Entitled zeolite membrane production method and separation method using the same that
Technical field

[0001]
　The present invention is a zeolite membrane, to a separation method using the manufacturing method and the same. Zeolite membrane according to the present invention can be separated and recovered by the processing amount high separation performance desired compound, among others, it can be suitably used for dehydration of organic acids and other organic compounds containing water.
Background technique

[0002]
　Zeolite has a regularly arranged micropores, which are generally used in various fields since it are stable can be obtained many also high chemical heat resistance. Zeolites are aluminosilicates part of Si is substituted with Al, it has pores of molecular order of oxygen 8-membered ring to 14-membered ring (about 0.3 ~ 1 nm), stereoselective adsorption for example because of its liquid separation, vapor separation, gas separation, membrane reactor, a solid acid catalyst, separating the adsorbent, it is widely used in the fields such as ion exchange agents. In recent years, to separate recovered the compound from a mixture containing organic compound, in place of distillation which requires more heat energy, is proposed a membrane separation method using a zeolite membrane, also examples already commercialized .
[0003]
　To produce the zeolite is generally hydrothermal synthesis, i.e., a large amount of water and an aluminum source, a silica source, an alkali metal, an organic template such as amines, formulated to become the product zeolite composition of interest, and containment formulation pressure vessel such as an autoclave, by heating coexist porous support, to synthesize a zeolite membrane on a support. The support of alumina or mullite, is configured by a porous metal or Vycor glass, to which is deposited a seed crystal in some cases.
[0004]
　For example, Patent Document 1, Si element source, Al element source, with an aqueous reaction mixture containing 1-adamantanamine derivatives as alkali source and an organic template containing potassium, by hydrothermal synthesis, having the CHA crystal structure a method of forming a zeolite membrane on a porous support are described.
[0005]
　However, a zeolite membrane having a CHA crystal structure obtained in this manner using as a separation membrane, for example, a mixture of water / acetic acid, or each from a mixture of water / 2-propanol be separated recovering acetic acid or 2-propanol When, permeation flux (unit time, the mass of permeate per unit area) for processing amount is low is small, it takes a long time for separation tasks.
CITATION

Patent Document

[0006]
Patent Document 1: Laid-Open Patent Publication No. 2011-121854
Summary of the Invention

Problems that the Invention is to Solve

[0007]
　In view of the problems of the prior art described above, the holding in the separation by zeolite separation membrane, practically sufficient not only it is possible to achieve both high separation performance and throughput, a long-term stable separation performance and to provide a zeolite membrane can be.
[0008]
　The present invention also relates to processes for the manufacture of zeolite membranes can be formed zeolite membrane such high performance, and, with the zeolite membrane, be separated and recovered by the processing amount high separation performance desired compound and to provide a possible separation method.
Means for Solving the Problems

[0009]
　The present invention is to solve the above problems, to provide a manufacturing method and a separation method using the zeolite membrane below.
(1) A zeolite membrane having CHA crystal structure formed as a film on the intermediate layer of the porous support having an intermediate layer, Si / Al (molar ratio) of the CHA-type zeolite particles from 9.5 to 100 a .5, in X-ray diffraction pattern obtained by irradiating X-rays on the zeolite membrane surface, 2 [Theta] = 18 peak intensity around ° is 0.5 times less than the peak intensity in the vicinity of 2 [Theta] = 21 °, and / or a process for preparing a zeolite membrane, wherein the peak intensity in the vicinity of 2 [Theta] = 10 ° is less than 4 times the peak intensity in the vicinity of 2 [Theta] = 21 °,
Si element source, Al element source, an alkali source and an organic template with an aqueous reaction mixture containing, by hydrothermal synthesis, de-Al zeolite membrane having a CHA crystal structure when forming the intermediate layer on the porous support, as a Si element source and Al element source Method for manufacturing a zeolite membrane, which comprises using a FAU-type zeolite which is not onium treated.
(2) using the seed crystal in the hydrothermal synthesis, the seed crystal, Si element source, Al element source, a Si element source and Al element source in the hydrothermal synthesis using an aqueous reaction mixture containing a source of alkalinity and organic template method for manufacturing a zeolite membrane according to (1), characterized in that it is prepared using a FAU-type zeolite.
(3) The method of producing zeolite membrane according to (2) the particle size of the CHA type crystal is characterized in that a 100 nm ~ 1 [mu] m.
(4) the (1) to the zeolite membrane obtained by the production method according to any one of (3), by contacting a mixture of liquid or gas containing to be separated compounds, high permeability from the mixture separation methods by transmitting material and separating the compound.
(5) If a mixture comprising the compound to be separated is a mixture of water content 10% or more by weight of 2-propanol and water, the temperature of 75 ° C., were isolated under a pressure difference 1 atmosphere before and after the film, transparent flux is 10 kg / (m 2 separation methods according to (4) to h) above, the water concentration of the permeate, characterized in that 99 wt% or more.
(6) a mixture containing a compound to be separated is a mixture of water content 30% or more by weight of acetic acid and water, temperature 75 ° C., when performing separation at a pressure difference 1 atmosphere before and after the membrane permeation flux There 10 kg / (m 2 separation methods according to (4) to h) above, the water concentration of the permeate, characterized in that 99 wt% or more.
(7) a mixture containing a separation to be compound, and carbon dioxide ratio of carbon dioxide is 50 wt% or more, a mixed gas of methane, ammonia, or sulfur hexafluoride, temperature 40 ° C., film pressure across when performing separation at three atmospheres, the transmission coefficient of carbon dioxide × 10 1 -6 mol / (m 2 separation methods according to (4), characterized in that at sPa) or more.
(8) a mixture containing a separation to be compound, and carbon dioxide ratio of carbon dioxide is 50 wt% or more, methane, a mixed gas of ammonia or sulfur hexafluoride, a temperature 100 ~ 120 ° C., film before and after when performing separation at a pressure differential 3 atmospheres, the transmission coefficient of carbon dioxide 1 × 10 -7 mol / (m 2 separation methods according to (4), characterized in that at sPa) or more.
[0010]
　The zeolite membrane having CHA-type crystal structure in the present invention, shows what the code that defines the structure of the International Zeolite Association (IZA) stipulated zeolite chabazite (CHA) structure, equivalent chabazite of naturally occurring it is a zeolite having a crystal structure.
[0011]
　In the present invention, even when 5 days immersed in an aqueous organic acid solution such as common inorganic acids and acetic acid and acid-resistant, no change in its structure, and hardly causes de Al in skeletal, the Si / Al chemical composition it is meant that almost unchanged before and after treatment.
Effect of the Invention

