JP2002249311A - Zeolite molded product, zeolite laminated intermediate body, zeolite laminated composite and method for producing these - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a zeolite molded product enabling to form and maintain a zeolite film thereon without generating cracks and also satisfying both decrease in pressure loss and the maintenance and improvement of mechanical strength when used as a gas separation membrane such as a molecular sieve membrane, or an osmotic evaporating membrane, and also provided a zeolite laminated intermediate body which forms on the zeolite molded product a zeolite membrane containing a template, and further provide a zeolite laminated composite formed by calcining the zeolite laminated intermediate body, and still further provide a method for producing these efficiently. SOLUTION: This porous zeolite molded product has the difference of <=1.0 atm in pressure between the feeding and permeation sides in permeating amount of 10 ml/cm<2> per min when it has average particle diameter of 1.0 μm or more, bending strength of 1.5 MPa or more and thickness of 1.8 mm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a zeolite molded product, a zeolite laminated intermediate, a zeolite laminated composite, and a method for producing the same. More specifically, a zeolite membrane can be formed and maintained thereon without generating cracks, and when used as a gas separation membrane such as a molecular sieve membrane or a pervaporation membrane, pressure loss is reduced and mechanical strength is maintained. A zeolite molded article satisfying all of the improvements, a zeolite laminated intermediate formed by forming a zeolite membrane containing a template agent on the zeolite molded article, a zeolite laminated composite formed by calcining the zeolite laminated intermediate, and the like. And a method for efficiently manufacturing the same.

[0002]

2. Description of the Related Art In recent years, a porous zeolite molded body composed of particles made of zeolite has become a molecular sieve membrane (gas separation membrane, pervaporation membrane) as a zeolite membrane laminated composite having a zeolite membrane formed thereon. Including
It is widely used for catalysts, catalyst carriers, adsorbents, and the like. Under such circumstances, various zeolite molded bodies (substrates), laminated zeolite intermediates, laminated zeolite composites, and methods for producing them have been proposed. For example,
As a base of the zeolite membrane, a method using glass, mullite, cordierite-based ceramics, alumina, silica, or the like, or a method using a metal or other base material coated with an inorganic material has been proposed (Japanese Patent Laid-Open No. 59-21
No. 3615).

Further, a cage-type zeolite thin film is made of metal,
A composite formed by combining an inorganic or polymeric substance on one surface of a porous support has been proposed (JP-A-60-2882).
No. 6). Among them, it is proposed that it is particularly preferable to use a support having a high affinity for a gel substance, and specifically, a product name: No. 1 manufactured by Corning Glass Works Co., Ltd. It has been proposed that it is particularly preferred to use 7930 or what is commonly referred to as Vycor glass.

Further, the present invention relates to a method for crystallizing zeolite on the surface of a monolithic ceramic support as a substrate, comprising an oxide comprising 45-4% by mass silica, 8-45% by mass alumina, and 7-20% by mass magnesia. A monolithic support having a composition has been proposed (Japanese Unexamined Patent Publication No.
Specifically, a sintered monolithic support made of cordierite, glass, or glass ceramic has been proposed.

In addition, the present invention relates to a method for producing an A-type or faujasite-type zeolite membrane, and proposes a method using a substrate made of a substance containing silicon oxide as a main component (JP-A-6-32610). . The purpose of this method is to improve the problem of poor adhesion of the zeolite membrane to the substrate, using the raw material of the zeolite membrane as the substrate itself, and that the substrate surface is converted into a zeolite membrane due to its configuration. Therefore, the synthesis and the attachment can proceed at the same time, and the process can be simplified. Specifically, borosilicate glass, quartz glass, silica alumina,
A substrate made of mullite or the like has been proposed.

The present invention also relates to a method for producing a supported zeolite membrane and to the resulting membrane, wherein the support comprises a ceramic substance based on alumina, zirconia or titanium oxide, a metal, carbon, silica, zeolite, clay and a polymer. There has been proposed an inorganic, organic or mixed substance selected from the group consisting of (JP-A-9-173799).

[0007] Further, the porous ceramic substrate to be subjected to the zeolite treatment has a large number of internal pores of a predetermined size,
A porous zeolite having a compressive breaking strength of 5 MPa or more has been proposed (Japanese Patent Application Laid-Open No. H11-292651).

As described above, conventionally, various zeolite laminated composites in which a zeolite membrane is laminated and formed on a substrate have been proposed, but these composites have the following problems. That is, as shown in FIG.
The coefficient of thermal expansion of zeolite is a very small value at about 200 ° C., but shows a negative coefficient at a high temperature. For this reason, when the zeolite membrane is used at a temperature exceeding 200 ° C., the difference in thermal expansion between the zeolite membrane and a substrate, for example, an alumina substrate, becomes extremely large, and cracks are generated in the zeolite membrane due to thermal stress.

Further, depending on the type of zeolite membrane,
In some cases, it is necessary to add a template agent or a crystallization accelerator during synthesis. The zeolite membrane containing the template is calcined at about 500 ° C. to remove the template. As shown in the thermal expansion curve of the MFI type zeolite in FIG. 15, the thermal expansion behavior of the zeolite membrane containing the template (FIG. 15) Is extremely different from the thermal expansion behavior of the zeolite membrane without the template agent (thermal expansion curve after calcination in FIG. 15).
The difference in thermal expansion from a substrate such as an alumina substrate becomes extremely large, and cracks occur in the zeolite film due to thermal stress during calcination.

[0010] Such a problem cannot be adequately dealt with by the above-mentioned conventional proposal example.

[0011] Further, assuming that the substrate and the zeolite membrane have a two-layer structure, a macroporous layer formed of substantially only molecular sieve crystals having a predetermined thickness, and a macroporous layer having a predetermined thickness and a predetermined pore effective diameter. An asymmetric membrane consisting essentially of the material of the macroporous layer and an upper layer for molecular separation formed only of the same kind of molecular sieve crystals (Japanese Patent Application Laid-Open No. 7-50 / 1990)
No. 5333), a structure comprising a carrier, an intermediate layer and an upper layer, wherein the intermediate layer and the upper layer contain a predetermined crystalline molecular sieve (Japanese Patent Application Laid-Open No. 11-511885),
And a zeolite composite membrane (International Publication No. WO 00/23378) in which a zeolite membrane containing a template is coated on a zeolite porous substrate containing a template and then calcined to remove the template from the membrane and the substrate simultaneously. Have been. These films and structures are excellent in that the size of the pores can be accurately adjusted and the generation of cracks can be effectively prevented.

[0012]

However, when these membranes or structures (laminate zeolite composite) are used as a gas separation membrane such as a molecular sieve membrane or a pervaporation membrane, gas-liquid passes through the membrane or the inside of the substrate. To reduce the pressure loss when
Although it is necessary to improve its use efficiency, if the particle size of the substrate, which is a main cause of the increase in pressure loss to reduce the pressure loss, is increased, the mechanical strength of the substrate supporting the zeolite membrane is reduced. (Since the reduction in pressure loss and the improvement in mechanical strength of the substrate are in a trade-off relationship), it is extremely difficult to obtain a material that satisfies both the reduction in pressure loss and the maintenance and improvement of mechanical strength. It is difficult, and such a thing has not yet been obtained.

