JP6172239B2 - Method for recovering alcohol from alcohol-water mixture - Google Patents

Description

  The present invention relates to a method for recovering alcohol from an alcohol-water mixture, and more particularly to a method for recovering alcohol using a zeolite membrane.

  The recovery of alcohol from alcohol-water mixtures is performed in many fields in chemical processes. For example, in the case of production of bioethanol for fuel, since the ethanol concentration in the mash liquid obtained by the fermentation method is usually about 6 to 12% by weight, first, it is concentrated to 40 to 50 wt% in the mash concentration tower, Concentrate to about 95% by weight of hydrous ethanol near the azeotropic point in the concentrating tower. And in order to utilize as ethanol for fuels etc. which are directly mixed with gasoline, it is necessary to further dehydrate to at least 99.5% by weight or more of absolute ethanol.

  By the way, the amount of heat required for the alcohol recovery method by the above concentrated dehydration process reaches about half of the ethanol combustion heat, so energy saving is an important issue both industrially and in life cycle assessment (LCA). ing.

  Thus, as a dehydration process replacing the conventional azeotropic distillation method, a PSA method excellent in energy saving and a membrane dehydration method using an A-type zeolite membrane have been proposed. The membrane dehydration method is superior to the PSA method in further energy saving, and has an advantage that water-containing ethanol having a concentration of about 85 to 90% by weight, which is lower than normal water-containing ethanol, can be treated. (Non-Patent Document 1).

  However, if water-containing ethanol having a lower alcohol concentration than the above can be treated, the amount of heat of the distillation column arranged in the previous step of the separation membrane module can be further reduced, and in some cases the distillation column Can be omitted, and significant energy saving can be achieved.

Chemical Engineering Vol.1 No.12 812-816 (2007)

The present invention has been made in view of the above circumstances, and an object of the present invention is a method for recovering alcohol using a zeolite membrane, which is intended for treatment with hydrous alcohol having an alcohol concentration of 85% by weight or less. An object of the present invention is to provide a method for recovering alcohol that can be carried out with a permeation flux of (m ² · h) or more.

That is, the present invention is as follows.
(1) used for alcohol concentration,
An inorganic porous support-zeolite membrane composite having a zeolite membrane containing a CHA-type zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 5 or more and 100 or less and having a thickness of 0.5 mm or more and an inner diameter of 0.5 cm or more A manufacturing method of
A reaction mixture containing a Si element source, an Al element source and an alkali source, and the above inorganic porous support is immersed in a reaction mixture in which the alkali source is a hydroxide of Na or K, and a zeolite membrane is formed by hydrothermal synthesis. Characterized by forming,
A method for producing an inorganic porous support-zeolite membrane composite.
(2) The method for producing an inorganic porous support-zeolite membrane composite according to (1), wherein the zeolite membrane composite obtained by hydrothermal synthesis is heat-treated.
(3) The inorganic porous support-zeolite membrane composite as described in (1) or (2), wherein an inorganic porous support having 0.1 to 8 g of seed crystals attached per 1 m ^{2 in} advance is immersed in the reaction mixture. Body manufacturing method.
(4) The method for producing an inorganic porous support-zeolite membrane composite according to any one of (1) to (3), wherein the temperature at which the zeolite is crystallized is 100 to 200 ° C.
(5) The method for producing an inorganic porous support-zeolite membrane composite according to any one of (1) to (4), wherein the thickness of the zeolite membrane is 0.1 μm or more and 100 μm or less.
(6) Any of (1) to (5), wherein the ratio of Si element source to alkali source is 0.02 or more and 0.5 or less in terms of a molar ratio of M ₂ O / SiO ₂ (M is Na or K). A method for producing an inorganic porous support-zeolite membrane composite as described in 1.
(7) The method for producing an inorganic porous support-zeolite membrane composite according to any one of (1) to (6), wherein the molar ratio of K to K and Na is 0.01 to 1.
(8) Production of inorganic porous support-zeolite membrane composite according to any one of (1) to (7), wherein the ratio of Si element source to water is 50 to 150 as the molar ratio of water to SiO ₂ Method.
(9) A method for producing concentrated alcohol from an alcohol-water mixture using a separation membrane module, wherein the separation membrane housed in the separation membrane module is any one of (1) to (8) A method for producing concentrated alcohol, which is an inorganic porous support-zeolite membrane composite.
(10) The method for producing a concentrated alcohol according to (9) , wherein the alcohol concentration of the alcohol-water mixture is 85% by weight or less.
(11) The method for producing a concentrated alcohol according to (9) or (10) , wherein the separation membrane is contacted with a liquid of an alcohol-water mixture to permeate water by a pervaporation method.
(12) The method for producing a concentrated alcohol according to (11) , wherein the temperature of the alcohol-water mixture supplied to the separation membrane module is 25 to 200 ° C.
(13) The method for producing a concentrated alcohol according to (9) or (10) , wherein a gas of an alcohol-water mixture is brought into contact with the separation membrane by a vapor permeation method to permeate water.
(14) The method for producing concentrated alcohol according to (13) , wherein the temperature of the superheated steam of the alcohol-water mixture supplied to the separation membrane module is T + 1 to 100 ° C., where T is a saturated vapor pressure temperature.

According to the present invention, a method for recovering alcohol using a zeolite membrane is performed with a hydrous alcohol having an alcohol concentration of 85% by weight or less and a permeation flux of 1 kg / (m ² · h) or more. A method for recovering alcohol is provided.

FIG. 1 is a process explanatory diagram of an example of a pervaporation method (PV method) as an example of the present invention. FIG. 2 is a process explanatory diagram of an example of a vapor permeation method (VP method) as another example of the present invention. FIG. 3 is an explanatory diagram of an example of the adsorption device used in the present invention. FIG. 4 is an explanatory view of a simple pervaporation test apparatus used for obtaining the separation performance of the separation membrane in Reference Examples and Examples. FIG. 5 is an XRD measurement result of the zeolite membrane described in Reference Example 2. FIG. 6 is an XRD measurement result of the zeolite membrane described in Reference Example 5. FIG. 7 shows the XRD measurement results of the zeolite membrane described in Reference Example 6. FIG. 8 is an explanatory view of the dehydration method by various collection methods of the mixture in the present invention. FIG. 9 is a flow sheet and material balance employed in a simulation performed to confirm the effect of the present invention.

  First, an outline of a separation technique using a separation membrane module will be described based on the attached drawings. Separation techniques using the separation membrane module are roughly classified into PV method and VP method.

  In the PV method, a separation membrane is brought into contact with a liquid of an alcohol-water mixture to allow water to permeate. That is, this method is also called a pervaporation method or a permeation vaporization method, and the alcohol-water mixture liquid (feed liquid) is evaporated through the separation membrane, and at that time, only water is permeated to separate the alcohol. And concentrate. Since the supply liquid is cooled by the heat of vaporization, a heating means for supplementing it is necessary.

  In the case of the PV method shown in FIG. 1, two separation membrane modules are arranged in series, and the supply liquid is supplied to the first separation membrane module (1) by the supply pump (51) via the heater (11). Supplied. The water (gas) that has passed through the separation membrane is introduced into the cooler (3), condensed, and then stored in the tank (4). The alcohol aqueous solution concentrated without passing through the separation membrane is circulated to the first separation membrane module (1) and concentrated.

  The concentrated liquid taken out from the circulation path of the first separation membrane module (1) is supplied to the second separation membrane module (2) via the intermediate heater (21). In the same manner as above, the water (gas) that has passed through the separation membrane is introduced into the cooler (3), condensed, stored in the tank (4), and concentrated without passing through the separation membrane. Is circulated to the second separation membrane module (2) and concentrated. Then, the finally concentrated alcohol is taken out from the circulation path of the second separation membrane module (2).

  Circulation of the liquid in the first separation membrane module (1) and the second separation membrane module (1) is performed by circulation pumps (52) and (53). The vacuum required for driving the separation membrane module is given by a vacuum pump (54), and the degree of vacuum of each separation membrane module is controlled by pressure control valves (61) and (62) provided in the middle of the piping. The water stored in the tank (4) is discharged by a discharge pump (55).

  On the other hand, in the VP method, a water of an alcohol-water mixture is brought into contact with the separation membrane to allow water to permeate. That is, this method is also called a vapor permeation method, and is different from the PV method in that superheated steam (feed gas) of an alcohol-water mixture is brought into contact with a separation membrane. Therefore, in the case of the VP method shown in FIG. 2, in addition to the evaporator (12), the steam obtained by the evaporator (12) is heated in the introduction pipe of the first separation membrane module (1) to generate superheated steam. A heater (13) is arranged for this purpose. Reference numerals (10) and (20) represent heating means for maintaining the processing target in the separation membrane module in a vapor state. The significance of the other symbols is the same as in the PV method shown in FIG.

  Although the PV method shown in FIG. 1 adopts a circulation method, a non-circulation method may be adopted. In addition, the drive of the separation membrane module may employ a sweep gas system that supplies nitrogen, dry air, or the like to the permeate side instead of the vacuum system shown in FIGS.

  The alcohol recovery method according to the present invention may be used as an alternative to the above-described distillation column of the conventional method, and is used as a post-process means of the distillation column, that is, disposed in the preceding stage of the separation membrane module. The alcohol-water mixture recovered from the distillation tower may be supplied to the separation membrane module.

  When supplying the liquid (feed liquid) of the alcohol-water mixture recovered from the bottom of the distillation column and / or the middle stage of the distillation column to the separation membrane module, the PV method is generally applied, and the separation membrane module is supplied with the distillation column. When supplying the gas of the alcohol-water mixture recovered from the top of the column and / or the middle stage of the distillation column, the VP method is generally applied. In FIG. 8, (a) is a method of dehydrating the mixture gas recovered from the top of the distillation column by the VP method, (b) is a method of dehydrating the mixture gas recovered from the middle stage of the distillation column by the VP method, c) shows the method of dehydrating the mixture gas collect | recovered from the tower bottom of the distillation tower by PV method.

  In the present invention, the alcohol or water mixture liquid or gas recovered from the separation membrane module is supplied to a distillation column or adsorption device disposed in the subsequent stage of the separation membrane module to recover further concentrated alcohol. I can do it.