[0012]
　The present invention is constructed as described above, since the zeolite membrane on the average pore diameter is smaller intermediate layer is formed, a thin zeolite membrane from a dense while suppressing the formation of pinholes can be obtained. The support zeolite thin film is not in contact since the average pore diameter than the intermediate layer is large, it is possible to obtain a high gas flux in the support. Thus, practically sufficient not only it is possible to achieve both high separation performance and throughput, can be maintained for a long time stable separation performance. Especially, zeolite membrane according to the present invention has excellent acid resistance, by using a zeolite membrane according to the present invention, separation and recovery of organic acids of interest from a mixture of water and an organic acid such as acetic acid at a high permeation flux can do.
BRIEF DESCRIPTION OF THE DRAWINGS

[0013]
[Figure 1] is an electron microscope image of the obtained zeolite membranes in Example 1, (a) shows the surface of the membrane, the (b) the membrane cross-section, respectively.
[2] it is an X-ray diffraction pattern of the zeolite membrane obtained in Example 1.
[3] The 29th zeolite Research Workshop, Proceedings, published in 73 pages, is an electron microscope image of the surface of the zeolite membrane (Figure 1 and the same magnification) with small CHA structure of Al content .
DESCRIPTION OF THE INVENTION

[0014]
　Hereinafter, the present invention will be described in detail.
[Porous support with an intermediate layer]
　The porous support in the present invention has an intermediate layer on the surface to form the zeolite membrane. Porous support, as long as it can crystallize the zeolite as a thin film on the intermediate layer, alumina, silica, mullite, zirconia, titania, metal or various alloy porous typified by stainless steel or aluminum support, anodized film porous support, and the like. When using a material obtained by forming a zeolite membrane on a porous support as a molecular sieve or the like, (a) can be firmly supported zeolite membrane, (b) pressure loss is as small as possible, and (c) a porous support so as to satisfy the condition that the body has sufficient self-supporting property (mechanical strength), it is preferable to set the average pore diameter of the porous support. Specifically, the average pore diameter of the porous support is preferably 10 ~ 50 [mu] m. Preferably, the thickness of the porous support comprising an intermediate layer is 1 ~ 3 mm. The average pore diameter of the intermediate layer is preferably 0.1 ~ 1 [mu] m. It is difficult to form a dense zeolite layer if 1μm greater than. Also, if 0.1μm less is not suitable for substances permeation resistance of the intermediate layer is large. Preferably the thickness of the intermediate layer is 1 ~ 50 [mu] m, and more preferably 1 ~ 10 [mu] m. Further, it is preferable porosity of the porous support is 20-50%, and more preferably 35 to 40%.
[0015]
　The shape of the porous support is not particularly limited, it can be used a tubular, flat plate, honeycomb, hollow fiber, pellet form, etc., having various shapes. For example, in the case of a tubular, but are not limited to particular sizes of the porous support, practical length 2 ~ 200 cm approximately, inner diameter of 0.5 to 2 cm, a thickness of about 0.5 to 4 mm.
[0016]
　Porous support, washing, it is preferable to perform a surface treatment by a method such as ultrasonic cleaning. For example, by ultrasonic cleaning in 1-10 minutes with water, it may be performed to clean the substrate surface. To improve the surface smoothness, and the like sandpaper or grinder, it may be polished surface thereof.
[Zeolite synthesis of film]
　In the process according to the invention, on the intermediate layer of the porous support as described above, Si element source, Al element source, with an aqueous reaction mixture containing a source of alkalinity and organic template, hydrothermal synthesis This forms zeolite membrane having a CHA crystal structure.
[0017]
　In hydrothermal synthesis, in order to promote crystallization of the zeolite in the top of the intermediate layer of the support, it is preferred to add seed crystals to the synthesis system. As a method for adding a seed crystal, it is possible to use a method of adding a seed crystal to the aqueous reaction mixture, or a method which allowed to adhere seed crystal on the intermediate layer of the support. Dense By keeping by attaching pre-seed separation performance good zeolite membrane on the intermediate layer of the support is easily generated.
The seed crystals used in the hydrothermal synthesis, it is preferable to use a CHA crystals prepared by hydrothermal synthesis using an FAU-type zeolite which is not dealuminated as Si element source and Al element source.
It is preferably the particle size of the seed crystal small, it may be used by optionally milled. To deposit a seed crystal on the intermediate layer of the support, for example, a dip method in which a seed crystal is deposited the solvent is dispersed with a support to the dispersion seed crystals, such as water or a seed crystal and a method of rubbed by mixing with a solvent such as water which was slurried support surface can be used. The size of the seed crystal is preferably 100 nm ~ 1 [mu] m, more preferably 100 ~ 800 nm. If the seed crystal is greater than 1 [mu] m, the balance of the pore diameter of the support intermediate layer can not form a dense zeolite layer. The particle diameter of the seed crystal can be measured using Otsuka Electronics Co., Ltd. of particle size measuring instrument (trade name, FPAR-1000).