The present invention has been made in view of the above-described problems, and can form and maintain a zeolite membrane thereon without generating cracks, and can be used as a gas separation membrane such as a molecular sieve membrane or a pervaporation membrane. When used, a zeolite molded article that satisfies both of a reduction in pressure loss and maintenance and improvement of mechanical strength, a zeolite laminated intermediate in which a zeolite membrane containing a mold agent is formed on the zeolite molded article, and a zeolite laminated intermediate An object of the present invention is to provide a laminated zeolite composite formed by calcining a body and a method for efficiently producing the composite.

[0014]

Means for Solving the Problems In order to achieve the above-mentioned object, the present invention provides the following zeolite molded product, zeolite laminated intermediate, zeolite laminated composite, and methods for producing them.

[1] A porous zeolite molded body made of zeolite, having an average particle diameter of 1.0 μm or more,
The bending strength is 1.5 MPa or more, and the thickness is 1.8
mm, helium gas permeation amount 10 ml / c
A molded product of zeolite, wherein the difference between the supply side pressure and the permeation side pressure at m ² · min is 1.0 atm or less.

[2] The zeolite molded product according to the above [1] contains a template, and a zeolite membrane containing a template of the same or similar composition is laminated thereon. Zeolite laminated intermediate.

[3] The zeolite formed by calcining the zeolite laminate intermediate according to [2] to remove the template from the zeolite formed body and the zeolite membrane containing the template. A zeolite laminate composite comprising the molded body and the zeolite membrane laminated thereon.

[4] Tetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammonium bromide (TPABr) are added to the silica sol, and the total amount of these tetrapropylammonium ions (TPA), that is, (TPAOH + TPABr),
“Total amount of (TPA)” is changed to “(TPAOH + TPAB”
r) ") in each case [TPAOH / (TPAOH + TPAB) with respect to tetrapropylammonium hydroxide (TPAOH) and tetrapropylammonium bromide (TPABr).
r), and TPABr / (TPAOH + TPABr)]
Is added so as to be 0 to 99 mol% and 100 to 1 mol%, and the resulting preparation is kneaded and dried, and the resulting dried gel is shaped and crystallized. A method for producing a zeolite molded article.

[5] A tetrapropylammonium hydroxide (TPAOH) solution is added to the silica sol,
A method for producing a zeolite molded body, comprising spraying and drying the obtained preparation liquid, and forming and crystallizing the obtained dried gel.

[6] Tetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammonium bromide (TPABr) are added to the silica sol, and tetrapropylammonium hydroxide (TPAOH) and tetrapropylammonium hydroxide (TPAOH) are added to the total amount of these tetrapropylammonium ions (TPA). Propyl ammonium bromide (TPABr) [TPAOH /
(TPAOH + TPABr), and TPABr / (TP
AOH + TPABr)] is from 0 to 99 mol% and 100
１1 mol%, and the resulting solution was kneaded and dried, and the resulting dried gel was molded and crystallized to obtain a zeolite molded body. The zeolite molded body is immersed in a solution having the same or similar composition as the preparation liquid, and hydrothermally synthesized to form a zeolite membrane containing a template on the zeolite molded body, and the zeolite molded body and the A method for producing a zeolite laminate intermediate, comprising forming a laminate with a zeolite membrane containing a template agent.

[7] A tetrapropyl ammonium hydroxide (TPAOH) solution is added to the silica sol,
The obtained preparation is sprayed and dried, and the obtained dry gel is molded and crystallized to obtain a zeolite molded body, and the obtained zeolite molded body has the same or similar composition as the preparation liquid. Immersion in a solution, hydrothermal synthesis, to form a zeolite membrane containing a template on the zeolite molded body,
A method for producing a zeolite laminate intermediate, comprising forming a laminate of the zeolite molded body and a zeolite membrane containing the template agent.

[8] Tetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammonium bromide (TPABr) are added to the silica sol, and tetrapropylammonium hydroxide (TPAOH) and tetrapropylammonium hydroxide (TPAOH) are added to the total amount of these tetrapropylammonium ions (TPA). Propyl ammonium bromide (TPABr) [TPAOH /
(TPAOH + TPABr), and TPABr / (TP
AOH + TPABr)] is from 0 to 99 mol% and 100
１1 mol%, and the resulting solution was kneaded and dried, and the resulting dried gel was molded and crystallized to obtain a zeolite molded body. The zeolite molded body is immersed in a solution having the same or similar composition as the preparation liquid, and hydrothermally synthesized to form a zeolite membrane containing a template on the zeolite molded body, and the zeolite molded body and the A method for producing a laminated zeolite composite, comprising forming a laminate with a zeolite membrane containing a template, and calcining the laminate to simultaneously remove the template.

[9] A tetrapropyl ammonium hydroxide (TPAOH) solution is added to the silica sol,
The obtained preparation is sprayed and dried, and the obtained dry gel is molded and crystallized to obtain a zeolite molded body, and the obtained zeolite molded body has the same or similar composition as the preparation liquid. Immersion in a solution, hydrothermal synthesis, to form a zeolite membrane containing a template on the zeolite molded body,
A method for producing a laminated zeolite composite, comprising forming a laminate of the zeolite molded body and a zeolite membrane containing the template, and calcining the laminate to simultaneously remove the template.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the zeolite molded article of the present invention will be specifically described.

The zeolite molded article of the present invention is a porous zeolite molded article made of zeolite, having an average particle diameter of 1.0 μm or more, a bending strength of 1.5 MPa or more,
Further, when the thickness is 1.8 mm, the difference between the supply side pressure and the permeation side pressure at a helium gas permeation amount of 10 ml / cm ² · min is 1.0 atm or less.

The zeolite molded article of the present invention is effectively used as a substrate, a zeolite membrane is laminated thereon, and a formed zeolite composite is effectively used for a gas separation membrane such as a molecular sieve membrane or a pervaporation membrane. Therefore, it is necessary that the zeolite membrane laminated and formed thereon can be prevented from cracking. Therefore, when the zeolite molded article of the present invention is used to obtain a zeolite laminated composite by laminating a zeolite membrane thereon, from the zeolite having the same or similar composition as the zeolite membrane laminated thereon, It is preferable that the zeolite is composed of porous zeolite.

In particular, when a zeolite laminated composite is formed using a template or the like, the thermal expansion behavior of the zeolite membrane containing the template is extremely higher than that of the zeolite membrane without the template as shown in FIG. Considering that the substrate has a coefficient of thermal expansion similar to that of a zeolite membrane (for example,
(Quartz glass or the like) alone cannot eliminate the difference in thermal expansion when calcining at about 500 ° C. to remove the mold agent, and causes cracks in the zeolite membrane. The zeolite molded body is preferably a porous zeolite having the same or similar composition as the zeolite membrane in all aspects of the composition including the template.

The zeolite used in the present invention is not particularly limited. For example, MFI, AFI, DDR, etc. (ParkS.H.eta.
l.Stud.Surf.Sci.Catal.1997,105,1989-1994)
It is usually difficult to prevent the occurrence of cracks in the zeolite membrane when a zeolite laminate composite is formed from a zeolite membrane using these zeolites and a zeolite molded body serving as a substrate. It will be used effectively.