  As the distillation column, any type of distillation column such as a packed distillation column or a shelf distillation column can be adopted. Further, the adsorption device may be any of a pressure swing adsorption device (PSA), a temperature swing adsorption device (TSA), and a pressure temperature swing adsorption device (PTSA) in which both are combined. The PSA has a function of adsorbing a gas to the adsorbent by increasing the pressure and desorbing the gas from the adsorbent by decreasing the pressure. On the other hand, TSA has a function of desorbing liquid from the adsorbent by adsorbing the liquid to the adsorbent and supplying a heated gas (such as nitrogen) to raise the temperature. PSA, TSA, and PTSA are widely used due to their relatively simple equipment configuration, and “Molecular Sieve” (trade name), which is a synthetic zeolite, is preferably used as the adsorbent because of its high dehydrating ability. The

  The PSA (7) shown in FIG. 3 is disposed in the subsequent stage of the second separation membrane module (2) of the VP method shown in FIG. 2, and is mainly switched between two adsorption towers: the first adsorption tower (7a ) And the second adsorption tower (7b). The switching is performed by lowering the adsorption capacity in each adsorption tower, and the adsorption tower whose adsorption operation (dehydration operation) is stopped is switched to the desorption operation (drying operation). In this manner, the adsorption operation and the desorption operation are alternately performed between the two adsorption towers. The switching operation is performed by a valve (not shown) arranged in each pipeline.

  First, the vapor of the alcohol-water mixture concentrated in the separation membrane module is transferred to the first adsorption tower (7a) or the second adsorption tower (7b) in a state of being pressurized to a constant pressure while maintaining the vapor state. be introduced. Thereby, the adsorption operation is started. Then, substantially only water vapor is adsorbed on the molecular sieve, and the dehydrated alcohol vapor is condensed and recovered by the cooler (71). And desorption of the water vapor | steam from the 1st adsorption tower (7a) or the 2nd adsorption tower (7b) in which adsorption capacity fell is performed by reducing the pressure in a tower. The desorbed water vapor is condensed and recovered by the cooler (72). In addition, you may heat-recover using a heat exchanger for the cooler (71) and / or (72).

  Next, the alcohol-water mixture used as a concentration target in the present invention will be described. Examples of the alcohol contained in the alcohol-water mixture include methanol, ethanol, propanol and the like.

  Next, the operating conditions of the separation membrane module will be described. The optimum range of operating conditions cannot be determined unconditionally because it varies depending on the type of alcohol-water mixture supplied to the separation membrane module, but general conditions such as temperature and operating pressure are the range of conditions for known operating methods. The following ranges are selected as appropriate.

  In the case of the PV method shown in FIG. 1, the temperature of the alcohol-water mixture (liquid) supplied to the separation membrane module is usually 25 to 200 ° C., preferably 70 to 150 ° C. The operating pressure is usually 0.1 to 1.5 MPa, preferably 0.2 to 0.8 MPa.

  In the case of the VP method shown in FIG. 2, the temperature of the superheated steam of the alcohol-water mixture supplied to the separation membrane module is usually T + 1 to 100 ° C., preferably T + 5 to 30 ° C., where T is the saturated vapor pressure temperature. . The operating pressure is usually 0.1 to 1.5 MPa, preferably 0.2 to 0.8 MPa.

  The number of separation membrane modules installed is appropriately selected depending on the conditions, and may be one or may be two or more as shown. As a result, alcohol concentrated to a concentration of 95% by weight or more can be recovered. As described above, the further concentration can be performed by a distillation column or an adsorption device arranged in the subsequent stage of the separation membrane module. The adsorption apparatus is not applicable to all alcohol aqueous solutions, and it is necessary to determine whether or not the application is possible in consideration of the boiling point of the alcohol, the adsorption dependency on the molecular sieve, and the like.

Next, the separation membrane module used in the present invention will be described. The separation membrane module used in the present invention comprises an inorganic porous support-zeolite membrane composite having a zeolite membrane on the surface of the inorganic porous support as a separation membrane. The greatest feature of the present invention is that a porous support-zeolite membrane composite in which the zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 5 or more is used.

  First, each component which comprises the inorganic porous support body-zeolite membrane composite used by this invention is demonstrated concretely. In the following description, “inorganic porous support-zeolite membrane composite” may be simply referred to as “zeolite membrane composite”.

  The inorganic porous support used in the present invention is not particularly limited as long as it has chemical stability such that zeolite can be crystallized in the form of a film on the surface and is porous. Examples include sintered ceramics such as silica, α-alumina, γ-alumina, mullite, zirconia, titania, yttria, silicon nitride, silicon carbide, sintered metals such as iron, bronze, and stainless steel, glass, and carbon molded products. Can be mentioned.

Among inorganic porous supports, porous supports including sintered ceramics, which are solid materials whose basic components or most of them are composed of inorganic non-metallic substances, are partly zeolite. Zeolite formation during membrane synthesis is particularly preferred because it has the effect of increasing the adhesion at the interface.
Specific examples include ceramic sintered bodies containing silica, α-alumina, γ-alumina, mullite, zirconia, titania, yttria, silicon nitride, silicon carbide, and the like. Among them, the inorganic porous support containing at least one of alumina, silica, and mullite is easy to partially zeoliticize the inorganic porous support. Therefore, the inorganic porous support and zeolite, particularly CHA-type zeolite This is more preferable in that the bond becomes strong and a dense membrane with high separation performance is easily formed.

  The shape of the inorganic porous support used in the present invention is not limited as long as it can effectively separate a gas mixture or a liquid mixture. Specifically, a flat plate shape, a tubular shape, or a cylindrical shape, A honeycomb or monolith having a large number of cylindrical or prismatic holes may be mentioned, and any shape may be used.

  The inorganic porous support used in the present invention crystallizes zeolite on its surface (hereinafter also referred to as “inorganic porous support surface”).

The average pore diameter of the surface of the inorganic porous support is not particularly limited, but those having a controlled pore diameter are preferred, usually 0.02 μm or more, preferably 0.05 μm or more, more preferably 0. 0.1 μm or more, usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less.
If the average pore diameter is too small, the amount of permeation tends to be small. If it is too large, the strength of the support itself may be insufficient, and the proportion of pores on the surface of the support will increase, forming a dense zeolite membrane. It may be difficult to be done.

The surface of the inorganic porous support is preferably smooth, and the surface may be polished with a file or the like as necessary.
The surface of the inorganic porous support means, for example, the surface of the inorganic porous support that crystallizes zeolite, and may be any surface of any shape as long as the surface is a plurality of surfaces. Also good. For example, in the case of a cylindrical tube support, it may be the outer surface or the inner surface, and in some cases both the outer and inner surfaces.

Further, the pore diameter of the portion other than the surface of the inorganic porous support of the inorganic porous support used in the present invention is not limited and need not be particularly controlled.
The porosity of the porous support is usually 20% or more, preferably 25% or more, more preferably 30% or more, and usually 70% or less, preferably 60% or less, more preferably 50% or less. The porosity of the inorganic porous support affects the permeation flow rate when separating gases and liquids, and tends to inhibit the permeation of the permeate if less than the lower limit, and the strength of the inorganic porous support if the upper limit is exceeded. Tends to decrease.

Next, a zeolite crystal having a SiO ₂ / Al ₂ O ₃ molar ratio of 5 or more will be described. The SiO ₂ / Al ₂ O ₃ molar ratio is preferably 8 or more, more preferably 10 or more, and still more preferably 12 or more. The upper limit is usually 2000 or less, preferably 1000 or less, more preferably 500 or less, and still more preferably 100 or less. If the SiO ₂ / Al ₂ O ₃ molar ratio is less than the lower limit, the durability tends to decrease, and if the upper limit is exceeded, the hydrophobicity is too strong and the permeation flux tends to be small. The SiO ₂ / Al ₂ O ₃ molar ratio can be adjusted by the reaction conditions of hydrothermal synthesis described later.

Incidentally, _SiO 2 / _Al 2 _{O 3} molar ratio in the present invention, a scanning electron microscope - is a value obtained by energy dispersive X-ray spectroscopy (SEM-EDX). In order to obtain information on only a film of several microns, the X-ray acceleration voltage is usually measured at 10 kV.

The framework density of the main zeolite constituting the zeolite membrane in the present invention is not particularly limited, but is usually 17T / 1000Å or less, preferably 16T / 1000Å or less, particularly preferably 15.5T / 1000Å or less, most preferably , 15T / 100
0 or less.

The framework density means the number of T elements constituting a skeleton other than oxygen per 1000 ³ of the zeolite, and this value is determined by the structure of the zeolite. The relationship between the framework density and the structure of zeolite is shown in ATLASOFZEOLITE FRAMEWORK TYPES Fifth Revised Edition 2001 ELSEVIER.

The main zeolite constituting the zeolite membrane in the present invention usually contains a zeolite having an oxygen 6-10 membered ring structure, and preferably contains a zeolite having an oxygen 6-8 membered ring structure.
Here, the value of n of the zeolite having an oxygen n-membered ring indicates the one having the largest number of oxygen among the pores composed of oxygen and T element forming the zeolite skeleton. For example, when there are 12-membered and 8-membered pores of oxygen, such as MOR type zeolite, it is regarded as a 12-membered ring zeolite.

  An example of a zeolite having an oxygen 6-10 membered ring structure is AEI, AEL, AFG, ANA, BRE, CAS, CDO, CHA, DAC, DDR, DOH, EAB, EPI, ESV, EUO, FAR, FRA, FER, GIS, GIU, GOO, HEU, IMF, ITE, ITH, KFI, LEV, LIO, LOS, LTN, MAR, MEP, MER, MEL, MFI, MFS, MON, MSO, MTF, MTN, MTT, MWW, NAT, NES, NON, PAU, PHI, RHO, RRO, RTE, RTH, RUT, SGT, SOD, STF, STI, STT, TER, TOL, TON, TSC, TUN, UFI, VNI, VSV, WEI, YUG, etc. There is.

  An example of a zeolite having a preferable oxygen 6-8 membered ring structure is AEI, AFG, ANA, CHA, EAB, ERI, ESV, FAR, FRA, GIS, ITE, KFI, LEV, LIO, LOS, LTN, MAR , PAU, RHO, RTH, SOD, STI, TOL, UFI, etc.

The oxygen n-membered ring structure determines the pore size of the zeolite, and in the zeolite smaller than the 6-membered ring, the pore diameter is smaller than the kinetic radius of the H ₂ O molecule, so the permeation flux is reduced and is practical. Not. Moreover, when it is larger than the oxygen 10-membered ring structure, the pore diameter becomes large, and the separation performance is lowered with a small-sized organic substance, so that the use is limited.