[0018]
　The hydrothermal synthesis may be used to pressure vessel such as an autoclave. Placement of the porous support of the pressure vessel, since the vertical there is a possibility that unevenness of concentration of hydrothermal synthesis solution by the effect of gravity occurs, preferably horizontal with respect to the pressure vessel.
[0019]
　In the present invention method uses a FAU-type zeolite which is not dealuminated as Si element source and Al element source. It is possible to briefly synthesized using the FAU-type zeolite. In the present invention it has been successfully synthesized in 5 hours. In JP 2011-121854, and using colloidal silica and aluminum hydroxide as Si element source and Al element source rests 48 hours synthesis. In JP 2013-126649, although using a FAU zeolite was de Al, this is not necessary industrial that steps such acid removal was treated with sulfuric acid. Since FAU-type zeolite which is not dealuminated is converted into CHA-type zeolite in the hydrothermal synthesis reaction, Si / Al (molar ratio) ratio high-silica CHA-type zeolite membrane that 9.5 to 100.5 can be formed .
The hydrothermal treatment, the surface of the porous support, FAU type zeolite powder once, after decomposing, starting from the seed crystal to form a zeolite of the nuclei with the same crystal structure as the seed crystal (i.e., CHA structure). Alternatively, after the FAU-type zeolite is decomposed by the action of an organic template, to form a nucleus of the zeolite having the CHA structure. From the formed nuclei, crystals produced zeolite is grown. For structural unit of FAU and CHA are the same, it contributes to the crystallization of part of intact CHA structure of FAU. Therefore, defects are unlikely to occur in the crystal structure.
Furthermore, in the present invention, due to the use of FAU type zeolite that has not been dealumination, high crystallinity of the FAU, thereby enabling more synthetic CHA film utilizing the structure of the FAU.
[0020]
　Some of the formed nuclei, grown on the surface of the porous support to form a zeolite membrane that covers the surface of the porous support. At this time, since the nuclei are generated in a large amount, CHA crystal film surface to remain in particulate size, dense and permeable excellent CHA film is produced. Moreover, since it is composed of fine particles, grain boundaries i.e. cracks between crystal is unlikely to occur.
[0021]
　FAU-type zeolite commercially available products, e.g., HSZ-350HUA (USY = Ultra Stable Y, Si / Al ( molar ratio) = 10, Na 2 O / Al 2 O 3 = 0.007, manufactured by Tosoh Corp.) and HSZ-360HUA (USY = Ultra Stable Y, Si / Al ( molar ratio) = 14, Na 2 O / Al 2 O 3 = 0.006, manufactured by Tosoh Corporation), to FAU-type zeolite may be used one, two or more it may be used in combination.
[0022]
　In the method of the present invention, N as organic template, N, it is preferable to use the N- trimethyl-1-adamantan ammonium hydroxide. N, N, by using N- trimethyl-1-adamantan ammonium hydroxide, it is possible in a short time synthesis. Was possible even synthesized in 5 hours at the present invention. JP uses benzyltrimethylammonium In 2013-126649, but industrially unsuitable synthesis time is 7 days.
[0023]
　In the process of the present invention, the synthesis conditions of the hydrothermal synthesis time and temperature, and the like may be of a conventional method but, 100 ° C.-200 ° C., preferably from 120 ° C.-0.99 ° C., 5 hours to 15 days, preferably 3 is a day to 7 days. Further, after the completion of the hydrothermal synthesis takes the film from the pressure vessel, washed with water to remove excess gel material of the film surface, dried at room temperature ~ 0.99 ° C. in air, and removes the organic template present in the membrane layer and baked for. Firing conditions for 3 hours to 100 hours at 400 ° C. or higher, preferably a 10 hours 500 ~ 600 ° C., a Atsushi Nobori and cooling performed at 0.1 ~ 1 ° C. / min, the zeolite membrane due to thermal expansion prevent the occurrence of cracks.
[Zeolite membrane]
　by the production method of the present invention, the porous zeolite membrane having a film formation has been CHA crystal structure on the intermediate layer of the support, Si / Al (molar ratio) of the CHA-type zeolite particles having an intermediate layer There 9.5 to 100.5, preferably 10 to 100, more preferably from 20 to 80, in X-ray diffraction pattern obtained by irradiating X-rays on the zeolite membrane surface, the peak intensity in the vicinity of 2 [Theta] = 18 ° There 0.5 times less than the peak intensity in the vicinity of 2 [Theta] = 21 °, preferably less than 0.4, more preferably less than 0.35, a most preferably less than 0.25, the peak intensity near 2 [Theta] = 10 ° 4 times less than the peak intensity in the vicinity of 2 [Theta] = 21 °, preferably less than 3, more preferably less than 2.5, but most preferably is less than 0.2. The lower limit of (2θ = 18 ° peak intensity in the vicinity of) / (2θ = 21 peak intensity at around °) is not limited, it is usually 0.1. (2θ = 10 ° peak intensity in the vicinity of) / lower limit of (2θ = 21 ° peak intensity in the vicinity) is also not limited, but it is usually 1.