When a template is required when forming a zeolite membrane, the template may be, for example,
Tetraethylammonium hydroxide (tetrapropylammonium hydroxide (TPAOH)) and bromide (tetrapropylammonium bromide (TPABr)) contained in a zeolite membrane composed of MFI, and tetraethylammonium (TEA) contained in a zeolite membrane composed of BEA Hydroxide or bromide, etc., the thermal expansion behavior of a zeolite membrane containing such a template agent and a zeolite membrane not containing a template agent,
There is a significant difference as shown in FIG.

Therefore, as the zeolite molded article of the present invention, a zeolite laminated composite formed by using a zeolite such as MFI, AFI, DDR or the like containing a template agent and laminating a zeolite membrane thereon is formed. In the case of using a zeolite membrane, it is assumed that the zeolite is composed of zeolites of the same or similar composition including the same as the zeolite membrane, and a zeolite membrane such as MFI, AFI, DDR, etc., which does not contain a template agent. When used for a laminated zeolite composite formed thereon, it is preferable that the zeolite be composed of zeolites having the same or similar composition, including the absence of a template agent.

The zeolite molded article of the present invention has an average particle diameter of 1.0 μm or more, preferably 2.5 μm or more, and a bending strength of 1.5 MPa or more, preferably 6.0 MPa.
As described above, when the thickness is 1.8 mm, the difference (pressure loss) between the supply side pressure and the permeation side pressure at a helium gas permeation amount of 10 ml / cm ² · min is 1.0 atm or less, preferably Is 0.6 atm or less.

By satisfying this condition, the zeolite molded article of the present invention can form and maintain a zeolite membrane thereon without generating cracks,
When used as a gas separation membrane such as a molecular sieve membrane or a pervaporation membrane, both of the reduction of pressure loss and the maintenance and improvement of mechanical strength are satisfied.

The average particle diameter was determined by measuring the maximum length of each particle by an image analyzer and averaging the measured lengths. That is, the fracture surface (the part extracted at random) of the zeolite molded article of the present invention was measured using a scanning electron microscope (SE).
M) and an SEM photograph was taken (FIG. 16). Based on this SEM photograph, a replica diagram was prepared in which black and white were color-coded (FIG. 17). In this case, the white part indicates particles, and the black part indicates voids between particles and the particles are unclear.However, select particles in which the entire zeolite particles are visible. Particles with visible diameter were selected. In addition, the measurement was not performed on particles that were not clear as a whole due to overlapping of the particles. Image analysis is performed using an image analysis device (Toyobo Co., Ltd.)
Product name: Image Analyzer V10), capture the replica image into a personal computer, set the measurement area, scale, and binarization processing (white parts in the replica diagram are zeolite particles, black parts are between particles). (Process for causing recognition as a non-measurement part such as a void)), the maximum length of each particle was measured based on the criteria shown in FIGS.

The flexural strength is measured according to JIS R 160
1 was measured.

Further, the pressure loss was measured by the method shown in FIG. That is, the zeolite molded product (diameter 18 mm, thickness 1.8 mm) 11 of the present invention and quartz glass tube 12
And were joined with an epoxy resin, and disposed in a metal (stainless steel) container 13. At room temperature, helium gas was used as the supply gas 14, and the pressure was increased to a maximum of 8 kgf / cm ^2. 18 respectively. Helium gas permeation amount 10ml / cm ²
The difference between the supply side pressure and the permeation side pressure in min was defined as the pressure loss.

Since the pressure loss of the porous material increases in proportion to the thickness of the sample to be measured (the pressure loss is doubled when the thickness is doubled), the pressure loss is measured. In such a case, it is necessary to make the thickness of the measurement sample always the same or to perform correction by calculation in consideration of the thickness. In the present invention, the thickness of the sample was adjusted to 1.8 mm, and the pressure difference between the supply side and the permeation side in the shape was measured and defined as pressure loss.

In the method for producing a zeolite molded article of the present invention, a tetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammonium bromide (TPABr) are mixed with a silica sol to mix these tetrapropylammonium ions (TPA) with the silica sol. The ratio (TPA / SiO ₂ ) is set to a predetermined molar ratio, and tetrapropyl ammonium ion (TP
The respective mixing ratios of tetrapropylammonium hydroxide (TPAOH) and tetrapropylammonium bromide (TPABr) based on the total amount of A) [TPA
OH / (TPAOH + TPABr) and TPABr /
(TPAOH + TPABr)] is adjusted to be 0 to 99 mol% and 100 to 1 mol%, and the obtained preparation is kneaded and dried, and the obtained dried gel is formed.
It is characterized by performing a crystallization treatment.

Here, the mixing ratio of the tetrapropylammonium ion (TPA) and the silica sol (TPA / S
iO ₂ molar ratio) is from 0.015 to 0.0
In the range of 8, the average particle diameter of the zeolite molded body does not change,
The bending strength must be 1.5 MPa or more (strength that does not break down in a hydrothermal synthesis environment of the zeolite membrane and does not break down after the membrane is formed), which is necessary as a substrate capable of forming a zeolite laminate composite. Therefore, the adjustment may be made in any range. In the practice of the present invention, the TPA / SiO ₂ molar ratio was adjusted to 0.04, at which the bending strength was maximized.

If the molar ratio of TPA / SiO ₂ in the preparation solution and the respective proportions of TPAOH and TPABr with respect to the total amount of TPA are maintained at predetermined amounts, sodium hydroxide may be used to adjust the pH if necessary. And an alkali source such as potassium hydroxide.

Next, in order to dry the prepared solution, the prepared solution was placed in a Teflon (registered trademark) beaker, stirred with a magnetic stirrer, and then manually heated with a Teflon rod while being heated in a thermostat set at a predetermined temperature. Continue stirring and kneading to evaporate water to obtain a dry gel. The stirring and kneading at this time may be performed with a heating kneader or the like.

Next, the dry gel is formed into a predetermined shape by uniaxial press molding (total pressure of 1000 kgf), and then cold isostatic pressing is performed to obtain a dry gel molded body. At this time, the pressure of the cold isostatic pressing is set to 700 to 7000 kgf / c so as to obtain a desired dry gel molded article density.
It is preferable to adjust within the range of m ² .

Next, the dried gel molded body obtained as described above is placed in a stainless steel pressure-resistant container equipped with a Teflon inner cylinder filled with distilled water of the same weight as the molded body so as not to come in contact with water. Placed in a 180 ° C oven
The mixture is allowed to react for 0 hour under autogenous steam pressure to be crystallized to obtain a zeolite molded body. At this time, the amount of distilled water is the minimum amount that reaches the saturated water vapor pressure in the pressure vessel used, and if it is more than that, there is no restriction from the relationship between the molded body and the distilled water. As for the reaction temperature and time, 13
Since crystallization proceeds at 0 ° C. or more and for 2 hours or more, there is no particular limitation as long as the temperature and time are longer than that.

