • 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.
  • FIG. 2 shows this SEM image.
  • I is a zeolite crystal layer (film)
  • II is a zeolite particle Z organic polymer binder layer
  • ⁇ is an alumina porous support layer.
  • 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.
  • FIG. 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.
  • Q permeation flux
  • the separation factor was determined. Specifically, the weight concentrations of ethanol and water on the supply side are
  • 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.
  • 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.
  • the permeation flux of the composite membrane with a separation factor of 10000 or more was 5. Okg / m or more.
  • 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;
  • zeolite 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.
  • FIG. 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).
  • SEM scanning electron microscope
  • EDS energy dispersive X-ray spectroscopy
  • the porous support was taken out, thoroughly washed with water, and dried at 60 ° C for 3 hours.
  • 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.
  • 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
  • the water permeation flux (Q) was 3.6 kg / m 2 and the separation factor (s) was 14000.
  • 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.
  • 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.
  • Example 2 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.
  • 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.
  • 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.
  • Example 2 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.
  • 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.
  • 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.
  • 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.
  • poly (vinylidene fluoride) ARKEMAi ⁇ KYNAR—720 (trade name)
  • dimethylacetamide 18 g
  • A-type zeolite fine particles manufactured by Sigma-Aldrich, Molecular Sieve 4A, particle size: 5 m
  • Example 2 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.
  • the module was disassembled and individual separation experiments were performed on the composite membrane.
  • One of the 20 samples had an a force of 3 ⁇ 4000, but the remaining 19 samples all had a separation factor of 10,000 or more.
  • the permeation flux of the composite membrane with a separation factor of 10000 or more was 3.6 kg / m or more.
  • 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.
  • 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.
  • Example 2 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.
  • the module was disassembled and individual separation experiments were conducted on the composite membrane. As a result, all 20 ⁇ s had separation factors of 10000 or more, and all permeation fluxes were 4.0 kgZm 2 h or more.
  • zeolite fine particles 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.
  • Example 2 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.
  • the module was disassembled and a separation experiment was performed individually on the composite membrane. As a result, 2 of 20 ⁇ 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.
  • Example 2 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 ( ⁇ ) was 10,000.
  • 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.
  • Polysulfone (Aldrich, Mn 22000) 20g, A-type zeolite fine particles (Suilton-B (trade name), particle size 0.8 ⁇ m) 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.
  • 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 / ⁇ ⁇ , 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.
  • 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.
  • 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.
  • 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.
  • zeolite fine particle dispersion 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.
  • A-type zeolite fine particles Shilton I (Mizusawa Igaku Co., Ltd., trade name), particle size 0.8 m
  • 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.
  • the module was disassembled and the separation experiment was performed individually on the composite membrane.
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG. 4 A schematic diagram of a separation apparatus using a module using the composite membrane of the present invention.
  • 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.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

La présente invention concerne un procédé de production d’une membrane composite, comprenant la mise en contact d’un support poreux dont la surface est recouverte de microparticules de zéolite en utilisant un polymère organique en tant que liant, avec une solution synthétique contenant un matériau de départ de type zéolite et la réalisation d’une synthèse hydrothermique afin de former de ce fait une membrane de cristal de zéolite sur la surface du support poreux.
PCT/JP2006/316250 2005-12-28 2006-08-18 Procede de production d’une membrane composite WO2007077646A1 (fr)

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JP2010115610A (ja) * 2008-11-14 2010-05-27 Sumitomo Electric Ind Ltd ゼオライト複合分離膜及びその製造方法
JP2012236155A (ja) * 2011-05-12 2012-12-06 Hitachi Zosen Corp ゼオライト複合膜
CN106390767A (zh) * 2016-11-08 2017-02-15 华南理工大学 一种蜂窝陶瓷复合膜及其制备方法
EP3090798A4 (fr) * 2013-12-31 2017-09-13 Nanjing University of Technology Membrane de tamis moléculaire à fibres creuses de haute résistance et méthode de préparation de celle-ci
CN108939928A (zh) * 2018-06-29 2018-12-07 中国石油大学(华东) 一种以方钠石纳米晶为填充物的混合基质膜的制备方法

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CN105363352A (zh) * 2015-11-14 2016-03-02 大连理工大学 一种含氟稀溶液合成高耐酸mor沸石分子筛膜的方法
JP6940213B2 (ja) * 2015-11-20 2021-09-22 １９３４６１２ オンタリオ インク．１９３４６１２ Ｏｎｔａｒｉｏ Ｉｎｃ． 炭化シリコン・メンブレンを用いた流体の清浄化装置、システム、および方法
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CN112870992B (zh) * 2021-01-13 2022-01-25 同济大学 一种沸石膜及其制备方法

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JP2010115610A (ja) * 2008-11-14 2010-05-27 Sumitomo Electric Ind Ltd ゼオライト複合分離膜及びその製造方法
JP2012236155A (ja) * 2011-05-12 2012-12-06 Hitachi Zosen Corp ゼオライト複合膜
EP3090798A4 (fr) * 2013-12-31 2017-09-13 Nanjing University of Technology Membrane de tamis moléculaire à fibres creuses de haute résistance et méthode de préparation de celle-ci
CN106390767A (zh) * 2016-11-08 2017-02-15 华南理工大学 一种蜂窝陶瓷复合膜及其制备方法
CN108939928A (zh) * 2018-06-29 2018-12-07 中国石油大学(华东) 一种以方钠石纳米晶为填充物的混合基质膜的制备方法
CN108939928B (zh) * 2018-06-29 2021-06-04 中国石油大学(华东) 一种以方钠石纳米晶为填充物的混合基质膜的制备方法

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