Throughout this specification and claims, the peak in the vicinity of 2 [Theta] = 18 ° and to refer to the largest of the peaks present in the range of 18 ° ± 0.6 ° of the peaks that are not derived from the base material, the peak around 2 [Theta] = 21 ° and that refers to the maximum one in peaks present in the range of 21 ° ± 0.6 ° of the peaks that are not derived from the substrate, the substrate is a peak in the vicinity of 2 [Theta] = 10 ° and to refer to the largest of the peaks present in the range of 10 ° ± 0.6 ° of the peaks that are not derived from.
[0024]
　Si / Al (molar ratio) indicate the zeolite membrane densely generated further generated zeolite strongly hydrophilic when in the above range, the hydrophilic compound from the mixture containing the organic substance, especially water selectively it can be transmitted. The de-Al hardly zeolite membrane is obtained strong acid resistance.
[0025]
　Si / Al (molar ratio), scanning electron microscope - is a value obtained by energy dispersive X-ray spectroscopy (SEM-EDX).
[0026]
　The thickness of the zeolite membrane is preferably 1 ~ 10 [mu] m, more preferably 1 ~ 4 [mu] m.
[0027]
　In the present invention, it is preferable that the size of the CHA-type zeolite particles are nanoparticles of 10 nm ~ 1 [mu] m, an nanoparticles more preferably 10 ~ 100 nm. If 1μm greater than the grain boundary between the zeolite crystals occurs, not a dense film.
[0028]
　Note that the CHA-type zeolite are those in code that defines the structure of the zeolite prescribed by International Zeolite Association (IZA) of the CHA structure, a zeolite having a chabazite and crystal structure equivalent to naturally occurring. CHA zeolite have the structure characterized by having a three-dimensional pore consisting of oxygen 8-membered ring having a diameter of 3.8 × 3.8 Å, its structure is characterized by X-ray diffraction data.
[Separation Method]
　In the separation method of the present invention, by using a zeolite membrane according to the present invention, it is possible to perform separation operation according to a conventional method. Pervaporation (pervaporation), the separation and concentration method called vapor permeation method (vapor permeation) can be suitably carried out using a zeolite membrane according to the present invention. For example, the case of a mixture of water and an organic compound, usually water because of its high permeability to zeolite membrane, the water is separated from the mixture, the organic compound is concentrated in the original mixture.
[0029]
　Separation method according to the invention comprises the separation of carboxylic acids from an aqueous solution containing a carboxylic acid represented by acetic acid, the separation of alcohols from aqueous solutions containing alcohols such as 2-propanol, esters such as acetic acid ester esters isolated from the aqueous solution, more is preferably applied to a carbon dioxide separation from carbon dioxide and nitrogen, methane, a mixed gas of ammonia or sulfur hexafluoride.
[0030]
　Specifically, a mixture of moisture content 10% or more by weight of 2-propanol and water, by the method of the present invention, the temperature 75 ° C., when separating process under a pressure difference 1 atmosphere before and after the membrane permeation flux 10 kg / (m 2 h) or more, transmitting water in permeate water concentration of 99 wt% or more, it can be separated and recovered 2-propanol.
[0031]
　Further, a mixture of moisture content 30% or more by weight of acetic acid and water, temperature 75 ° C., when separating process under a pressure difference 1 atmosphere before and after the membrane permeation flux 10 kg / (m 2 h) above, the permeate water concentration of 99 wt% or more transmitting water can be separated and recovered acetic acid.
[0032]
　Furthermore, carbon dioxide and methane ratio of carbon dioxide is 50 wt% or more, a mixed gas of a mixed gas of ammonia or sulfur hexafluoride, temperature 40 ° C., separated under conditions of a pressure difference 3 atmospheres before and after the film If carbon dioxide permeability coefficient × 10 1 -6 mol / (m 2 sPa) or more, preferably × 10 2.5 -6 mol / (m 2 is transmitted through the sPa) above, it is possible to separate carbon dioxide . High-silica CHA film of the present invention, it is possible to separate the material by molecular sieve effect. Pore size of the CHA film is 0.38 nm, carbon dioxide can be transmitted for less than, not penetrate methane, ammonium, sulfur hexafluoride by molecular sieve effect for more is the size.
[0033]
　Also, carbon dioxide ratio of carbon dioxide is 50 wt% or more, methane, a mixed gas of ammonia or sulfur hexafluoride, a temperature 100 ~ 120 ° C., the separation at a pressure differential 3 atmospheres before and after the film went If, permeability coefficient of carbon dioxide × 10 1 -7 mol / (m 2 sPa) is transmitted through the above, it is possible to separate carbon dioxide.
[0034]
　Next, specifically described the present invention based on examples, but the scope of the present invention is not intended to be construed as limited by the following examples.
[Example 1]