Among them, the zeolite structure preferably has the above-mentioned SiO ₂ / Al ₂ O ₃ molar ratio, more preferably AEI, CHA, KFI, PAU, RHO, RTH, UFI, and more preferably , CHA, LEV, UFI, most preferably CHA. The zeolite is preferably an aluminosilicate.

  Next, the CHA type zeolite will be described. The CHA-type zeolite suitably used in the present invention indicates a CHA structure with a code that defines the structure of the zeolite defined by International Zeolite Association (IZA). It is a zeolite having a crystal structure equivalent to that of naturally occurring chabasite. The CHA-type zeolite has a structure characterized by having three-dimensional pores composed of 8-membered oxygen rings having a diameter of 3.8 × 3.8 mm, and the structure is characterized by X-ray diffraction data.

  The framework density of the CHA-type zeolite used in the present invention is 14.5 T / 1000 kg.

In the present invention, the zeolite membrane may be a zeolite alone or a membrane formed by dispersing the zeolite powder in a binder such as a polymer to form a membrane on various supports. It may be a zeolite membrane composite fixed to the surface.
Among them, a zeolite membrane composite in which the zeolite is fixed in a film form on a porous support described in detail later is particularly preferable. Since the zeolite membrane composite has a support, mechanical strength is increased, handling becomes easy, various device designs are possible, and since it is composed entirely of inorganic substances, it has excellent heat resistance and chemical resistance. It is because it is excellent.

  As a component constituting the membrane, an inorganic binder such as silica and alumina, an organic substance such as a polymer, a silylating agent for modifying the surface of the zeolite, or the like may be included as necessary in addition to zeolite.

  The zeolite membrane in the present invention may partially contain an amorphous component or the like, but is preferably a zeolite membrane substantially composed only of zeolite. Preferably, it is a zeolite membrane containing CHA-type zeolite as a main component, and may contain a part of zeolite of other structure such as mordenite type and MFI type, or may contain an amorphous component, etc. Preferably, the zeolite membrane is substantially composed of only CHA-type zeolite.

  The thickness of the zeolite membrane used in the present invention is not particularly limited, but is usually 0.1 μm or more, preferably 0.6 μm or more, more preferably 1.0 μm or more. Moreover, it is 100 micrometers or less normally, Preferably it is 60 micrometers or less, More preferably, it is the range of 20 micrometers or less. If the film thickness is too large, the amount of permeation tends to decrease, and if it is too small, the selectivity and film strength tend to decrease.

  The particle diameter of the zeolite forming the zeolite membrane in the present invention is not particularly limited, but if it is too small, the grain boundary tends to increase and the like, and the permselectivity tends to be reduced. Preferably it is 50 nm or more, More preferably, it is 100 nm or more, and an upper limit is below the thickness of a film | membrane. More preferably, the particle diameter of the zeolite is the same as the film thickness. This is because when the particle diameter of the zeolite is the same as the thickness of the membrane, the grain boundary of the zeolite is the smallest. Zeolite membranes obtained by hydrothermal synthesis are preferred because the zeolite particle size and membrane thickness may be the same.

  In the present invention, the inorganic porous support-zeolite membrane composite is one in which zeolite is fixed in the form of a membrane on the surface of the inorganic porous support, and a part of the zeolite is inside the inorganic porous support. The thing of the state which has adhered to is preferable.

  In order to form such a zeolite membrane composite, the zeolite is crystallized into a film on an inorganic porous support, and the zeolite is fixed to the inorganic porous support with an inorganic binder or an organic binder. And a method of fixing the zeolite-dispersed polymer, a method of fixing the zeolite to the inorganic porous support by impregnating a slurry of zeolite into the inorganic porous support, and optionally sucking it.

In a preferred embodiment of the present invention, zeolite is crystallized in the form of a film on the surface of the inorganic porous support.
Specifically, for example, CHA-type zeolite is crystallized in the form of a film on the surface of the inorganic porous support, and is usually crystallized in the form of a film by hydrothermal synthesis.
The position of the zeolite membrane used in the present invention on the inorganic porous support is not particularly limited. However, when a tubular inorganic porous support is used, a zeolite membrane may be attached to the outer surface or the inner surface. It may be attached to both sides depending on the system to be applied. Moreover, it may be laminated on the surface of the inorganic porous support, or may be crystallized so as to fill the pores on the surface of the porous support. In this case, it is important that there are no cracks or continuous micropores inside the crystallized film layer, and forming a so-called dense film improves the separability.

In the X-ray diffraction pattern of the inorganic porous support-zeolite membrane composite of the present invention, the peak intensity near 2θ = 17.9 ° is 0.5 times or more the peak intensity near 2θ = 20.8 °. It is preferable that it is the magnitude | size of.
The peak intensity here refers to the value obtained by subtracting the background value from the measured value. Speaking of the peak intensity ratio represented by (the intensity of the peak around 2θ = 17.9 °) / (the intensity of the peak around 2θ = 20.8 °), it is desirably 0.5 or more, preferably 1 or more. More preferably, it is 1.2 or more, Most preferably, it is 1.5 or more. The upper limit is not particularly limited, but is usually 1000 or less.

In the inorganic porous support-zeolite membrane composite of the present invention, when the zeolite membrane contains CHA type zeolite, the intensity of the peak around 2θ = 9.6 ° in the X-ray diffraction pattern is around 2θ = 20.8 °. It is preferable that it is 4 times or more the intensity of the peak.
In terms of the peak intensity ratio represented by (the intensity of the peak near 2θ = 9.6 °) / (the intensity of the peak near 2θ = 20.8 °), it is desirably 4 or more, preferably 6 or more, and more preferably. Is 8 or more, particularly preferably 10 or more. The upper limit is not particularly limited, but is usually 1000 or less.

  Here, the X-ray diffraction pattern is obtained by irradiating the surface on which zeolite is mainly attached with X-rays using CuKα as a radiation source to obtain a scanning axis of θ / 2θ. The shape of the sample to be measured may be any shape that can irradiate X-rays on the surface of the membrane composite on which the zeolite is mainly attached. The body itself or the one cut into an appropriate size restricted by the apparatus is preferable.

  The X-ray diffraction pattern here may be measured by fixing the irradiation width using an automatic variable slit when the surface of the membrane composite is a curved surface. An X-ray diffraction pattern using an automatic variable slit refers to a pattern subjected to variable → fixed slit correction.

The peak in the vicinity of 2θ = 17.9 ° here refers to the maximum one of the peaks existing in the range of 17.9 ° ± 0.6 ° among the peaks not derived from the base material, and 2θ = 20.8. The peak in the vicinity of ° indicates the maximum peak in the range of 20.8 ° ± 0.6 ° among peaks not derived from the base material.
Further, the peak near 2θ = 9.6 ° refers to the maximum peak among the peaks not derived from the base material and present in the range of 9.6 ° ± 0.6 °.

  According to the X-ray diffraction pattern, the peak near 2θ = 9.6 ° is a rhombohedral space according to COLLECTIONOF SIMULATED XRD POWTER PATTERNS FOR ZEOLITE Third Revised Edition 1996 ELSEVIER.

(No. 166), it is a peak derived from the plane having an index of (1, 0, 0) in the CHA structure.

The peak near 2θ = 17.9 ° in the X-ray diffraction pattern is COLLECTIONOF.
According to SIMULATED XRD POWDER PATTERNSFOR ZEOLITE Third Revised Edition 1996 ELSEVIER, the space group is set by rhombohedral.

(No. 166) is a peak derived from the (1,1,1) index in the CHA structure.

The peak near 2θ = 20.8 ° in the X-ray diffraction pattern is COLLECTIONOFSI.
According to MULATED XRD POWDER PATTERNS FORZEOLITE Third Revised Edition 1996 ELSEVIER, the space group is set by rhombohedral.

(No. 166) is a peak derived from the (2, 0, -1) index in the CHA structure.

  A typical ratio of peak intensity from the (1,0,0) plane to peak intensity from the (2,0, -1) plane is 2 according to COLLECTIONOF SIMULATEDXRDPOWERS PATTERNS FOR ZEOLITE Third Revised Edition 1996 ELSEVIER. .5. Therefore, when this ratio is 4 or more, for example, the zeolite crystal is oriented so that the (1,0,0) plane when the CHA structure is rhombohedral setting is oriented almost parallel to the surface of the membrane composite. It is thought to mean growing. Orientation and growth of zeolite crystals in the zeolite membrane composite is advantageous in that a dense membrane with high separation performance can be formed.

  A typical ratio of peak intensity from the (1,1,1) plane to the peak from the (2,0, -1) plane is according to COLLECTIONOF SIMULATEDXRDPOWDER PATTERNS FOR ZEOLITE Third Revised Edition 1996 ELSEVIER. 3. Therefore, if this ratio is 0.5 or more, for example, the orientation of the zeolite crystals is such that the (1, 1, 1) plane is close to the parallel surface of the membrane composite when the CHA structure is rhombohedral setting. This means that it is growing. Orientation and growth of zeolite crystals in the zeolite membrane composite is advantageous in that a dense membrane with high separation performance can be formed.

Next, the manufacturing method of a zeolite membrane is demonstrated. The method for producing the zeolite membrane is not particularly limited as long as it can form a membrane containing zeolite. For example, (1) a method of crystallizing zeolite in a membrane form on a porous support, (2) porous support (3) A method of fixing a zeolite-dispersed polymer, (4) A porous support is impregnated with a slurry of zeolite, and in some cases, sucked Thus, any method such as a method of fixing the zeolite to the porous support can be used.
Among these, a method of crystallizing zeolite on a porous support in a film form is particularly preferable. Among these, a method of crystallizing zeolite on the surface of the inorganic porous support by placing the inorganic porous support in a reaction mixture used for zeolite production and directly hydrothermal synthesis is preferable.

  Specifically, as a method of crystallizing zeolite in the form of a membrane on the surface of the inorganic porous support, an aqueous reaction mixture that has been homogenized by adjusting the composition is loosely fixed inside the inorganic porous support. Put it in a heat and pressure resistant container such as an autoclave and heat it.

  Examples of the reaction mixture include an Si element source, an Al element source, an organic template (if necessary), and water, and an alkali source is preferably added as necessary.

