JP2003183020A - Production method for zeolite, zeolite prepared thereby, and steam-adsorptive material containing the zeolite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an industrially suitable method for producing zeolite having a desired Si content in a relatively short synthesis time by using a low-priced templet. <P>SOLUTION: This method is characterized in that in producing zeolite having a skeletal structure containing aluminum, phosphorus, and silicon by subjecting a mixture of a silicon source, an aluminum source, a phosphorus source, and a templet to hydrothermal synthesis, the templet used comprises compounds selected from at least two groups of the following three groups: (1) a group consisting of alicyclic heterocyclic compounds having nitrogen atoms as heteroatoms, (2) a group consisting of cycloalkylamines, and (3) a group consisting of alkylamines, provided that at least one compound is selected from each group of the above at least two groups. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a skeleton of Si, A
The present invention relates to a method for producing a zeolite containing 1, P (hereinafter referred to as SAPO), a zeolite obtained by the production method, and a water vapor adsorbent containing the zeolite.

[0002]

2. Description of the Related Art As a method of synthesizing SAPO, a method of hydrothermal synthesis using a template is generally known.
However, for SAPOs having various structures, no systematic study has been made on a method for producing a zeolite having a desired structure and composition on an industrial level.

For example, Japanese Patent Laid-Open No. 59-35018 discloses a method for synthesizing SAPO having various structures, and shows that quaternary ammonium salts and amines are generally used as templates. ing. And C
An example using tetraethylammonium hydroxide (TEAOH) as a template to prepare SAPO-34, which is a SAPO of HA structure, and TEAO.
Examples in which H and di-n-iropropylamine are used in combination are described. When TEAOH is used as a template, SAPO-34 having a desired silicon content can be produced relatively easily, but TEAOH is very expensive and the particle size of SAPO-34 obtained by synthesis is small. Therefore, it is difficult to perform separation operation after synthesis such as filtration. Therefore, from an industrial point of view, selection of a template that does not use TEAOH and that is cheaper, has a large particle size, and is easy to perform a separation operation has been desired.

The Journal of Physical Chemistry Vol.
97, 1993, 8109-8112 discloses a method using an amine as a template. In this example, the composition of the aqueous gel is 0.5SiO ₂ : Al ₂ O ₃ : 0.9P ₂ O ₅ : 2 triethylamine: 60H ₂ O, and the synthesis is carried out at 190 ° C. for 7 days. However, when triethylamine is used as the template, it is inexpensive, but SAPO with the desired skeletal structure is used.
On the other hand, it was difficult to stably produce SAPO-34 having a high purity, which is easily mixed with SAPO having an AFI structure and having a low framework density. In addition, a long synthesis time is required to synthesize high-purity SAPO-34.

Further, morpholine as a template is inexpensive and can be synthesized in a relatively short time by reacting at a high temperature. J. Chem. Soc. Faraday Trans., 1994,
90,2291-2296, in the aqueous gel composition which is usually the reaction raw material for hydrothermal synthesis, SiO ₂ / A
If the ratio of l ₂ O ₃ is 0.3 or less, a pure CHA structure cannot be obtained. For example, if the composition of the aqueous gel is 0.3 SiO ₂ : Al
_When hydrothermal synthesis was carried out at 200 ° C. for 48 hours with ₂ O ₃ : P ₂ O ₅ : 2morpholine: 60H ₂ O, a mixture of SAPO-34 and cristobalite as a dense component was obtained.

In the case of SAPO-34, for example,
S other than including TEAOH as template
There is no reported case where the i content is 9% or less in terms of the molar ratio of silicon to the total of aluminum, phosphorus and silicon having a skeletal structure.

[0007]

In view of widespread industrial use in catalysts and adsorbents, a relatively short synthesis time can be obtained by using an inexpensive template without using an expensive quaternary ammonium salt such as TEAOH. There has been a demand for a production method suitable for industrial production in which a zeolite having a desired Si content is obtained.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that when two or more compounds from a specific compound group are used in combination as a template for hydrothermal synthesis of zeolite, Si Low SAP content
The present invention has been accomplished by finding that O can be produced using an inexpensive template with high purity and in a synthesis time that is industrially applicable.

That is, the first aspect of the present invention is that when a silicon source, an aluminum source, a silicon source and a template are mixed and then hydrothermally synthesized to produce a zeolite containing aluminum, phosphorus and silicon in a skeleton structure, At least one member selected from two or more groups out of three groups of (1) an alicyclic heterocyclic compound containing nitrogen as a hetero atom as a template, (2) cycloalkylamine, and (3) alkylamine A method for producing zeolite is characterized in that the template is a compound selected.

The second subject matter of the present invention lies in the zeolite obtained by the production method. The third gist of the present invention resides in a water vapor adsorbent containing the zeolite.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. Zeolite Production Method The zeolite production method of the present invention is characterized by the type of template used for hydrothermal synthesis. Other manufacturing conditions are not particularly limited, and can be manufactured by a known hydrothermal synthesis method. Usually, after mixing an aluminum source, a silicon source, a phosphorus source and a template, hydrothermal synthesis is performed to remove the template to obtain a zeolite. Hereinafter, an example of the manufacturing method will be described.