Further, in the method for producing a zeolite molded article of the present invention, a tetrapropylammonium hydroxide (TPAOH) solution is added to a silica sol, and the mixing ratio (TPA / SiO ₂ ) of the tetrapropylammonium ion (TPA) and the silica sol. ) May be added so as to have a predetermined molar ratio, and the resulting preparation is sprayed and dried, and the resulting dried gel may be formed and characterized by a crystallization treatment.

Here, as a method of spraying and drying the prepared liquid, for example, a spray drier of a solution or a slurry such as a spray drier or a fluidized-granulation drier can be mentioned. A spray drier was used for drying the preparation in the present invention. The preparation liquid is conveyed to the tip of the spray nozzle by a liquid sending pump, where it is sprayed with pressurized air, and then dried and collected in a drying chamber through which dry air flows. At this time, the air circulated in the drying chamber is previously heated to 180 ° C. in the vicinity of the spray port of the preparation liquid and the pressurized air, but this temperature varies depending on the volume of the drying chamber. There is no particular limitation.

Here, the mixing ratio of the tetrapropylammonium ion (TPA) and the silica sol (TPA / S
iO ₂ molar ratio) is from 0.015 to 0.0
In the range of 8, the average particle diameter of the zeolite molded body does not change,
In addition, the flexural strength may be adjusted in any range since it has 1.5 MPa or more, which is necessary for a substrate capable of forming a laminated zeolite composite. In the embodiment of the present invention, the TPA / SiO ₂ molar ratio of 0.1 at which the bending strength is maximized.
Adjusted to 04. If the molar ratio of TPA / SiO ₂ in the preparation is maintained at a predetermined amount, an alkali source such as sodium hydroxide or potassium hydroxide may be added to adjust the pH if necessary.

Next, the prepared liquid is sprayed by the above-described spraying method and dried to obtain a dried gel.

Next, the dry gel is molded into a predetermined shape by uniaxial press molding (total pressure of 1000 kgf), and then cold isostatically molded to obtain a dry gel molded body. At this time, the pressure of the cold isostatic pressing is set to 700 to 7000 kgf / c so as to obtain a desired dry gel molded article density.
It is preferable to adjust within the range of m ² .

Next, the dried gel molded body obtained as described above is placed in a stainless steel pressure-resistant container equipped with a Teflon inner cylinder filled with distilled water of the same weight as the molded body so that it does not come in contact with water. Placed in a 180 ° C oven
The mixture is allowed to react for 0 hour under autogenous steam pressure to be crystallized to obtain a zeolite molded body. At this time, the amount of distilled water is the minimum amount that reaches the saturated water vapor pressure in the pressure vessel used, and if it is more than that, there is no restriction from the relationship between the molded body and the distilled water. As for the reaction temperature and time, 13
Since crystallization proceeds at 0 ° C. or more and for 2 hours or more, there is no particular limitation as long as the temperature and time are longer than that.

Thus, the method of spraying and drying is as follows:
Making the drying more homogeneous than the above-mentioned method of kneading and drying,
The microstructure after the crystallization treatment can be effectively prevented from being densified and shattered.

The zeolite laminated intermediate of the present invention is obtained by forming the above-mentioned zeolite molded body containing a template, and further stacking a zeolite membrane containing a template of the same or similar composition. Features.

The method for forming the zeolite membrane containing the template agent is not particularly limited, and examples thereof include a hydrothermal synthesis method and a gas phase transport method.

Further, the laminated zeolite composite of the present invention is formed by calcining the above-described intermediate laminated zeolite and removing the template from the zeolite formed body and the zeolite membrane containing the template. It is characterized in that a zeolite membrane is laminated on the body.

Here, since the zeolite laminated composite is effectively used for a gas separation membrane such as a molecular sieve membrane, a pervaporation membrane, and the like, a zeolite membrane containing a template agent laminated on a zeolite molded body is used. The zeolite membrane from which the zeolite molded body has been removed must have a sufficient thickness so that the zeolite molded body is not exposed, and must be a dense membrane. In addition, when using a zeolite molded product containing a template agent, the zeolite membrane containing a template agent to be laminated, is composed of zeolite of the same or similar composition including the same template agent. Need to be.

In the method for producing a zeolite laminate intermediate of the present invention, a tetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammonium bromide (TPABr) are added to a silica sol to form a mixture of these tetrapropylammonium ions (TPA) with the silica sol. The mixing ratio (TPA / SiO ₂ ) is set to a predetermined molar ratio, and tetrapropyl ammonium ion (TP
The respective mixing ratios of tetrapropylammonium hydroxide (TPAOH) and tetrapropylammonium bromide (TPABr) based on the total amount of A) [TPA
OH / (TPAOH + TPABr) and TPABr /
(TPAOH + TPABr)] is adjusted to be 0 to 99 mol% and 100 to 1 mol%, and the obtained preparation is kneaded and dried, and the obtained dried gel is formed.
The crystallization treatment is performed to obtain a zeolite molded body, and the obtained zeolite molded body is immersed in a solution having the same or similar composition as the preparation liquid, hydrothermally synthesized, and contains a mold agent on the zeolite molded body. It is characterized in that a zeolite membrane is formed to form a laminate of a zeolite molded body and a zeolite membrane containing a template agent. Specifically, the method for producing a zeolite laminated composite of the present invention will be described.

Further, a tetrapropylammonium hydroxide (TPAOH) solution is added to the silica sol such that the mixing ratio (TPA / SiO ₂ ) of these tetrapropylammonium ions (TPA) and silica sol becomes a predetermined molar ratio. The obtained preparation is sprayed and dried, and the obtained dried gel is molded and crystallized to obtain a zeolite molded body.The obtained zeolite molded body has the same or similar composition as the preparation liquid. Immerse in the solution, hydrothermal synthesis,
It may be characterized in that a zeolite membrane containing a template agent is formed on a zeolite molded body to form a laminate of the zeolite molded body and a zeolite membrane containing a template agent. Specifically, the method for producing a zeolite laminated composite of the present invention will be described.

In the method for producing a laminated zeolite composite according to the present invention, a tetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammonium bromide (TPABr) are added to a silica sol, and these tetrapropylammonium ions (TPA) and the silica sol are combined. So that the compounding ratio (TPA / SiO ₂ ) of the compound has a predetermined molar ratio, and a tetrapropyl ammonium ion (T
PA) to the total amount of tetrapropylammonium hydroxide (TPAOH) and tetrapropylammonium bromide (TPABr) [TP
AOH / (TPAOH + TPABr) and TPABr
/ (TPAOH + TPABr)] is adjusted to be 0 to 99 mol% and 100 to 1 mol%, and the obtained preparation liquid is kneaded and dried, and the obtained dried gel is formed and crystallized. Treatment, to obtain a zeolite molded body, the obtained zeolite molded body is immersed in a solution having the same or similar composition as the preparation liquid, hydrothermally synthesized, a zeolite membrane containing a template on the zeolite molded body To form a laminate of a zeolite molded body and a zeolite membrane containing a template, and simultaneously calcine the laminate to remove the template.