The Si element source and Al element source used in the reaction mixture are not particularly limited. As the Si element source, any of amorphous silica, colloidal silica, silica gel, sodium silicate, amorphous aluminum silicate gel, tetraethoxysilane (TEOS), trimethylethoxysilane and the like can be used. As the Al element source, any of sodium aluminate, aluminum hydroxide, aluminum sulfate, aluminum nitrate, aluminum oxide, amorphous aluminosilicate gel and the like can be used.
In addition to the Al element, other element sources, for example, element sources such as Ga, Fe, B, Ti, Zb Chichi ASn, and Zn may be included.

  In the production of zeolite in the present invention, an organic template (structure directing agent) can be used as necessary, and those synthesized using an organic template are preferred. This is because, when synthesized using an organic template, the ratio of silicon atoms to aluminum atoms in the crystallized zeolite is increased, and the acid resistance is improved. The organic template is not particularly limited as long as it can form a desired zeolite membrane.

  One type of template may be used, or two or more types may be used in combination. In the case of the CHA type, organic templates described in US Pat. No. 4,544,538 and US 2008/0075656 A1 may be suitably combined and used. Specifically, a cation derived from an alicyclic amine such as a cation derived from 1-adamantanamine, a cation derived from 3-quinacridinal, a cation derived from 3-exo-aminonorbornene, and the like, More preferred are cations derived from 1-adamantanamine. When a cation derived from 1-adamantanamine is used as an organic template, CHA-type zeolite capable of forming a dense film is crystallized. In addition, a CHA-type zeolite having hydrophilicity sufficient for the membrane to selectively permeate water can be formed, and a CHA-type zeolite excellent in acid resistance can be obtained.

Of the cations derived from 1-adamantanamine, the N, N, N-trialkyl-1-adamantanammonium cation is more preferred. The three alkyl groups in the case of the N, N, N-trialkyl-1-adamantanammonium cation are three independent alkyl groups, usually lower alkyl groups, preferably methyl groups. Specifically preferred is the N, N, N-trimethyl-1-adamantanammonium cation. Such cations are accompanied by anions that do not harm the formation of CHA-type zeolite. Representative examples of such anions include halogen ions such as Cl ⁻ , Br ⁻ and I ⁻ , hydroxide ions, acetates, sulfates, and carboxylates. Hydroxide ions are particularly preferably used. As other organic templates, N, N, N-trialkylbenzylammonium cations can also be used. Again, alkyl is three independent alkyls, usually lower alkyl. Preferably it is methyl. Most preferred is the N, N, N-trimethylbenzylammonium cation.

As the alkali source used in the reaction mixture, a hydroxide ion of a counter anion of an organic template, an alkali metal hydroxide such as NaOH or KOH, an alkaline earth metal hydroxide such as Ca (OH) ₂ or the like is used. it can.
The type of alkali is not particularly limited, but is usually Na, K, Li, Rb, Cs, Ca, Mg, Sr, Ba, preferably Na, K, and more preferably K. Two or more alkalis may be used in combination, and specifically, Na and K are preferably used in combination.

The ratio of the Si element source and Al element source in the reaction mixture is typically the molar ratio of the oxides of the respective _elements, sometimes referred to SiO 2 / _Al 2 _{O 3} molar ratio (hereinafter simply _SiO 2 / _Al 2 _{O 3} ratio .) The SiO ₂ / Al ₂ O ₃ ratio is 5 or more, preferably 8 or more from the viewpoint that a CHA-type zeolite membrane can be densely formed, more preferably 10 or more, and still more preferably 15 or more. . Moreover, it is 10,000 or less normally, Preferably it is 1000 or less, More preferably, it is 300 or less, More preferably, it is 100 or less.

When the SiO ₂ / Al ₂ O ₃ ratio is within this range, a CHA-type zeolite membrane is preferable because it can be densely formed. Further, the produced CHA-type zeolite exhibits strong hydrophilicity, and is hydrophilic from a mixture containing organic matter. It is preferable at the point which can selectively permeate | transmit the compound of this, especially water. Further, a CHA-type zeolite that is strong in acid resistance and difficult to remove from Al is obtained. In addition to Al, other elements such as Ga, Fe, B, Ti, Zr, Sn, Zn and the like may be included.

When the SiO ₂ / Al ₂ O ₃ ratio is in this range, CHA-type zeolite that can form a dense film is crystallized, which is preferable. Further, it is preferable in that a CHA-type zeolite having hydrophilicity sufficient for the membrane to selectively permeate water can be produced and a CHA-type zeolite excellent in acid resistance can be obtained.

The ratio of the silica source and an organic template in the reaction mixture, the molar ratio of the organic template for SiO ₂ as (organic template / SiO ₂ ratio) is usually 0.005 or more and 1 or less, preferably 0.01 or more 0.4 Hereinafter, it is more preferably 0.02 or more and 0.2 or less. In addition to being able to produce a dense CHA-type zeolite membrane within this range, the produced CHA-type zeolite has strong acid resistance and Al is not easily desorbed.

The ratio of the Si element source to the alkali source is expressed as M _{(2 / n) 2} O / SiO ₂ molar ratio when the alkali metal or alkaline earth metal is represented by M and the valence is represented by n (1 or 2). Usually, it is 0.02 or more and 0.5 or less, preferably 0.04 or more and 0.4 or less, more preferably 0.05 or more and 0.3 or less.

  Further, the case where K is contained in the alkali metal is preferable in terms of forming a denser and higher crystalline film. In this case, the molar ratio of K to all alkali metals and / or alkaline earth metals containing K is usually 0.01-1, preferably 0.1-1, and more preferably 0.3-1. is there. In addition, the addition of K can be done by changing the space group by rhomboborealsetting.

(No. 166), the peak intensity around 2θ = 9.6 °, which is a peak derived from the (1, 0, 0) index in the CHA structure, or the (1, 1, 1) surface. There is a tendency to increase the ratio of the peak intensity in the vicinity of 2θ = 17.9 ° which is the peak derived from the peak intensity in the vicinity of 2θ = 20.8 ° which is the peak derived from the (2, 0, −1) plane. is there.

The ratio of Si element source to water is usually 10 or more and 1000 or less, preferably 30 or more and 500 or less, more preferably 40 or more and 200 or less, and particularly preferably 50 or more and 150 or less, as the molar ratio of water to SiO ₂ . . When the molar ratio of the substances in the reaction mixture is within these ranges, a dense CHA-type zeolite membrane can be formed. The amount of water is particularly important in the production of a dense CHA-type zeolite membrane, and fine crystals are more likely to be produced under conditions where the amount of water is greater than that of the general powder synthesis method. There is a tendency. The amount of water when synthesizing the powdered CHA-type zeolite is generally about 15-50 as the H ₂ O / SiO ₂ molar ratio, but the H ₂ O / SiO ₂ molar ratio is high. It is preferable to use a large number of conditions. Specifically, when the conditions are 50 or more and 150 or less, the CHA-type zeolite is crystallized into a dense membrane on the surface of the inorganic porous support, and a membrane composite having high separation performance is obtained. It is preferable at the point obtained.

  Next, the manufacturing method of a composite_body | complex is demonstrated. In order to crystallize a membrane-like CHA-type zeolite that can be applied to separation of a gas or liquid mixture and can achieve a sufficient permeation flow rate on the surface of the support, the above document is simply applied as it is. However, it is not sufficient, and it is necessary to study various conditions for film formation from these methods.

  When the CHA zeolite is crystallized in the form of a film on the surface of the inorganic porous support in the present invention, the seed crystal may not be present, but the crystal of the CHA zeolite is added by adding the seed crystal in the reaction system. It is preferable in that it can be accelerated. There is no particular limitation on the method of adding the seed crystal, but the method of adding the seed crystal to the reaction mixture as in the synthesis of the powdered CHA-type zeolite or the method of attaching the seed crystal on the surface of the inorganic porous support. It is preferable to leave a seed crystal on the surface of the inorganic porous support as a method for producing the membrane composite. By attaching a seed crystal in advance to the surface of the support, a dense zeolite membrane with good separation performance can be easily formed.

  The seed crystal used in the present invention may be of any type as long as it is a zeolite that promotes crystallization, but is preferably a CHA-type zeolite for efficient crystallization. The CHA-type zeolite used as the seed crystal is not particularly limited, but it is desirable that the particle diameter is small, and it may be used after pulverization if necessary. Usually, it is 0.5 nm or more, preferably 1 nm or more, usually 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less.

  The method for attaching the seed crystal on the inorganic porous support in the present invention is not particularly limited, but the seed crystal is dispersed in a solvent such as water and the support is immersed in the dispersion to seed the seed crystal on the surface. There are a dipping method in which a seed crystal is adhered, and a method in which a seed crystal is mixed with a solvent such as water to form a slurry, and is coated on the surface of the inorganic porous support. The dip method is desirable for controlling the amount of seed crystals attached and producing a membrane composite with good reproducibility.

  In the present invention, the solvent in which the seed crystals are dispersed is not particularly limited, but water is preferable. The amount of the seed crystal to be dispersed is not particularly limited, but is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight with respect to the total weight of the dispersion. The above is preferable, usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 4% by weight or less, and particularly preferably 3% by weight or less. If the amount of seed crystals to be dispersed is too small, the amount of seed crystals adhering to the inorganic porous support will be small, so there may be a part where CHA-type zeolite is not partially formed on the support surface during hydrothermal synthesis. There is a possibility of becoming a film with. If the amount of seed crystals in the dispersion is too large, the amount of seed crystals adhering to the surface of the inorganic porous support by the dipping method will be almost constant, so if too much seed crystals are dispersed, the seed crystals will be wasted. It is more disadvantageous in terms of cost.

The inorganic porous support in the present invention is preferably synthesized after a seed crystal is attached by dipping or slurry coating and then dried.
The weight of the seed crystal to be attached in advance on the surface of the support is not particularly limited, but is usually 0.01 g or more, preferably 0.05 g or more, more preferably as the weight per 1 m ^{2 of the} substrate. Is 0.1 g or more, usually 100 g or less, preferably 50 g or less, more preferably 10 g or less, and still more preferably 8 g or less. When the amount of the seed crystal is less than the lower limit, it becomes difficult to form a crystal, and when the film growth becomes insufficient or the film growth tends to be uneven, a dense film is formed. It may be difficult. If the amount of the seed crystal exceeds the upper limit, the surface irregularities are increased by the seed crystal, or the seed crystal falling from the surface of the support easily grows spontaneous nuclei, thereby inhibiting the film growth on the support. In some cases, it is difficult to form a dense film.
In the case of crystallizing by hydrothermal synthesis, when the inorganic porous support is fixed, it can take any form such as vertical placement and horizontal placement. In this case, it may be crystallized by a stationary method or may be crystallized by stirring the reaction mixture.