　Production Example 1 below, to form a CHA type zeolite membrane by direct synthesis hydrothermal on the intermediate layer of an inorganic porous support the CHA-type zeolite.
Preparation Example 1
　Intermediate layer (thickness of about 50 [mu] m, an average pore diameter 0.8 [mu] m) on the surface a cylindrical alumina support having (Hitachi Zosen Corp., a diameter of 16 mm, length 60 mm, average pore diameter 10 [mu] m) prepared, its the CHA-type zeolite on the surface of the intermediate layer as a seed crystal 25 g / m 2 were deposited. Measurement of the average pore diameter of the intermediate layer was carried out in accordance with JIS K 3832.
[0035]
　Seed crystals, the FAU type zeolite as a starting material, N, N, N-trimethyl-1-adamantan ammonium hydroxide (TMAdaOH) as organic template, is obtained by pre-prepared in the following way.
[0036]
　First 50ml beaker TMAdaOH solution (SACHEM, Inc., 25 wt%) was placed 8.09g was added 0.38g of sodium hydroxide, and the whole was agitated for 5 minutes. Thereafter, the FAU-type zeolite, HSZ-360 and HSZ-390 (manufactured by Tosoh Corporation) was added 2.1g and 0.9g, respectively, were stirred for 15 minutes. Thus the molar composition of each material of the mixed liquid is TMAdaOH / SiO 2 = 0.2, NaOH / SiO 2 = 0.2, H 2 O / SiO 2 was = 7, Si / Al = 10 .
[0037]
　Then, were charged the mixture into inner tube of the autoclave Teflon, the autoclave was sealed and subjected to 40 hours hydrothermal synthesis at 160 ° C.. Thereafter, the autoclave was cooled, the gel in the Teflon inner cylinder was washed with deionized water and centrifuged, the supernatant liquid Once became neutral, to which was added water. Thus the 5 wt% of a seed crystal dispersion was prepared. In this case, the particle diameter of the CHA seed crystals was 300 ~ 500 nm.
[0038]
　This seed crystal dispersion liquid, the support was immersed for 30 minutes, then removed the support from the liquid and dried overnight at 40 ° C.. Thus it was deposited a seed crystal to a support.
[0039]
　It was then prepared secondary growth solution for forming a film of zeolite membrane by the following method.
[0040]
　1.04g put TMAdaOH in 100ml beaker, was added 28.1g of ion-exchanged water to here. Further NaOH was added 0.13 g, and the whole was agitated for 5 minutes. Thereafter, the mixture in the FAU-type zeolite HSZ-360 and HSZ-390, respectively added 0.64g and 0.32 g, it was stirred for 3 hours. Thus prepared the secondary growth solution. The molar composition of each substance in the secondary growth solution, TMAdaOH / SiO 2 = 0.076, NaOH / SiO 2 = 0.2, H 2 O / SiO 2 was = 100, Si / Al = 10 .
[0041]
　Then, the inner tube of the autoclave Teflon, established the alumina support having an intermediate layer was deposited a seed crystal, after filling the inner cylinder with the secondary growth solution, the autoclave was sealed, 160 was 16 hours hydrothermal synthesis at ° C.. Thus was formed a CHA type zeolite membrane on the intermediate layer of the substrate by hydrothermal synthesis in secondary growth solution.
[0042]
　Thereafter, the autoclave was cooled, the support was taken out from the inner cylinder having formed zeolite membrane was washed with deionized water.
Finally, to remove the organic template, it was subjected to 10 hours firing at 500 ° C. in an electric furnace.
The electron microscope image of the resulting zeolite membrane shown in FIG. (A) the surface of the membrane of FIG. 1 is a cross section of (b) the membrane. The surface of the zeolite membrane is covered without a gap in the 10 ~ 100 nm particles, the thickness was 2 ~ 3 [mu] m.
[0043]
　As comparison, the surface electron microscopic image of a known zeolite membrane having a small CHA structure of Al content (FIG. 1 and the same magnification) in FIG. FIGS. 1 (a) and as is apparent from a comparison of FIG. 3, a zeolite membrane obtained in Preparation Example 1 has a dense structure, maintaining the Si / Al = 10.
[0044]
　　Then, X-rays diffraction measurement of the obtained zeolite membranes (Rigaku Co., Ultima IV) was carried out.
The resulting X-ray diffraction pattern shown in FIG. This X-ray diffraction pattern, the film was confirmed to be composed of CHA-type zeolite. In X-ray diffraction pattern, the peak intensity in the vicinity of 2 [Theta] = 18 ° is 0.3 times the peak intensity in the vicinity of 2 [Theta] = 21 °, peak intensity in the vicinity of 2 [Theta] = 10 ° at 2.7 times the peak intensity in the vicinity of 2 [Theta] = 21 ° it has been found that there is.
Production Example 2 (Si / Al ratio of impact = 25)