Here, in the production of the zeolite molded body, the mixing ratio (TPA / SiO ₂ molar ratio) of tetrapropylammonium ion (TPA) and silica sol is such that the molar ratio of zeolite is in the range of 0.015 to 0.08. The average particle size of the molded article does not change, and the flexural strength is necessary for a substrate capable of forming a zeolite laminated composite.
Since it has 5 MPa or more, it may be adjusted in any range. In the examples of the present invention, the TPA / SiO ₂ molar ratio was adjusted to be 0.04 at which the bending strength was maximized.

Further, if the molar ratio of TPA / SiO ₂ in the preparation solution and the respective mixing ratios of TPAOH and TPABr to the total amount of TPA are maintained at predetermined amounts, sodium hydroxide may be used to adjust the pH if necessary. And an alkali source such as potassium hydroxide.

Next, in order to dry the prepared solution, the prepared solution was put into a Teflon beaker, stirred by a magnetic stirrer, and then manually stirred and kneaded using a Teflon rod while heating in a constant temperature bath set at a predetermined temperature. Continue to evaporate the water to obtain a dry gel. The stirring and kneading at this time may be performed with a heating kneader or the like.

Next, the dry gel is molded into a predetermined shape by uniaxial press molding (total pressure 1000 kgf), and then cold isostatically pressed to obtain a dry gel molded body. At this time, the pressure of the cold isostatic pressing is set to 700 to 7000 kgf / c so as to obtain a desired dry gel molded article density.
It is preferable to adjust within the range of m ² .

Next, the dried gel molded body obtained as described above is placed in a stainless steel pressure-resistant container with a Teflon inner cylinder filled with distilled water of the same weight as the molded body so as not to come in contact with water. Placed in a 180 ° C oven
The mixture is allowed to react for 0 hour under autogenous steam pressure to be crystallized to obtain a zeolite molded body. At this time, the amount of distilled water is the minimum amount that reaches the saturated water vapor pressure in the pressure vessel used, and if it is more than that, there is no restriction from the relationship between the molded body and the distilled water. As for the reaction temperature and time, 13
Since crystallization proceeds at 0 ° C. or more and for 2 hours or more, there is no particular limitation as long as the temperature and time are longer than that.

The thus obtained zeolite molded body was
The lamination of the zeolite membrane containing the template agent is performed by adding a TPAOH solution, TPABr, and distilled water to silica sol.
The mixture is adjusted to a predetermined molar ratio of SiO ₂ / TPAOH / TPABr / water, adjusted, put into a pressure vessel, and the zeolite molded body is immersed in the prepared solution, and is then left in an oven at 100 ° C. or more for 1 hour or more Reaction, having a sufficient thickness on the zeolite molded body, and forming a zeolite membrane containing a template agent consisting of a dense layer, to obtain a zeolite laminated intermediate, and calcining this zeolite laminated intermediate To obtain a laminated zeolite composite. In an embodiment of the present invention,
In an oven for 18 hours to form a zeolite membrane having a thickness of 20 μm or more and consisting of a dense layer on the zeolite molded body.

In addition, if the molar ratio of SiO ₂ / tetrapropylammonium ion (TPA) / water in the preparation liquid is maintained at a predetermined amount, the pH may be adjusted if necessary.
An alkali source such as sodium hydroxide and potassium hydroxide may be added.

The method for forming the zeolite membrane is not particularly limited, and examples thereof include a hydrothermal synthesis method and a gas phase transport method.

In the method for producing a zeolite laminate composite of the present invention, a tetrapropylammonium hydroxide (TPAOH) solution is added to a silica sol, and the mixing ratio of these tetrapropylammonium ions (TPA) and silica sol (TPA / SiO ₂ ) is added so as to have a predetermined molar ratio, and the obtained preparation is sprayed and dried, and the obtained dried gel is molded and crystallized to obtain a zeolite molded body. The obtained zeolite molded body is immersed in a solution having the same or similar composition as the preparation liquid, and hydrothermally synthesized,
Forming a zeolite membrane containing a template agent on the zeolite molded body to form a laminate of the zeolite molded body and the zeolite membrane containing the mold agent, and simultaneously calcining the laminate to remove the mold agent simultaneously It may be characterized in that

In the production of the zeolite molded body, the mixing ratio (TPA / SiO ₂ molar ratio) of tetrapropylammonium ion (TPA) and silica sol is such that the molar ratio is in the range of 0.015 to 0.08. The average particle size of the body does not change, and the flexural strength is required for a substrate capable of forming a zeolite laminated composite.
Since it has 5 MPa or more, it may be adjusted in any range. In the examples of the present invention, the TPA / SiO ₂ molar ratio was adjusted to be 0.04 at which the bending strength was maximized.

Next, a spray drier was used for drying the preparation liquid. The preparation liquid is sprayed by pressurized air and then dried in a drying chamber through which dry air flows. At this time, the air circulated in the drying chamber is previously heated to 180 ° C. in the vicinity of the spray port, but this temperature is not limited because it varies depending on the volume of the drying chamber.

Next, the dry gel is formed into a predetermined shape by uniaxial press molding (total pressure of 1000 kgf), and then cold isostatic pressing is performed to obtain a dry gel molded body. At this time, the pressure of the cold isostatic pressing is set to 700 to 7000 kgf / c so as to obtain a desired dry gel molded article density.
It is preferable to adjust within the range of m ² .

Next, the dried gel molded body obtained as described above is placed in a stainless steel pressure-resistant container with a Teflon inner cylinder filled with distilled water of the same weight as the molded body so as not to come in contact with water. Placed in a 180 ° C oven
The mixture is allowed to react for 0 hour under autogenous steam pressure to be crystallized to obtain a zeolite molded body. At this time, the amount of distilled water is the minimum amount that reaches the saturated water vapor pressure in the pressure vessel used, and if it is more than that, there is no restriction from the relationship between the molded body and the distilled water. As for the reaction temperature and time, 13
Since crystallization proceeds at 0 ° C. or more and for 2 hours or more, there is no particular limitation as long as the temperature and time are longer than that.

On the thus obtained zeolite molded body,
The lamination of the zeolite membrane containing the template agent is performed by adding a TPAOH solution, TPABr, and distilled water to silica sol.
The mixture is adjusted to a predetermined molar ratio of SiO ₂ / TPAOH / TPABr / water, adjusted, put into a pressure vessel, and the zeolite molded body is immersed in the prepared solution, and is then left in an oven at 100 ° C. or more for 1 hour or more. Reaction, having a sufficient thickness on the zeolite molded body, and forming a zeolite membrane containing a template agent consisting of a dense layer, to obtain a zeolite laminated intermediate, and calcining this zeolite laminated intermediate To obtain a laminated zeolite composite. In an embodiment of the present invention,
In an oven for 18 hours to form a zeolite membrane having a thickness of 20 μm or more and consisting of a dense layer on the zeolite molded body. In addition, if the molar ratio of SiO ₂ / tetrapropylammonium ion (TPA) / water in the preparation solution is maintained at a predetermined amount, an alkali such as sodium hydroxide or potassium hydroxide may be used to adjust the pH if necessary. Sources may be added. The method for forming the zeolite membrane is not particularly limited, and examples thereof include a hydrothermal synthesis method and a gas phase transport method.