  The temperature at which the zeolite is crystallized is not particularly limited, but is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and usually 200 ° C. or lower, preferably 190 ° C. Below, it is 180 degrees C or less more preferably. If the reaction temperature is too low, the CHA-type zeolite may be difficult to crystallize. When the reaction temperature is higher than this range, a zeolite different from the CHA type is likely to be produced.

  The heating time is not particularly limited, but is usually 1 hour or more, preferably 5 hours or more, more preferably 10 hours or more, usually 10 days or less, preferably 5 days or less, more Preferably it is 3 days or less, More preferably, it is 2 days or less. If the reaction time is too short, the CHA-type zeolite may be difficult to crystallize. If the reaction time is too long, a zeolite different from the CHA type may be easily formed.

  Although the pressure at the time of crystallization is not particularly limited, the self-generated pressure generated when the reaction mixture placed in a closed vessel is heated to this temperature range is sufficient, but an inert gas such as nitrogen is added. It doesn't matter.

The zeolite membrane composite obtained by hydrothermal synthesis is washed with water, then heated and dried. Here, the heat treatment means that the template is fired when heat is applied to dry the zeolite membrane composite or the template is used.
The temperature of the heat treatment is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, usually 200 ° C. or lower, preferably 150 ° C. or lower when drying is intended. The temperature of the heat treatment is usually 350 ° C. or higher, preferably 400 ° C. or higher, more preferably 430 ° C. or higher, more preferably 480 ° C. or higher, and usually 900 ° C. or lower, preferably 850 ° C. or lower, when the template is fired. More preferably, it is 800 ° C. or less, particularly preferably 750 ° C. or less. The heating time is not particularly limited as long as the zeolite membrane is sufficiently dried or the template is calcined, and preferably 0.5 hours or more, more Preferably it is 1 hour or more. The upper limit is not particularly limited, and is usually within 200 hours, preferably within 150 hours, and more preferably within 100 hours.
When hydrothermal synthesis is performed in the presence of an organic template, the obtained zeolite membrane composite can be washed with water, and then the organic template can be removed by, for example, heat treatment or extraction, preferably by heat treatment, that is, baking. Is appropriate.
The firing temperature is usually 350 ° C. or higher, preferably 400 ° C. or higher, more preferably 430 ° C. or higher, more preferably 480 ° C. or higher, usually 900 ° C. or lower, preferably 850 ° C. or lower, more preferably 800 ° C. or lower, particularly preferably Is 750 ° C. or lower. If the calcination temperature is too low, the proportion of the remaining organic template tends to increase, and the pores of the zeolite are small, which may reduce the permeation flux during separation and concentration. If the calcination temperature is too high, the difference in the coefficient of thermal expansion between the support and the zeolite will be large, so the zeolite membrane may be prone to cracking, and the denseness of the zeolite membrane will be lost, leading to poor separation performance. Sometimes.

  The firing time varies depending on the rate of temperature rise or the rate of temperature fall, but is not particularly limited as long as the organic template is sufficiently removed, but is preferably 1 hour or longer, more preferably 5 hours or longer. The upper limit is not particularly limited, but is, for example, usually within 200 hours, preferably within 150 hours, more preferably within 100 hours, and most preferably within 24 hours. The firing is generally performed in an air atmosphere, but can be performed in an atmosphere containing oxygen.

  It is desirable that the rate of temperature increase during firing be as slow as possible in order to reduce the difference in the thermal expansion coefficient between the support and the zeolite from causing cracks in the zeolite membrane. Usually, it is 5 ° C./min or less, preferably 2 ° C./min or less, more preferably 1 ° C./min or less, particularly preferably 0.5 ° C./min or less. Usually, it is 0.1 ° C./min or more in consideration of workability. Moreover, it is necessary to control the temperature drop rate after firing in order to avoid cracks in the zeolite membrane. Similar to the rate of temperature increase, the slower the better. Usually, it is 5 ° C./min or less, preferably 2 ° C./min or less, more preferably 1 ° C./min or less, particularly preferably 0.5 ° C./min or less. Usually, it is 0.1 ° C./min or more in consideration of workability.

The inorganic porous support-zeolite membrane composite may be ion-exchanged as necessary. When ion exchange is performed using a template, the ion exchange is usually performed after removing the template such as baking. Ions to be ion-exchanged include protons, alkali metal ions such as Na ⁺ , K ⁺ and Li ⁺ , and alkaline earth metal ions such as Ca ²⁺ , Mg ²⁺ , Sr ²⁺ and Ba ²⁺ , Fe, Cu, Zn and the like Examples thereof include transition metal ions. Of these, protons and alkali metal ions such as Na ⁺ , K ⁺ and Li ⁺ are preferred.

As an ion exchange method, the inorganic porous support-zeolite membrane complex after calcination (such as when using a template) is mixed with an aqueous solution containing an ammonium salt such as NH ₄ NO ₃ or NaNO ₃ or an ion to be exchanged. Usually, it is treated with an acid such as hydrochloric acid at a temperature of room temperature to 100 ° C., washed with water, and calcined at 200 ° C. to 500 ° C. as necessary.

  The shape of the zeolite membrane composite used in the present invention is not particularly limited, and any shape such as a tubular shape, a hollow fiber shape, a monolith type, and a honeycomb type can be adopted. Although the size is not particularly limited, for example, in the case of a tubular shape, a length of 2 cm to 200 cm, an inner diameter of 0.5 cm to 2 cm, and a thickness of 0.5 mm to 4 mm are practical and preferable.

  Next, for reference, the overall separation / concentration function of the inorganic porous support-zeolite membrane composite used in the present invention will be described. This function is achieved by bringing a gas or liquid mixture containing an organic substance into contact with one side of the support side or the zeolite membrane side through an inorganic porous support provided with a zeolite membrane, and the side on which the mixture is in contact on the opposite side. This is a function of selectively permeating a substance (a substance having a high permeability in the mixture) that is permeable to the zeolite membrane from the mixture by setting a lower pressure. Thereby, a highly permeable substance can be separated from the mixture. As a result, the specific organic substance is separated and recovered or concentrated by increasing the concentration of the specific organic substance (substance having low permeability in the mixture) in the mixture containing the organic substance. Specifically, in the case of a mixture of water and organic matter, since water is usually highly permeable to the zeolite membrane, water and organic matter are separated from the mixture, and the organic matter is concentrated in the original mixture. The separation / concentration method called pervaporation and vapor permeation is one form.

  One of the separation functions of the zeolite membrane composite used in the present invention is separation as a molecular sieve. In the case of CHA-type zeolite, gas molecules or liquid molecules having an effective pore diameter of 3.8 mm or more and those molecules It is preferably used for separation from the following gas or liquid molecules. There is no upper limit to the molecules used for separation, but the size of the molecules is usually about 100 mm or less.

Another separation function of the zeolite membrane composite used in the present invention is separation utilizing the difference in hydrophilicity. Although depending on the type of zeolite, a hydrophilic property generally appears when a certain amount of Al is contained in the zeolite framework. By controlling the crystallization conditions of the zeolite membrane, it is possible to control the SiO ₂ / Al ₂ O ₃ molar ratio in the crystal. If such a hydrophilic membrane is used, the organic matter can be separated and concentrated by selectively allowing water molecules to permeate through a mixed solution of the organic matter and water. That is, organic acids / water, alcohols / water, ketones / water such as acetone and methyl isobutyl ketone, aldehydes / water, ethers such as dioxane and tetrahydrofuran, amides such as dimethylformamide and N-methylpyrrolidone, etc. The organic substance can be separated and concentrated by selectively permeating water from a mixed aqueous solution of the organic substance and water, such as organic compounds containing nitrogen (N-containing organic substance) / water, esters such as acetate ester / water, and the like. In this case, the content of water in the mixture of the organic substance and water is not particularly limited, and the structure is broken even in a mixture having a high water content, for example, a water content of 20% by weight or more, in which the structure is broken in the A-type zeolite. High selectivity and transmission performance can be achieved without any problems.
The high permeation performance here indicates a sufficient throughput, for example, a mixture of 2-propanol and water having a permeation flux of a substance that permeates the membrane (water in the present invention), for example, a water content of 30% by weight. Is transmitted at a temperature difference of 70 ° C. and a pressure difference of 1 atm (1.01 × 10 ⁶ Pa), 1 kg / (m ² × h) or more, preferably 3 kg / (m ² × h) or more, more preferably Means 5 kg / (m ² × h) or more. The upper limit of the permeation flux is not particularly limited, and is usually 20 kg / (m ² × h) or less, preferably 5 kg / (m ² × h) or less.
Further, in systems other than organic acid / water, even in the presence of an organic acid or an inorganic acid, it can be used because of its high acid resistance.

  The present invention utilizes the separation / concentration function for the alcohols / water system in the separation / concentration function.

  Thus, the zeolite membrane composite of the present invention can realize high selectivity and permeation amount even in separation from a mixture with an organic substance having a high water content or separation under acidic conditions. Therefore, by separating the mixture usually separated by distillation using the zeolite membrane composite of the present invention, energy required for separation can be reduced as compared with distillation. Since the zeolite membrane composite of the present invention can be separated from a mixture having a wide range of water content, it can be separated even in a system that has not been possible so far. For example, since the A-type zeolite membrane could not be separated from a mixture with an organic substance having a high water content, it is necessary to concentrate the organic substance to about 90% by distillation before using the A-type zeolite membrane. there were. However, if the zeolite membrane composite of the present invention is used, water and organic matter can be separated and the organic matter can be concentrated even from a mixture with an organic matter having a high water content of, for example, 50% or more.

  Hereinafter, the present invention will be described more specifically based on reference examples and examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

-X-ray diffraction (XRD) measurement method XRD measurement was performed based on the following conditions.
Device name: X'PertPro MPD manufactured by PANalytical, the Netherlands
Optical system specifications Incident side: Enclosed X-ray tube (CuKα)
Soller Slit (0.04 rad)
Divergence Slit (Variable Slit)
Sample stage: XYZ stage
Light receiving side: Semiconductor array detector (X 'Celerator)
Ni-filter
SolarSlit (0.04 rad)
Goniometer radius: 240mm
Measurement conditions X-ray output (CuKα): 45 kV, 40 mA
Scanning axis: θ / 2θ
Scanning range (2θ): 5.0-70.0 °
Measurement mode: Continuous
Reading width: 0.05 °
Counting time: 99.7 sec
Automatic variable slit (Automatic-DS): 1 mm (irradiation width)
Horizontal divergence mask: 10 mm (irradiation width)
X-rays were irradiated in a direction perpendicular to the axial direction of the cylindrical tube. Also, the X-ray is not the sample table surface, but the sample table surface, out of the two lines where the cylindrical tubular membrane complex placed on the sample table and the plane parallel to the sample table surface are in contact with each other so that noise and the like are not introduced as much as possible. It was made to hit mainly on the other line above the surface.