intermediate layer on the surface (thickness of about 50 [mu] m, an average pore diameter of 0.8 [mu] m) cylindrical alumina support having (Hitachi Zosen Corp., a diameter of 16 mm, length 60 mm, mean pore diameter 10 [mu] m) was prepared, the CHA-type zeolite 25 g / m on a surface of the intermediate layer as a seed crystal 2 were deposited.
[0045]
　Seed crystals were prepared in the same manner as in Production Example 1. Further, deposition method of the seed crystal to the support was also carried out in the same manner as in Preparation Example 1.
[0046]
　Were then prepared secondary growth solution for forming a film of zeolite membranes in Production Example 1 a similar manner. The molar composition of each substance in the secondary growth solution, TMAdaOH / SiO 2 = 0.076, NaOH / SiO 2 = 0.2, H 2 O / SiO 2 was = 100, Si / Al = 25 .
Subsequent steps were performed in the same manner as in Preparation Example 1.
The obtained results of X-ray diffraction measurement of the zeolite membrane, showed the same X-ray diffraction pattern with the zeolite membrane obtained in Production Example 1.
Production Example 3 (Effect = 50 Si / Al ratio)
intermediate layer on the surface (thickness of about 50 [mu] m, an average pore diameter of 0.8 [mu] m) cylindrical alumina support having (Hitachi Zosen Corp., a diameter of 16 mm, length 60 mm, mean pore diameter 10 [mu] m) was prepared, the CHA-type zeolite 25 g / m on a surface of the intermediate layer as a seed crystal 2 were deposited.
[0047]
　Seed crystals were prepared in the same manner as in Production Example 1. Further, deposition method of the seed crystal to the support was also carried out in the same manner as in Preparation Example 1.
[0048]
　Were then prepared secondary growth solution for forming a film of zeolite membranes in Production Example 1 a similar manner. The molar composition of each substance in the secondary growth solution, TMAdaOH / SiO 2 = 0.076, NaOH / SiO 2 = 0.2, H 2 O / SiO 2 was = 100, Si / Al = 50 .
Subsequent steps were performed in the same manner as in Preparation Example 1.
The obtained results of X-ray diffraction measurement of the zeolite membrane, showed the same X-ray diffraction pattern with the zeolite membrane obtained in Production Example 1.
Production Example 4 (Si / Al ratio of impact = 100)
intermediate layer on the surface (thickness of about 50 [mu] m, an average pore diameter of 0.8 [mu] m) cylindrical alumina support having (Hitachi Zosen Corp., a diameter of 16 mm, length 60 mm, mean pore diameter 10 [mu] m) was prepared, the CHA-type zeolite 25 g / m on a surface of the intermediate layer as a seed crystal 2 were deposited.
[0049]
　Seed crystals were prepared in the same manner as in Production Example 1. Further, deposition method of the seed crystal to the support was also carried out in the same manner as in Preparation Example 1.
[0050]
　Were then prepared secondary growth solution for forming a film of zeolite membranes in Production Example 1 a similar manner. The molar composition of each substance in the secondary growth solution, TMAdaOH / SiO 2 = 0.076, NaOH / SiO 2 = 0.2, H 2 O / SiO 2 was = 100, Si / Al = 100 .
Subsequent steps were performed in the same manner as in Preparation Example 1.
The obtained results of X-ray diffraction measurement of the zeolite membrane, showed the same X-ray diffraction pattern with the zeolite membrane obtained in Production Example 1.
Production Example 5 (Si / Al ratio of impact = 110)
intermediate layer on the surface (thickness of about 50 [mu] m, an average pore diameter of 0.8 [mu] m) cylindrical alumina support having (Hitachi Zosen Corp., a diameter of 16 mm, length 60 mm, mean pore diameter 10 [mu] m) was prepared, the CHA-type zeolite 25 g / m on a surface of the intermediate layer as a seed crystal 2 were deposited.
[0051]
　Seed crystals were prepared in the same manner as in Production Example 1. Further, deposition method of the seed crystal to the support was also carried out in the same manner as in Preparation Example 1.
[0052]
　Were then prepared secondary growth solution for forming a film of zeolite membranes in Production Example 1 a similar manner. The molar composition of each substance in the secondary growth solution, TMAdaOH / SiO 2 = 0.076, NaOH / SiO 2 = 0.2, H 2 O / SiO 2 was = 100, Si / Al = 110 .
Subsequent steps were performed in the same manner as in Preparation Example 1.
The obtained results of X-ray diffraction measurement of the zeolite membrane, showed the same X-ray diffraction pattern with the zeolite membrane obtained in Production Example 1.