[0071]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

(Examples 1 to 5) 200 ml Teflon Bee
About 30 mass% silica sol (Nissan Chemical Co., Ltd.
Product name: Snowtex S) and 10% tetrapropyl alcohol
Ammonium hydroxide (TPAOH) solution (Wako Pure Chemical Industries, Ltd.)
Industrial Co., Ltd.) and tetrapropylammonium bromide
(TPABr) (manufactured by Wako Pure Chemical Industries, Ltd.)
Of tetrapropylammonium ion (TPA)
Mixing ratio with Cazol (TPA / SiO _Two) In molar ratio
0.04 and tetrapropyl ammonium
Tetrapropyl alcohol based on the total amount of potassium ion (TPA)
Ammonium hydroxide (TPAOH) and tetrapro
Pyrammonium bromide (TPABr)
Compounding ratio [TPAOH / (TPAOH + TPABr),
And TPABr / (TPAOH + TPABr)]
% Adjusted to be as shown in Table 1 and added.
In addition, tetrapropylammonium bromide (TPAB)
sodium hydroxide having the same amount (mole) as the addition amount (mole) of r)
Using a 2% by weight aqueous sodium hydroxide solution
And stir with a magnetic stirrer at room temperature for 30 minutes.
After that, use a Teflon rod while further heating to 80 ° C.
By continuing stirring and kneading manually and evaporating water
A colorless dried gel was obtained. X-ray diffraction of the resulting dried gel
When the crystal structure was examined, it was found to be amorphous.

This dried gel is ground in an agate mortar,
The powder having passed through the mesh having a mesh size of 355 μm was subjected to uniaxial press molding (total pressure 1000 kgf) of 5 × 4 × 40 mm.
Into a disk with a diameter of 18 mmφ and a thickness of 1.8 mm, and cold isostatic pressing (1000 kgf / cm
² ) was performed to obtain a molded body. This molded body was placed on a Teflon plate in a stainless steel 100 ml pressure-resistant container with a Teflon inner cylinder filled with distilled water of the same weight as the molded body weight so as not to come in contact with water, and placed in a 180 ° C. oven. The reaction was carried out under autogenous steam pressure for hours. When the molded product after the reaction was examined by X-ray diffraction, it was found that all the compositions were MFI-type zeolites. The molded body was sufficiently dried at 80 ° C. to obtain a zeolite molded body.

The microstructure of the fractured surface of the thus obtained zeolite molded body was observed with a scanning electron microscope (SEM) as described above, and the average particle diameter was calculated from the photograph. As shown in FIG. 1, the blending ratio of tetrapropylammonium bromide (TPABr) [TPABr / (TPAOH + TPABr)] to the total amount of tetrapropylammonium ions (TPA) is
The average particle size became 1.5, 2.7, 6.4, and 8. as the content increased to 5, 12.5, 25, 37.5, and 50 mol%.
It turned out to be as large as 8, 13.9 μm.

The scanning electron microscope of Examples 1 to 5 (SE
M) The photographs are shown in FIGS.

In addition, the rod-shaped zeolite molded article is
When the four-point bending strength was measured in accordance with R 1601, as shown in Table 1 and FIG. 7, the mixing ratio of tetrapropylammonium bromide (TPABr) to the total amount of tetrapropylammonium ion (TPA) [TP
ABr / (TPAOH + TPABr)], 5,12.
As shown in FIG. 8, it was found that the bending strength was reduced as the average particle diameter was increased, and the bending strength was reduced as the average particle diameter was increased as 5, 25, 37.5, and 50 mol%.

When the pressure loss of the disk-shaped zeolite compact was measured, as shown in Table 1, the mixing ratio of tetrapropylammonium bromide (TPABr) to the total amount of tetrapropylammonium ion (TPA) [TPABr / ( TPAOH + TPABr)]
However, the pressure loss decreases as it increases to 5, 12.5, 25, 37.5, and 50 mol%, and as shown in FIG. 9, the pressure loss may decrease as the average particle diameter increases. all right.

Example 6 In a 200 ml Teflon beaker, about 30 mass% silica sol (trade name: Snowtex S, manufactured by Nissan Chemical Co., Ltd.) and tetrapropylammonium bromide (TPABr) (manufactured by Wako Pure Chemical Industries, Ltd.) ) Is mixed with the mixing ratio (TPA / Si) of tetrapropylammonium ion (TPA) of TPABr and silica sol.
O ₂ ) was adjusted to a molar ratio of 0.04 and added. Further, tetrapropylammonium bromide (T
The same amount (mol) of sodium hydroxide (PABr) was added using an aqueous solution of about 2% by mass of sodium hydroxide, and the mixture was stirred with a magnetic stirrer at room temperature for 30 minutes, and further heated to 80 ° C. The stirring and kneading were continued manually using a Teflon rod while evaporating water to obtain a colorless dry gel. When the crystal structure of the obtained dried gel was examined by X-ray diffraction, it was found to be amorphous. A zeolite molded body was obtained from the dried gel in the same manner as in Examples 1 to 5.

The microstructure of the fractured surface of this zeolite compact was measured in the same manner as in Examples 1 to 5 by using a scanning electron microscope (SE
M), and the average particle diameter was calculated from the photograph. The average particle diameter was 24 μm (see FIG. 1). A scanning electron microscope (SEM) photograph is shown in FIG. When the four-point bending strength of the rod-shaped zeolite molded body was measured in the same manner as in Examples 1 to 5, it was 2 MPa as shown in Table 1, FIG. 7 and FIG.

Further, as shown in Table 1 and FIG. 9, when the pressure loss of the disk-shaped zeolite compact was measured in the same manner as in Examples 1 to 5, it was 0.3 × 10 ⁻³ atm.

Example 7 In a 200 ml Teflon beaker, about 30% by mass of silica sol (trade name: Snowtex S, manufactured by Nissan Chemical Co., Ltd.) and 10% tetrapropylammonium hydroxide (TPAOH) solution (Wako Pure Chemical Industries, Ltd.) (Manufactured by K.K.) and adjusted so that the mixing ratio (TPA / SiO ₂ ) of tetrapropylammonium ion (TPA) and silica sol in the TPAOH solution becomes 0.04 in molar ratio, and the mixture is added at room temperature. The mixture was stirred with a magnetic stirrer for 30 minutes to prepare a mixed solution of tetrapropylammonium hydroxide (TPAOH) and silica sol for a spray dryer. The mixed solution is sprayed with a spray drier (trade name: Barvis Mini Spray GA32, manufactured by Yamato Scientific Co., Ltd.) at a spray air pressure of 1 kgf
/ Cm ² , dry air flow rate 0.4m ³ / min, liquid sending amount 3m
1 / min, dried under the condition of 180 ° C.
A dried gel was obtained. When the crystal structure of the obtained dried gel was examined by X-ray diffraction, it was found to be amorphous.

A zeolite molded body was obtained from the dried gel in the same manner as in Examples 1 to 5.

When the microstructure of the fractured surface of this molded product was observed with a scanning electron microscope (SEM) in the same manner as in Examples 1 to 5, it was found that there was no defect and the particle had a uniform structure with no coarse and fine particles. Was. Further, when the average particle diameter was calculated from the photograph, the average particle diameter was 7.5 μm. A scanning electron microscope (SEM) photograph is shown in FIG.