・ Measurement method of SEM-EDX Equipment:
SEM: FE-SEM Hitachi: S-4800
EDX: EDAX Genesis
Acceleration voltage: 10 kV
The entire field of view (25 μm × 18 μm) at a magnification of 5000 was scanned, and X-ray quantitative analysis was performed.

Reference example 1:
In order to prepare a CHA type zeolite membrane, an aqueous solution of N, N, N-trimethyl-1-adamantanammonium hydroxide (TMADAOH) was prepared with reference to the description in USP 4,454,538. An example is shown below.
5.5 g of 1-adamantanamine (manufactured by Aldrich) was dissolved in 75 ml of methanol, 24.2 g of potassium carbonate was added, and the mixture was stirred for 30 minutes. To this, 10 ml of iodomethane was added dropwise and stirred for one day. Thereafter, 50 ml of methylene chloride was added and the solid was filtered. The solvent of the obtained solution was removed by an evaporator to obtain a solid. To this solid, 130 ml of methylene chloride was added, and filtration and removal of the solvent were repeated twice. Thereafter, the obtained solid was recrystallized using methanol, and the recrystallized solid was filtered, washed with diethyl ether, dried and dried to give N, N, N-trimethyl-1-adamantanammonium iodide (TMADI). ) Thereafter, this TMADI was dissolved in water, ion-exchanged with an anion exchange resin (SA-10A manufactured by Mitsubishi Chemical Corporation), and concentrated with an evaporator to obtain an aqueous solution of N, N, N-trimethyl-1-adamantanammonium hydroxide. By titration, the concentration of N, N, N-trimethyl-1-adamantanammonium hydroxide in this aqueous solution was 0.75 mmol / g. The amount of K contained in this aqueous solution was 1.84% by weight.

The inorganic porous support- (CHA type) zeolite membrane composite was prepared by hydrothermal synthesis of CHA type zeolite directly on the inorganic porous support.
The following was prepared as a reaction mixture for hydrothermal synthesis.
To a mixture of 6.9 g of 1 mol / L-NaOH aqueous solution and 103.6 g of water, 0.43 g of aluminum hydroxide (containing 53.5% by weight of Al ₂ O ₃ , manufactured by Aldrich) was added, stirred and dissolved, and transparent It was set as the solution. To this was added 9.2 g of the above-mentioned N, N, N-trimethyl-1-adamantanammonium hydroxide (TMADAOH) aqueous solution (containing 0.17 g as K in the solution) as an organic template, and further colloidal. 10.4 g of silica (Snowtech-40 manufactured by Nissan Chemical Co., Ltd.) was added and stirred for 3 hours to prepare a hydrothermal synthesis mixture.

As an inorganic porous support, a mullite tube PM (external diameter: 12 mm, internal diameter: 9 mm) manufactured by Nikkato Co., Ltd. was cut to a length of 80 mm, and the outer surface was smoothed using water-resistant sandpaper. What was dried after washing with a washing machine was used. Prior to hydrothermal synthesis on the support, SiO ₂ / Al ₂ O ₃ / NaOH / H ₂ O / TMADAOH = 1 / 0.033 / 0.140 / by the dip method in the same manner as described above. A CHA-type zeolite seed crystal of about 0.5 μm, which was crystallized by hydrothermal synthesis at 160 ° C. for 2 days with a gel composition of 0.1, was attached.

The support was immersed in a dispersion of the seed crystal in about 1% by weight of water for a predetermined time, and then dried at 100 ° C. for 5 hours or more to adhere the seed crystal. The weight of the attached seed crystal was about 3 g / m ² . The support to which the seed crystal was attached was immersed in a Teflon (registered trademark) inner cylinder containing the reaction mixture in the vertical direction, the autoclave was sealed, and heated at 160 ° C. for 48 hours under an autogenous pressure. After the elapse of a predetermined time, after cooling, the support-zeolite membrane composite was taken out of the reaction mixture, washed, and dried at 100 ° C. for 5 hours or more. After drying, seal one end of the cylindrical tubular membrane composite in a state of zeolite before template firing (hereinafter sometimes referred to as as-made), and connect the other end to a vacuum line to reduce the pressure inside the tube. When the amount of air permeation was measured with a flow meter installed in a vacuum line, the amount of permeation was 0 ml / (m ² · min).
The zeolite (as-made) membrane composite before template firing was fired in an electric furnace at 550 ° C. for 10 hours. At this time, the rate of temperature increase and the rate of temperature decrease were both 0.5 ° C./min. From the difference between the weight of the membrane composite after firing and the weight of the support, the weight of the CHA-type zeolite crystallized on the support was 120 g / m ² . From SEM observation, the film thickness was about 15 μm.

  When XRD of the produced membrane was measured, it was found that CHA-type zeolite was produced. XRD measurement was performed under the above conditions. The irradiation width is fixed to 1 mm by an automatic variable slit, and XRD pattern is converted by variable slit → fixed slit conversion using XRD analysis software JADE 7.5.2 (Japanese version) of MaterialsData, Inc. Obtained. (Intensity of peak near 2θ = 17.9 °) / (Intensity of peak near 2θ = 20.8 °) = 2.9, and orientation to the (1,1,1) plane in rhombohedral setting is estimated It was done.

Moreover, as a result of observing the inorganic porous support-CHA type zeolite membrane composite cut into strips by SEM, crystals were densely formed on the surface.
Further, by SEM-EDX, was measured _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane was 22.
Reference example 2:
The inorganic porous support CHA-type zeolite membrane composite was prepared by hydrothermal synthesis of CHA-type zeolite directly on the inorganic porous support.

The following was prepared as a reaction mixture for hydrothermal synthesis.
A mixture of 10.5 g of 1 mol / L-NaOH aqueous solution, 7.0 g of 1 mol / L-KOH aqueous solution and 100.0 g of water was mixed with aluminum hydroxide (containing 53.5% by weight of Al ₂ O ₃ , manufactured by Aldrich). 88 g was added, stirred and dissolved to obtain a transparent solution. As an organic template, 2.95 g of an aqueous N, N, N-trimethyl-1-adamantanammonium hydroxide (TMADAOH) solution (containing 25% by weight of TMADAOH, manufactured by Seychem) was added, and colloidal silica (Snowtech, manufactured by Nissan Chemical Co., Ltd.) was added. −40) 10.5 g was added and stirred for 2 hours to prepare a hydrothermal synthesis mixture.

As the inorganic porous support, one treated in the same manner as in Reference Example 1 was used. Prior to hydrothermal synthesis, a CHA-type zeolite seed crystal having a particle size of about 0.5 μm was deposited on the support in the same manner as in Reference Example 1. The weight of the attached seed crystal was about 5 g / m ² .
As in Reference Example 1, the support on which the seed crystal was adhered was immersed vertically in a Teflon (registered trademark) inner cylinder containing the reaction mixture, and the autoclave was sealed, and the autoclave was sealed at 160 ° C. for 48 hours under an autogenous pressure. And heated. After the elapse of a predetermined time, after cooling, the support-zeolite membrane composite was taken out of the reaction mixture, washed, and dried at 100 ° C. for 5 hours or more. Seal one end of the cylindrical tubular membrane composite in an as-made state after drying, and connect the other end to a vacuum line to reduce the pressure inside the tube. When measured, the permeation amount was 0 ml / (m ² · min). The zeolite membrane composite before template firing was fired in an electric furnace at 500 ° C. for 5 hours. From the difference between the weight of the membrane composite after firing and the weight of the support, the weight of the CHA-type zeolite crystallized on the support was 120 g / m ² . From SEM observation, the film thickness was about 15 μm.

  When XRD of the produced zeolite membrane was measured, it was found that CHA-type zeolite was produced. XRD measurement was performed in the same manner as in Reference Example 1. Comparison of XRD of the produced membrane and XRD of SSZ-13 which is a powdered CHA type zeolite (zeolite generally referred to as SSZ-13 in US Pat. No. 4,544,538, hereinafter referred to as SSZ-13) used as a seed crystal. As shown in FIG. In FIG. 5, a) shows the XRD of SSZ-13, and b) shows the XRD of SSZ-13. Moreover, * in a figure is a peak derived from a support body. In the XRD of the produced film, it can be seen that the intensity of the peak in the vicinity of 2θ = 17.9 ° is significantly larger than that of SSZ-13, which is a powdered CHA-type zeolite. For the powdered CHA-type zeolite SSZ-13 (peak intensity around 2θ = 17.9 °) / (peak intensity around 2θ = 20.8 °) = 0.2, 2θ = 17.9 ° peak intensity) / (2θ = 20.8 ° peak intensity) = 12.6, and the orientation to the (1,1,1) plane in rhombohedral setting is estimated. It was.

Further, by SEM-EDX, was measured _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane was 17.

Reference Example 3:
The inorganic porous support-CHA type zeolite membrane composite was prepared by hydrothermal synthesis of CHA type zeolite directly on the inorganic porous support.

The following was prepared as a reaction mixture for hydrothermal synthesis.
A mixture of 10.5 g of 1 mol / L-NaOH aqueous solution, 7.0 g of 1 mol / L-KOH aqueous solution and 100.4 g of water was mixed with aluminum hydroxide (containing 53.5% by weight of Al ₂ O ₃ , manufactured by Aldrich). 88 g was added, stirred and dissolved to obtain a transparent solution. As an organic template, 2.37 g of an aqueous solution of N, N, N-trimethyl-1-adamantanammonium hydroxide (TMADAOH) (containing 25% by weight of TMADAOH, manufactured by Seychem) was added, and colloidal silica (Snowtech manufactured by Nissan Chemical Co., Ltd.) was added. −40) 10.5 g was added and stirred for 2 hours to prepare a hydrothermal synthesis mixture.