Test Example 1
　The separation performance of the zeolite film formed in the above Production Example 1 was evaluated in pervaporation. That were separated from a mixture of 50 wt% / 50 wt% water / 2-propanol selectively transmits water. Separation conditions, the temperature 75 ° C., with a pressure difference 1 atmosphere before and after the film. As a result, the permeation flux 32 kg / (m 2 h), and the separation factor alpha (water / 2-propanol
) at 386, the water concentration in the permeate was 99.7% by weight.
Test Example 2
　a separation object liquid changed to a mixture of 20 wt% / 80 wt% water / 2-propanol, other points were the same procedure as in Test Example 1. As a result, the permeation flux 20 kg / (m 2 h), and the separation factor alpha (water / 2-propanol) in 1128, water concentration of the permeate was 99.6% by weight.
Test Example 3
　The separation object liquid changed to a mixture of 10 wt% / 90 wt% water / 2-propanol, other points were the same procedure as in Test Example 1. As a result, the permeation flux 10 kg / (m 2 h), and the water concentration of the permeate was 99.6% by weight.
Test Example 4
　The separation object liquid changed to a mixture of 50 wt% / 50 wt% water / acetic acid, other points were the same procedure as in Test Example 1. As a result, the permeation flux 10 kg / (m 2 h), and the water concentration of the permeate was 99.9% by weight.
Test Example 5
　were evaluated gas separation performance of the zeolite film formed in the above Production Example 1. In other words, separation was performed which selectively permeates carbon dioxide from 50% / 50% mixture in moles of carbon dioxide / methane. Separation conditions, the temperature 40 ° C., with a pressure difference 3 atmospheres before and after the film. As a result, transmission coefficient-0.6 mol 1.2E / (m 2 sPa), and the separation factor α was 10.
Test Example 6
　changing the temperature in the test conditions 100 ° C., the otherwise operated in the same manner as in Test Example 5. As a result, transmission coefficient-0.6 mol 1.2E / (m 2 sPa), and the separation factor α was 22.
Test Example 7
　changing the temperature in the test conditions 120 ° C., the otherwise operated in the same manner as in Test Example 5. As a result, transmission coefficient-0.6 mol 1.0E / (m 2 sPa), and the separation factor α was 21.
[0053]
　Test conditions and test results of Test Examples 1 to 4 are summarized in Table 1, are summarized in Table 2. Test conditions and test results of Test Example 5-7. When these results are compared with Patent Document 1, it is seen superiority of the present invention showed a high permeation rate.
[0054]
[Table 1]