Further, when the four-point bending strength of the rod-shaped zeolite molded body was measured in the same manner as in Examples 1 to 5, it was 6 MPa as shown in Table 1. Table 1 and FIG.
As shown in Table 2, when the pressure loss of the disk-shaped zeolite molded body was measured in the same manner as in Examples 1 to 5,
× 10 ^-3 atm.

Comparative Example 1 In a 200 ml Teflon beaker, about 30 mass% silica sol (trade name: Snowtex S, manufactured by Nissan Chemical Co., Ltd.) and a 10% tetrapropylammonium hydroxide (TPAOH) solution (Wako Pure Chemical Industries, Ltd.) (Manufactured by K.K.) and adjusted so that the mixing ratio (TPA / SiO ₂ ) of tetrapropylammonium ion (TPA) and silica sol in the TPAOH solution becomes 0.04 in molar ratio, and the mixture is added at room temperature. After stirring with a magnetic stirrer for 30 minutes, the mixture was further manually stirred and kneaded with a Teflon rod while further heating to 80 ° C., and water was evaporated to obtain a colorless dry gel. When the crystal structure of the obtained dried gel was examined by X-ray diffraction, it was found to be amorphous.
A zeolite molded body was obtained from the dried gel in the same manner as in Examples 1 to 5.

The microstructure of the fractured surface of this zeolite molded body was measured in the same manner as in Examples 1 to 5 by using a scanning electron microscope (SE).
M), and the average particle diameter was calculated from the photograph. The average particle diameter was 0.8 μm (see FIG. 1). A scanning electron microscope (SEM) photograph is shown in FIG.

When the four-point bending strength of the rod-shaped zeolite molded body was measured in the same manner as in Examples 1 to 5, it was 26 MPa as shown in Table 1, FIG. 7 and FIG.

As shown in FIG. 9, when the pressure loss of the disk-shaped zeolite compact was measured in the same manner as in Examples 1 to 5, it was 1.8 atm.

The average particle size (μ) of the microstructure of the fractured surface of the zeolite molded bodies obtained in Examples 1 to 7 and Comparative Example 1
m) and the results of measuring the four-point bending strength (MPa) and the pressure loss (atm) of the zeolite molded bodies obtained in Examples 1 to 7 and Comparative Example 1 are shown in Table 1. Table 1
Therefore, the zeolite molded bodies obtained in Examples 1 to 7 are practically sufficiently large in average particle diameter and four-point bending strength as compared with the zeolite molded bodies obtained in Comparative Examples, and further, the pressure loss thereof is It turns out that it is very small. Therefore, a zeolite laminate composite having no defects such as cracks laminated on a molded body (substrate) having a very small pressure loss, such as the zeolite molded bodies obtained in Examples 1 to 7, was used as a molecular composite. It can be seen that when used as a gas separation membrane such as a sieve membrane or a pervaporation membrane, it can be used as a high-performance membrane having a large amount of gas and the like permeated.

[0090]

[Table 1]

Example 8 15.26 g of a 10% tetrapropylammonium hydroxide (TPAOH) solution (manufactured by Wako Pure Chemical Industries, Ltd.) and tetrapropylammonium bromide (TPABr) (manufactured by Wako Pure Chemical Industries, Ltd.) 2.
Then, 49.85 g of distilled water and about 30
6.00 g of a mass% silica sol (trade name: Snowtex S manufactured by Nissan Chemical Co., Ltd.) was added to these SiO ₂ / TPA.
The molar ratio of OH / TPABr / water is 1 / 0.25 / 0.2
5/125, and the mixture was stirred with a magnetic stirrer at room temperature for 30 minutes to prepare a sol for forming a zeolite membrane. This sol is made of stainless steel with Teflon inner cylinder 1
The zeolite molded product of Example 6 was immersed in a 00 ml pressure vessel and reacted in an oven at 180 ° C. for 18 hours. When the cross section after the reaction was observed with a scanning electron microscope (SEM), as shown in the SEM photograph of FIG. 20, a dense layer of about 25 μm was formed on the zeolite molded body. Was confirmed to be an MFI type zeolite membrane. The zeolite laminate intermediate obtained as described above was heated to 500 ° C. in an electric furnace and held for 4 hours to remove tetrapropylammonium (TPA). As shown in Table 2, cracks were observed in the rhodamine test. Further, it was confirmed that the composite was a dense zeolite laminate having no cracks and no passage of molecules even by the pervaporation method of triethylbenzene.

Example 9 A zeolite laminated intermediate was obtained on the zeolite molded product of Example 7 in the same manner as in Example 8. The zeolite laminated intermediate obtained as described above was heated to 500 ° C. in an electric furnace and held for 4 hours to remove tetrapropylammonium (TPA). As shown in Table 2, cracks were observed in the rhodamine test. It was confirmed that the composite was a dense zeolite laminate having no cracks and no permeation of molecules even by the pervaporation method of triethylbenzene.

The cracks generated in the zeolite membrane due to the difference in thermal expansion are at a molecular level of about 8 to 50 angstroms and cannot be detected by SEM. Therefore, in the present invention, the following method was used as a method for measuring the crack. The first method (rhodamine test) is a method in which rhodamine B is dropped on a zeolite membrane to visualize cracks, and observed with an optical microscope. The second method (pervaporation method) uses a triisopropylbenzene (TIPB) molecule 20 as shown in FIG.
Is suctioned by a vacuum pump 22 and passed through the zeolite membrane 21 to check for cracks with a vacuum gauge 23 or a gas chromatograph.

[0094]

As described above, according to the present invention, it is possible to form and maintain a zeolite membrane thereon without generating cracks and to use it as a gas separation membrane such as a molecular sieve membrane or a pervaporation membrane. A zeolite molded article satisfying both of the reduction of pressure loss and the maintenance and improvement of mechanical strength, a zeolite laminated intermediate in which a zeolite membrane containing a mold agent is formed on the zeolite molded article, and this zeolite laminated intermediate is temporarily The present invention can provide a laminated zeolite composite formed by calcination and a method for producing the same.

[Brief description of the drawings]

FIG. 1 shows the total amount of tetrapropylammonium ion (TPA) of tetrapropylammonium bromide (TPABr) in the zeolite molded bodies obtained in Examples 1 to 6 and Comparative Example 1 of the present invention, that is, (TPAOH + T)
PAPA) [TPABr / (TPAO)
H + TPABr)] and the average particle diameter.

FIG. 2 is an SEM photograph showing a microstructure of a fractured surface of the zeolite molded body obtained in Example 1 of the present invention.

FIG. 3 is an SEM photograph showing a microstructure of a fractured surface of the zeolite molded body obtained in Example 2 of the present invention.

FIG. 4 is an SEM photograph showing a microstructure of a fractured surface of the zeolite molded body obtained in Example 3 of the present invention.

FIG. 5 is an SEM photograph showing a microstructure of a fractured surface of the zeolite molded body obtained in Example 4 of the present invention.

FIG. 6 is an SEM photograph showing a microstructure of a fractured surface of the zeolite molded body obtained in Example 5 of the present invention.