As the inorganic porous support, one treated in the same manner as in Reference Example 1 was used. Prior to hydrothermal synthesis, a CHA-type zeolite seed crystal having a particle size of about 2 μm was deposited on the support in the same manner as in Reference Example 1. The weight of the attached seed crystal was about 2 g / m ² . The CHA-type zeolite having a particle size of about 2 μm used for the seed crystal is an SiO ₂ / Al ₂ O ₃ solution using a 25 wt% N, N, N-trimethyl-1-adamantanammonium hydroxide (TMADAOH) aqueous solution manufactured by Seychem. / NaOH / KOH / H ₂ O / TMADAOH = 1 / 0.066 / 0.15 / 0.1 / 100 / 0.1 gel composition hydrothermally synthesized for 2 days at 160 ° C. Filtered, washed with water and dried.
As in Reference Example 1, the support on which the seed crystal was adhered was immersed vertically in a Teflon (registered trademark) inner cylinder containing the reaction mixture, and the autoclave was sealed, and the autoclave was sealed at 160 ° C. for 48 hours under an autogenous pressure. And heated. After the elapse of a predetermined time, after cooling, the support-zeolite membrane composite was taken out of the reaction mixture, washed, and dried at 100 ° C. for 5 hours or more. Seal one end of the cylindrical tubular membrane composite in an as-made state after drying, and connect the other end to a vacuum line to reduce the pressure inside the tube. When measured, the permeation amount was 0 ml / (m ² · min). The zeolite membrane composite before template firing was fired in an electric furnace at 500 ° C. for 5 hours. From the difference between the weight of the membrane composite after firing and the weight of the support, the weight of the CHA-type zeolite crystallized on the support was 130 g / m ² .

  When XRD of the produced membrane was measured, it was found that CHA-type zeolite was produced. XRD measurement was performed in the same manner as in Reference Example 1. From the result of XRD of the formed film, it can be seen that the intensity of the peak around 2θ = 17.9 ° is remarkably high. It was (the intensity of the peak around 2θ = 17.9 °) / (the intensity of the peak around 2θ = 20.8 °) = 1.0.

Further, by SEM-EDX, was measured _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane was 20.

Reference example 4:
An inorganic porous support-CHA-type zeolite membrane composite was prepared in the same manner as in Reference Example 3 except that a porous alumina tube (outer diameter 12 mm, inner diameter 9 mm) was used as the inorganic porous support.
From the result of XRD of the produced CHA-type zeolite membrane, it was found that (the intensity of the peak near 2θ = 17.9 °) / (the intensity of the peak near 2θ = 20.8 °) = 1.2. Further, by SEM-EDX, was measured _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane was 17.

Reference example 5:
The inorganic porous support-CHA type zeolite membrane composite was prepared by hydrothermal synthesis of CHA type zeolite directly on the inorganic porous support.

The following was prepared as a reaction mixture for hydrothermal synthesis.
To a mixture of 32 g of 1 mol / L-NaOH aqueous solution, 48 g of 1 mol / L-KOH aqueous solution and 457 g of water, 4.0 g of aluminum hydroxide (containing 53.5% by weight of Al ₂ O ₃ , manufactured by Aldrich) was added and stirred. Dissolved to give a nearly clear solution. As an organic template, 13.5 g of an N, N, N-trimethyl-1-adamantanammonium hydroxide (TMADAOH) aqueous solution (containing 25% by weight of TMADAOH, manufactured by Seychem) was added, and colloidal silica (Snowtech, manufactured by Nissan Chemical Co., Ltd.) was added. −40) 48 g was added and stirred for 2 hours to prepare a hydrothermal synthesis mixture.

As the inorganic porous support, one treated in the same manner as in Reference Example 1 was used. Prior to hydrothermal synthesis, the same treatment as in Reference Example 1 was performed except that a seed crystal of CHA-type zeolite having a particle size of about 2 μm was deposited on the support. The weight of the attached seed crystal was about 5 g / m ² .
As in Reference Example 1, the support to which the seed crystal was attached was immersed in a Teflon (registered trademark) inner cylinder containing the reaction mixture in the vertical direction, and the Teflon (registered trademark) inner cylinder was immersed in 1 L of stainless steel. The autoclave was put into a manufactured autoclave, and the autoclave was sealed and heated for 5 hours, and then heated at 160 ° C. for 48 hours under autogenous pressure. During the reaction, the reaction mixture was mixed with a stirring blade rotating at 200 rpm. After the elapse of a predetermined time, after cooling, the support-zeolite membrane composite was taken out of the reaction mixture, washed, and dried at 100 ° C. for 4 hours or more. Seal one end of the cylindrical tubular membrane composite in an as-made state after drying, and connect the other end to a vacuum line to reduce the pressure inside the tube. When measured, the permeation amount was 0 ml / (m ² · min). The zeolite membrane composite before template firing was fired in an electric furnace at 500 ° C. for 5 hours. From the difference between the weight of the membrane composite after firing and the weight of the support, the weight of the CHA-type zeolite crystallized on the support was 120 g / m ² .

When XRD of the produced membrane was measured, it was found that CHA-type zeolite was produced. XRD measurement was performed in the same manner as in Reference Example 1. The XRD of the produced film is shown in FIG. * In the figure is a peak derived from the support.
In the XRD of the formed film, it can be seen that the intensity of the peak in the vicinity of 2θ = 9.6 ° is significantly larger than that of SSZ-13, which is a powdered CHA-type zeolite. The intensity (peak intensity around 2θ = 9.6 °) / (peak intensity around 2θ = 20.8 °) = 6.8 of the produced film and COLLECTION OF SIMULATED XRD POWTERNS FORZEOLITE Third Revised Edition 1996 The ratio of XRD of CHA of the powder ((peak intensity around 2θ = 9.6 °) / (peak intensity around 2θ = 20.8 °) = 2.5, which is significantly larger than the (1 in the rhombohedral setting). The orientation to the (0,0) plane was estimated, and the SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite membrane was measured by SEM-EDX and found to be 17.

Reference Example 6:
The inorganic porous support-CHA type zeolite membrane composite was prepared by hydrothermal synthesis of CHA type zeolite directly on the inorganic porous support.

The following was prepared as a reaction mixture for hydrothermal synthesis.
To a mixture of 30.1 g of 1 mol / L-NaOH aqueous solution and 66.0 g of water was added 0.057 g of aluminum hydroxide (containing 53.5% by weight of Al ₂ O ₃ , manufactured by Aldrich) and dissolved by stirring. A clear solution was obtained. As an organic template, 12.7 g of an N, N, N-trimethyl-1-adamantanammonium hydroxide (TMADAOH) aqueous solution (containing 25% by weight of TMADAOH, manufactured by Seychem) was added, and colloidal silica (Snowtech manufactured by Nissan Chemical Co., Ltd.) was added. −40) 23.6 g was added and stirred for 2 hours to prepare a hydrothermal synthesis mixture.

As the inorganic porous support, one treated in the same manner as in Reference Example 1 was used. Prior to hydrothermal synthesis, a CHA-type zeolite seed crystal of about 0.5 μm was deposited on the support in the same manner as in Reference Example 1. The weight of the attached seed crystal was about 3 g / m ² .
As in Reference Example 1, the support on which the seed crystal was adhered was immersed in a Teflon (registered trademark) inner cylinder containing the reaction mixture in the vertical direction, and the autoclave was sealed. And heated. After the elapse of a predetermined time, after cooling, the support-zeolite membrane composite was taken out of the reaction mixture, washed, and dried at 100 ° C. for 4 hours or more. Seal one end of the cylindrical tubular membrane composite in an as-made state after drying, and connect the other end to a vacuum line to reduce the pressure inside the tube. When measured, the permeation amount was 0 ml / (m ² · min). The zeolite membrane composite before template firing was fired in an electric furnace at 500 ° C. for 5 hours. From the difference between the weight of the membrane composite after firing and the weight of the support, the weight of the CHA zeolite crystallized on the support was 100 g / m ² .

When XRD of the produced membrane was measured, it was found that CHA-type zeolite was produced. XRD measurement was performed in the same manner as in Reference Example 1. The XRD of the resulting film is shown in FIG. * In the figure is a peak derived from the support.
In the XRD of the film formed, (peak intensity around 2θ = 9.6 °) / (peak intensity around 2θ = 20.8 °) = 1.7, (peak near 2θ = 17.9 °) Intensity) / (peak intensity around 2θ = 20.8 °) = 0.3.

Thus, none of the films produced showed a specific intensity in the XRD peak. From this, for example, it is presumed that the generated film is not oriented in any of the (1, 0, 0) plane and the (1, 1, 1) plane in rhombohedral setting.
Further, by SEM-EDX, tried to measure the _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane, since the _SiO 2 / _Al 2 _{O 3} molar ratio of the reaction mixture of the starting is 500 zeolite film SiO _{Since the 2} / Al ₂ O ₃ molar ratio was also very high, an accurate value could not be obtained. Zeolite membrane SEM-EDX In _general, since the measurement limit value of SiO 2 / _Al 2 _{O 3} molar ratio is considered to be about 100, when at least _SiO 2 / _Al 2 _{O 3} molar ratio of this zeolite membrane is more than 100 Guessed.

Example 1:
Using the inorganic porous support-CHA-type zeolite membrane composite obtained in Reference Example 4 to selectively permeate water from a 70 ° C. water / 2-propanol aqueous solution (30/70 wt%) by a pervaporation method. Separation was performed.

  The apparatus shown in FIG. 4 was used for the pervaporation method. In FIG. 4, the inside of the zeolite membrane composite (105) is depressurized by the vacuum pump (109), and the pressure difference is about 1 atm with the outside where the liquid to be separated (104) is in contact. Due to this pressure difference, the permeated water in the liquid to be separated (104) permeates and permeates through the zeolite membrane composite (105). The permeated material is collected by the trap (107). On the other hand, 2-propanol stays outside the zeolite membrane (105). The concentration of the liquid to be separated (104) was measured at regular intervals, and the separation factor for each time was calculated using the concentration. In FIG. 4, reference numeral (101) represents a stirrer, (102) represents a hot water bath, (103) represents a stirrer, (106) represents a Pirani gauge, and (108) represents a cold trap.

The composition analysis of the permeate collected in the trap and the liquid to be separated was performed by gas chromatography. Since it stabilizes in about 5 hours from the start of transmission, the transmission results after about 5 hours are shown.
The permeation flux was 7.7 kg / (m ² · h), the separation factor was 3000, and the concentration of water in the permeate was 99.92% by weight. The measurement results are shown in Table 1.