[0055]
[Table 2]

[0056]
As can be seen from the above table, in both systems, the zeolite membrane according to the invention exhibited a high separation performance.
Test Example 8
were evaluated gas separation performance of the zeolite film formed in the above Production Example 2. It was selectively transmitted to separate carbon dioxide from the mole at 50% / 50% mixture of CO / methane. Separation conditions, the temperature 40 ° C., with a pressure difference 3 atmospheres before and after the film. As a result, transmission coefficient-0.6 mol 1.4E / (m 2 sPa), and the separation factor α was 122.
Test Example 9
　changing the temperature in the test conditions 100 ° C., the otherwise operated in the same manner as in Test Example 8. As a result, transmission coefficient-0.7 mol 9.5E / (m 2 sPa), and the separation factor α was 66.
Test Example 10
　changed the temperature in the test conditions 120 ° C., the otherwise operated in the same manner as in Test Example 8. As a result, transmission coefficient-0.7 mol 7.1E / (m 2 sPa), and the separation factor α was 47.
[0057]
[table 3]

[0058]
The Si / Al ratio by 25, high separation performance of the carbon dioxide / methane was obtained.
Test Example 11
　The separation performance of the zeolite film formed in the above Production Example 3 was evaluated by pervaporation. The separated object liquid changed to a mixture of 30 wt% / 70 wt% water / acetic acid, other points were the same procedure as in Test Example 1. As a result, the permeation flux 10 kg / (m 2 h), and the separation coefficient was 155.
Test Example 12
　The separation performance of the zeolite film formed in the above Preparation Example 4 was evaluated by pervaporation. The separated object liquid changed to a mixture of 50 wt% / 50 wt% water / 2-propanol, other points were the same procedure as in Test Example 1. As a result, the permeation flux 50 kg / (m 2 h), and the separation factor was 30.
Test Example 13
　The separation performance of the zeolite film formed in the above Preparation Example 4 was evaluated by pervaporation. The separated object liquid changed to a mixture of 30 wt% / 70 wt% water / acetic acid, other points were the same procedure as in Test Example 1. As a result, the permeation flux 15 kg / (m 2 h), and the separation factor was 20.
Test Example 14
　The separation performance of the zeolite film formed in the above Preparation Example 5 was evaluated by pervaporation. The separated object liquid changed to a mixture of 50 wt% / 50 wt% water / 2-propanol, other points were the same procedure as in Test Example 1. As a result, the permeation flux 90 kg / (m 2 h), and the separation coefficient was 1. Thus, a dense film was not obtained.
[0059]
　The above Test Examples are summarized in Table 4.
[0060]
[Table 4]

The scope of the claims

[Claim 1]
　A zeolite membrane having CHA crystal structure formed as a film on a porous support of an intermediate layer having an intermediate layer, Si / Al (molar ratio) of the CHA-type zeolite particles is from 9.5 to 100.5 There, the X-ray diffraction pattern obtained by irradiating X-rays on the zeolite membrane surface, 2 [Theta] = 18 peak intensity around ° is 0.5 times less than the peak intensity in the vicinity of 2 [Theta] = 21 °, and / or, 2 [Theta] = a method of manufacturing a zeolite membrane, wherein the peak intensity around 10 ° is less than 4 times the peak intensity in the vicinity of 2 [Theta] = 21 °,
an aqueous containing Si element source, Al element source, an alkali source and an organic template using reaction mixtures, by hydrothermal synthesis, in forming the zeolite membrane having a CHA crystal structure as the porous support of the intermediate layer, as the Si element source and Al element source de aluminum Method for manufacturing a zeolite membrane, which comprises using a not treated FAU type zeolite.
[Claim 2]
　Using a seed crystal in the hydrothermal synthesis, the seed crystal, Si element source, Al element source, an alkali source and FAU type zeolite as a Si element source and Al element source in the hydrothermal synthesis using an aqueous reaction mixture containing an organic template method for manufacturing a zeolite membrane according to claim 1, characterized in that it is prepared with.
[Claim 3]
　Method for manufacturing a zeolite membrane according to claim 2 having a particle diameter of CHA-type crystals, characterized in that a 100 nm ~ 1 [mu] m.
[Claim 4]
　Obtained by the production method according to any of claims 1 to 3,
the zeolite film, by contacting the mixture of liquid or gas containing to be separated compounds, is transmitted through the high permeability material from the mixture by the separation method characterized by separating the compounds.
[Claim 5]
　Mixture containing the to be separated compound is a mixture of water content 10% or more by weight of 2-propanol and water, temperature 75 ° C., when performing separation at a pressure difference 1 atmosphere before and after the membrane permeation flux is 10 kg / (m 2 h) above, the method of separation according to claim 4, water concentration of the permeate is characterized in that 99 wt% or more.
[Claim 6]
　Mixture containing the to be separated compound is a mixture of water content 30% or more by weight of acetic acid and water, temperature 75 ° C., when performing separation at a pressure difference 1 atmosphere before and after the membrane permeation flux is 10 kg / (m 2 h) above, the method of separation according to claim 4, water concentration of the permeate is characterized in that 99 wt% or more.
[Claim 7]
　Mixture containing the to be separated compounds, and carbon dioxide ratio of carbon dioxide is 50 wt% or more, methane, a mixed gas of ammonia or sulfur hexafluoride, temperature 40 ° C., the film before and after the pressure difference 3 atm If the separation was carried out in conditions, the permeability coefficient of carbon dioxide × 10 1 -6 mol / (m 2 method of separating according to claim 4, characterized in that at sPa) or more.
[8.]
　Mixture containing the to be separated compound is a mixed gas of carbon dioxide ratio of carbon dioxide is 50 wt% or more, methane, ammonia, or sulfur hexafluoride, a temperature 100 ~ 120 ° C., the pressure differential across membrane If the separation was carried out at three atmospheres conditions, the permeability coefficient of carbon dioxide × 10 1 -7 mol / (m 2 method of separating according to claim 4, characterized in that at sPa) or more.

Drawing

[ Figure 1]

[Figure 2]

[Figure 3]