FIG. 7 shows a blending ratio (TPAB) of tetrapropylammonium bromide (TPABr) to the total amount of tetrapropylammonium ions (TPA) in the zeolite compacts obtained in Examples 1 to 6 and Comparative Example 1 of the present invention.
4 is a graph showing the relationship between (r / TPA) and bending strength.

FIG. 8 is a graph showing the relationship between the average particle diameter and the four-point bending strength of the zeolite molded bodies obtained in Examples 1 to 6 and Comparative Example 1 of the present invention.

FIG. 9 is a graph showing the relationship between the average particle diameter and the pressure loss in the zeolite molded articles obtained in Examples 1 to 7 and Comparative Example 1 of the present invention.

FIG. 10 is an SEM photograph showing a microstructure of a fractured surface of the zeolite molded body obtained in Example 6 of the present invention.

FIG. 11 is an SEM photograph showing a microstructure of a fractured surface of the zeolite molded body obtained in Example 7 of the present invention.

FIG. 12 is an SEM photograph showing a microstructure of a fractured surface of the zeolite molded body obtained in Comparative Example 1 of the present invention.

FIG. 13 is an explanatory view showing a crack measuring method by a pervaporation method in Example 8 of the present invention.

FIG. 14 is a graph showing a thermal expansion curve of the MFI zeolite.

FIG. 15: MFI-type zeolite (before and after calcining)
4 is a graph showing a thermal expansion curve of alumina and alumina.

FIG. 16 is an SEM photograph showing a method for measuring an average particle diameter.

FIG. 17 is a replica view of an SEM photograph showing a method for measuring an average particle diameter.

FIG. 18 is an explanatory diagram showing a method for measuring an average particle diameter.

FIG. 19 is an explanatory diagram showing a method for measuring pressure loss.

FIG. 20 is an SEM photograph showing a microstructure of a fractured surface of the zeolite laminated intermediate obtained in Example 8 of the present invention.

[Explanation of symbols]

11 ... zeolite molded body, 12 ... quartz glass tube, 13 ...
Stainless steel container, 14 ... supply gas (helium gas), 1
5: Permeated gas, 16: Pressure gauge, 17: Pressure gauge, 18: Flow meter, 19: O-ring, 20: Triisopropylbenzene (TIPB) solution, 21: Zeolite membrane, 22: Vacuum pump, 23: Vacuum gauge .

 ──────────────────────────────────────────────────続 き Continued on front page F-term (reference) 4D006 GA25 GA41 MA03 MA31 MB03 MB16 MC01 MC01X NA05 NA54 NA64 NA65 PB70 4G073 BD06 BD07 BD15 BD18 BD26 DZ01 FB30 FC30 FD01 FD15 FD17 FD23 FD27 UA01 UA02 UA02 UA06

Claims (9)

[Claims] 1. A porous zeolite molded body made of zeolite, having an average particle diameter of 1.0 μm or more and a bending strength of 1.5 MPa.
As described above, when the thickness is 1.8 mm, the difference between the supply side pressure and the permeation side pressure at a helium gas permeation rate of 10 ml / cm ² · min is 1.0 atm or less. Zeolite molded body. 2. The zeolite molded article according to claim 1, comprising a template, on which a zeolite membrane containing a template having the same or similar composition is laminated. Zeolite laminated intermediate. 3. The zeolite molded body formed by calcining the zeolite laminated intermediate according to claim 2 to remove the template from the zeolite molded body and the zeolite membrane containing the template. A laminated zeolite composite comprising the zeolite membrane laminated thereon. 4. A silica sol is provided with a tetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammonium bromide (TPABr), and tetrapropylammonium hydroxide (TPA) based on the total amount of these tetrapropylammonium ions (TPA).
OH) and tetrapropylammonium bromide (TP
ABr) [TPAOH / (TPA
OH + TPABr) and TPABr / (TPAOH +
TPABr)] is adjusted to be 0 to 99 mol% and 100 to 1 mol%, and the resulting preparation is kneaded and dried, and the resulting dried gel is molded and crystallized. A method for producing a zeolite molded article, characterized in that: 5. A method comprising adding a tetrapropylammonium hydroxide (TPAOH) solution to a silica sol, spraying the obtained preparation, drying the obtained preparation, and subjecting the obtained dry gel to a molding and crystallization treatment. Of producing a molded zeolite body. 6. A silica sol is provided with a tetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammonium bromide (TPABr), and tetrapropylammonium hydroxide (TPA) based on the total amount of these tetrapropylammonium ions (TPA).
OH) and tetrapropylammonium bromide (TP
ABr) [TPAOH / (TPA
OH + TPABr) and TPABr / (TPAOH +
TPABr)] is adjusted so as to be 0 to 99 mol% and 100 to 1 mol%, and the obtained preparation liquid is kneaded and dried, and the obtained dry gel is formed and crystallized. Then, to obtain a zeolite molded body, the obtained zeolite molded body is immersed in a solution having the same or similar composition as the preparation liquid, and hydrothermally synthesized, the zeolite containing a template agent on the zeolite molded body A method for producing a zeolite laminate intermediate, comprising forming a membrane and forming a laminate of the zeolite molded body and the zeolite membrane containing the template agent. 7. A solution of tetrapropylammonium hydroxide (TPAOH) is added to the silica sol, and the obtained preparation is sprayed and dried to form a dry gel,
A crystallization treatment is performed to obtain a zeolite molded body, and the obtained zeolite molded body is immersed in a solution having the same or similar composition as the preparation liquid, hydrothermally synthesized, and a mold agent is formed on the zeolite molded body. The method for producing a zeolite laminate intermediate, comprising: forming a zeolite membrane containing a zeolite membrane; and forming a laminate of the zeolite molded body and the zeolite membrane containing the template agent. 8. A silica sol is provided with tetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammonium bromide (TPABr), and tetrapropylammonium hydroxide (TPA) based on the total amount of these tetrapropylammonium ions (TPA).
OH) and tetrapropylammonium bromide (TP
ABr) [TPAOH / (TPA
OH + TPABr) and TPABr / (TPAOH +
TPABr)] is added so as to be 0 to 99 mol% and 100 to 1 mol%, and the obtained preparation liquid is kneaded and dried, and the obtained dry gel is molded and crystallized. Then, to obtain a zeolite molded body, the obtained zeolite molded body is immersed in a solution having the same or similar composition as the preparation liquid, and hydrothermally synthesized, the zeolite containing a template agent on the zeolite molded body Forming a membrane and forming a laminate of the zeolite molded body and the zeolite membrane containing the template, and calcining the laminate to simultaneously remove the template; How to make the body. 9. A solution of tetrapropylammonium hydroxide (TPAOH) is added to the silica sol, and the resulting preparation is sprayed and dried to form the resulting dried gel.
A crystallization treatment is performed to obtain a zeolite molded body, and the obtained zeolite molded body is immersed in a solution having the same or similar composition as the preparation liquid, hydrothermally synthesized, and a mold agent is formed on the zeolite molded body. Forming a zeolite membrane containing, and forming a laminate of the zeolite formed body and the zeolite membrane containing the template agent, and simultaneously calcining the laminate to remove the template agent simultaneously, Of producing a laminated zeolite composite.