Reference example 7:
An inorganic porous support-CHA type zeolite membrane composite was prepared in the same manner as in Reference Example 2 except that the following was prepared as a reaction mixture for hydrothermal synthesis. The reaction mixture used for the hydrothermal synthesis was a mixture of 12.9 g of 1 mol / L-NaOH aqueous solution, 8.6 g of 1 mol / L-KOH aqueous solution and 92.4 g of water, and aluminum hydroxide (Al ₂ O ₃ 53 1.16 g (containing 5% by weight, manufactured by Aldrich Co., Ltd.) was added and stirred to dissolve it to obtain a substantially transparent solution. As an organic template, N, N, N-trimethyl-1-adamantanammonium hydroxide (TMADAOH) aqueous solution 2.91 g (containing 25% by weight of TMADAOH, manufactured by Sechem Co.) was added, and 12.9 g of colloidal silica (Snowtech-40 manufactured by Nissan Chemical Co., Ltd.) was further added and stirred for 2 hours to prepare. From the difference between the weight of the obtained membrane composite after firing and the weight of the support, the weight of the CHA zeolite crystallized on the support was 150 g / m ² .
XRD measurement was performed in the same manner as in Reference Example 1.
It was (the intensity of the peak near 2θ = 9.6 °) / (the intensity of the peak near 2θ = 20.8 °) = 12.8.
Further, by SEM-EDX, was measured _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane was 15.

Example A :
Using the inorganic porous support-CHA-type zeolite membrane composite obtained in the same manner as in Reference Example 2, a 70 ° C. water / 2-propanol solution (10/90 wt. %) To selectively permeate water.
The permeation flux was 4.0 kg / (m ² · h), the separation factor was 36000, and the concentration of water in the permeate was 99.97% by weight. The measurement results are shown in Table 1.

Example 2:
Using the inorganic porous support-CHA type zeolite membrane composite obtained in the same manner as in Reference Example 2, a water / 2-propanol solution (30/70 wt. %) To selectively permeate water.
The permeation flux was 5.8 kg / (m ² · h), the separation factor was 31000, and the concentration of water in the permeate was 99.99 wt%. The measurement results are shown in Table 1.

Example 3:
Using an inorganic porous support-CHA type zeolite membrane composite obtained in the same manner as in Reference Example 2, a 50 / 2C water / 2-propanol solution (30/70 wt.%) Was obtained by the pervaporation method in the same manner as in Example 1. %) To selectively permeate water.
The permeation flux was 2.5 kg / (m ² · h), the separation factor was 29000, and the concentration of water in the permeate was 99.99 wt%. The measurement results are shown in Table 1.

Example 4:
Using the inorganic porous support-CHA type zeolite membrane composite obtained in the same manner as in Reference Example 2, a 70 ° C. water / ethanol solution (86/14 wt%) was obtained by the pervaporation method in the same manner as in Example 1. Separation allowing selective permeation of water was performed.
The permeation flux was 1.3 kg / (m ² · h), the separation factor was 500, and the concentration of water in the permeate was 99.97% by weight. The measurement results are shown in Table 1.

Reference Example 8:
The inorganic porous support-CHA type zeolite membrane composite was prepared by hydrothermal synthesis of CHA type zeolite directly on the inorganic porous support.
The following was prepared as a reaction mixture for hydrothermal synthesis.
To 126 g of 1 mol / L-KOH aqueous solution, 5.7 g of aluminum hydroxide (containing 53.5% by weight of Al ₂ O ₃ , manufactured by Aldrich) was added and dissolved by stirring to obtain a substantially transparent solution. To this was added 27 g of colloidal silica (Snowtech-40, Nissan Chemical Co., Ltd.) and stirred for 2 hours to prepare a mixture for hydrothermal synthesis.

As the inorganic porous support, one treated in the same manner as in Reference Example 1 was used. Prior to hydrothermal synthesis, a CHA-type zeolite seed crystal of about 0.2 μm was deposited on the support in the same manner as in Reference Example 1. The weight of the attached seed crystal was about 3 g / m ² .
The seed crystal of about 0.2 μm of CHA type zeolite was synthesized as follows. 10 g of Y-type zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 7 manufactured by Catalyst Kasei Co., Ltd. was added to an aqueous solution in which 5 g of KOH was dissolved in 100 g of water, and the mixture was stirred for 2 hours. The reaction mixture was placed in a Teflon (registered trademark) inner cylinder, the autoclave was sealed, and the mixture was heated at 100 ° C. for 7 days. Then, it was allowed to cool, filtered and washed with water to obtain a CHA type zeolite.
As in Reference Example 1, the support on which this seed crystal was attached was immersed in a Teflon (registered trademark) inner cylinder containing the above reaction mixture in the vertical direction, and the autoclave was sealed. And heated. After the elapse of a predetermined time, after cooling, the support-zeolite membrane composite was taken out of the reaction mixture, washed, and dried at 100 ° C. for 4 hours or more. Seal one end of the cylindrical tubular membrane composite in an as-made state after drying, and connect the other end to a vacuum line to reduce the pressure inside the tube. When measured, the permeation amount was 0 ml / (m ² · min). From the difference between the weight of the membrane composite and the weight of the support, the weight of the CHA-type zeolite crystallized on the support was 50 g / m ² .

  When XRD of the produced membrane was measured, it was found that CHA-type zeolite was produced. In the XRD of the film formed, (peak intensity near 2θ = 9.6 °) / (peak intensity near 2θ = 20.8 °) = 0.3, and (peak near 2θ = 17.9 °) Intensity) / (peak intensity around 2θ = 20.8 °) = 0.1.

Thus, none of the films produced showed a specific intensity in the XRD peak. From this, for example, it is presumed that the generated film is not oriented in any of the (1, 0, 0) plane and the (1, 1, 1) plane in rhombohedral setting.
Further, by SEM-EDX, was 6 was measured _SiO 2 / _Al 2 _{O 3} ratio of the zeolite membrane.

Example 5:
Using the inorganic porous support-CHA type zeolite membrane composite obtained in Reference Example 8 from a water / 2-propanol aqueous solution (30/70% by weight) at 70 ° C. by the pervaporation method as in Example 1. Separation with selective permeation of water was performed.
The permeation flux was 3.9 kg / (m ² · h), the separation factor was 21, and the concentration of water in the permeate was 90% by weight. The measurement results are shown in Table 1.

[simulation]
In order to confirm the effects of the present invention, various effects were simulated using the zeolite membrane used in the present invention. The simulation was performed using commercially available software ASPEN Plus Ver.7.2.

Example 6:
A simulation was performed using the data of the separation membrane of Reference Example 2 and the data shown in the material balance in FIG. The results are shown in Table 2.

  According to Example 6, when the purity is increased to some extent by distillation and dehydration is performed by the zeolite separation membrane (VP membrane), the mixture can be dehydrated to high purity more efficiently than the conventional technique.

1: First separation membrane module 2: Second separation membrane module 3: Cooler 4: Tank 10: Heating means 11: Heater 12: Evaporator 13: Heater 20: Heating means 21: Intermediate heater 51: Supply pump 52: Circulation pump 53: Circulation pump 54: Vacuum pump 55: Discharge pump 61-63: Pressure control valve 7: Pressure swing adsorption device 7a: First adsorption tower 7b: Second adsorption tower 71: Cooler 72: Cooler 101: Stirrer 102: Hot water bath 103: Stirrer 104: Liquid to be separated 105: Zeolite membrane complex 106: Pirani gauge 107: Trap for permeate collection 108: Cold trap 109: Vacuum pump

Claims (14)

Used to concentrate alcohol,
An inorganic porous support-zeolite membrane composite having a zeolite membrane containing a CHA-type zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 5 or more and 100 or less and having a thickness of 0.5 mm or more and an inner diameter of 0.5 cm or more A manufacturing method of
A reaction mixture containing a Si element source, an Al element source and an alkali source, and the above inorganic porous support is immersed in a reaction mixture in which the alkali source is a hydroxide of Na or K, and a zeolite membrane is formed by hydrothermal synthesis. Characterized by forming,
A method for producing an inorganic porous support-zeolite membrane composite.   The method for producing an inorganic porous support-zeolite membrane composite according to claim 1, wherein the zeolite membrane composite obtained by hydrothermal synthesis is subjected to heat treatment. The method for producing an inorganic porous support-zeolite membrane composite according to claim 1 or 2, wherein an inorganic porous support to which 0.1 to 8 g of seed crystal per 1 m ^{2 is} previously attached is immersed in the reaction mixture.   The method for producing an inorganic porous support-zeolite membrane composite according to any one of claims 1 to 3, wherein the temperature at which the zeolite is crystallized is 100 to 200 ° C.   The method for producing an inorganic porous support-zeolite membrane composite according to any one of claims 1 to 4, wherein the thickness of the zeolite membrane is 0.1 µm or more and 100 µm or less. The ratio of the Si element source to the alkali source is from 0.02 to 0.5 in terms of a molar ratio of M ₂ O / SiO ₂ (M is Na or K). For producing a porous support-zeolite membrane composite. The method for producing an inorganic porous support-zeolite membrane composite according to any one of claims 1 to 6, wherein the molar ratio of K to K and Na is 0.01 to 1. Inorganic porous support according to any one of claims 1 to 7 ratio of Si element source and water is 50 to 150 as the molar ratio of water to SiO ₂ - the manufacturing method of the zeolite membrane composite. An inorganic porous support according to any one of claims 1 to 8 , which is a method for producing concentrated alcohol from an alcohol-water mixture using a separation membrane module, wherein the separation membrane accommodated in the separation membrane module. A method for producing concentrated alcohol, which is a zeolite membrane composite. The method for producing a concentrated alcohol according to claim 9 , wherein the alcohol concentration of the alcohol-water mixture is 85% by weight or less. The manufacturing method of the concentrated alcohol of Claim 9 or 10 which makes the liquid of an alcohol-water mixture contact a separation membrane, and permeate | transmits water by a pervaporation method. The manufacturing method of the concentrated alcohol of Claim 11 whose temperature of the alcohol-water mixture supplied to a separation membrane module is 25-200 degreeC. The manufacturing method of the concentrated alcohol of Claim 9 or 10 which makes the gas of an alcohol-water mixture contact a separation membrane, and permeate | transmits water by a vapor permeation method. The method for producing concentrated alcohol according to claim 13 , wherein the temperature of the superheated steam of the alcohol-water mixture supplied to the separation membrane module is T + 1 to 100 ° C, where T is a saturated vapor pressure temperature.

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