First, aluminum source, silicon source, phosphorus
Mix the source and template. Aluminum source The aluminum source is not particularly limited and is usually pseudo boehmite.
Aluminum, aluminum isopropoxide, aluminum tri
Aluminum alkoxides such as ethoxide, hydroxides
With minium, alumina sol, sodium aluminate, etc.
Therefore, pseudo-boehmite is preferable.Silicon source The silicon source is not particularly limited, and is usually fumed silica or silicic acid.
Kasol, colloidal silica, water glass, ethyl silicate,
Fumed silica is preferred, such as methyl silicate.Phosphorus source The source of phosphorus is usually phosphoric acid, but aluminum phosphate is used.
You may stay.template Template is (1) alicyclic ring containing nitrogen as a hetero atom
A heterocyclic compound, (2) cycloalkylamine, and
(3) two or more of three groups of alkylamines
One or more compounds are selected from each group and used.(1) Alicyclic heterocyclic compound containing nitrogen as a hetero atom Hetero of alicyclic heterocyclic compounds containing nitrogen as a hetero atom
The ring is usually a 5- to 7-membered ring, preferably a 6-membered ring.
It The number of heteroatoms contained in a heterocycle is usually 3 or more.
Lower, preferably 2 or less. Heteroatom type
Other than elemental, it is not particularly limited, but contains oxygen in addition to nitrogen
Those are preferable. The position of the hetero atom is not particularly limited
However, it is preferable that the hetero atoms are not adjacent to each other.
The molecular weight is usually 250 or less, preferably 200 or less.
Lower, more preferably 150 or less.

As such alicyclic heterocyclic compounds containing nitrogen as a hetero atom, morpholine, N-methylmorpholine, piperidine, piperazine, N, N'-dimethylpiperazine, 1,4-diazabicyclo (2,2,2 ) Octane, N-methylpiperidine, 3-methylpiperidine, quinuclidine, pyrrolidine, N-methylpyrrolidone, hexamethyleneimine and the like are mentioned, and morpholine, hexamethyleneimine and piperidine are preferable, and morpholine is particularly preferable. (2) Cycloalkylamine The number of cycloalkyl groups in cycloalkylamine is 2 or less, and preferably 1 in 1 molecule of amine. The carbon number of the cycloalkyl group is usually 5 to 7, preferably 6. The number of cyclo rings of cycloalkyl is not particularly limited, but usually 1 is preferable. Further, it is preferable that the cycloalkyl group is bonded to the nitrogen atom of the amine compound. The molecular weight is usually 250 or less, preferably 2
It is 00 or less, more preferably 150 or less.

Such cycloalkylamines include cyclohexylamine, dicyclohexylamine,
Examples thereof include N-methylcyclohexylamine and N, N-dimethylcyclohexylamine, with cyclohexylamine being preferred. (3) Alkylamine The alkyl group of the alkylamine of the present invention is a chain alkyl group and may be contained in one molecule of the amine.
Individuals are particularly preferred. The alkyl group preferably has 4 or less carbon atoms, and more preferably has 10 or less carbon atoms in total in all the alkyl groups in one molecule. The molecular weight is usually 250 or less,
It is preferably 200 or less, more preferably 150 or less.

Examples of such alkylamines include di-n-propylamine, tri-n-propylamine, tri-isopropylamine, triethylamine, triethanolamine, N, N-diethylethanolamine, N,
N-dimethylethanolamine, N-methyldiethanolamine, N-methylethanolamine, di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, t-butylamine, ethylenediamine, di-isopropyl-ethylamine, N- Methyl-n-butylamine and the like, such as di-n-propylamine, tri-n-propylamine, tri-isopropylamine, triethylamine, di-n-butylamine,
Isopropylamine, t-butylamine, ethylenediamine, di-isopropyl-ethylamine, N-methyl-
n-Butylamine is preferred and triethylamine is particularly preferred. Preferable Combination of Templates (1) to (3) As a preferable combination, two or more kinds selected from morpholine, triethylamine and cyclohexylamine, among which morpholine and triethylamine are more preferable. The mixing ratio of each group of these templates needs to be selected according to the conditions. When mixing two templates, usually the molar ratio of the two templates to be mixed is 1:20 to 20: 1, preferably 1:10 to 10: 1, more preferably 1: 5 to 5: 1. Is. When mixing 3 types of template, usually 3
The molar ratio of the template of the seed is 1:20 to 20: with respect to the two templates mixed in the above molar ratio.
1, preferably 1:10 to 10: 1, more preferably 1: 5 to 5: 1.

Other templates may be contained, but the other templates are usually 20% or less, preferably 10% or less in molar ratio with respect to the entire template. SAP with low Si content using the method of the present invention
The reason why O can be synthesized is not clear, but the following is presumed. For example, when synthesizing SAPO having a CHA type structure, an alicyclic heterocyclic compound containing nitrogen as a hetero atom, such as morpholine, is added to Si as described above.
If the content is high, the synthesis is relatively easy, but if you try to synthesize the content of Si is low,
A large amount of dense components and amorphous components are created. As described above, alkylamines such as triethylamine can also be synthesized with CHA-structured SAPO under limited conditions, but usually, SAPOs with various structures are easily mixed. However, conversely, it tends to have a crystalline structure rather than a dense component or an amorphous component. In addition, cycloalkylamines, such as cyclohexylamine, easily form CHA-structure SAPO when the Si content is high, and when the Si-content is low, SA of ERI structure may be obtained under certain conditions.
PO is created and rarely becomes a dense component. That is,
Each template has the characteristics for leading the CHA structure, the characteristics for promoting the crystallization of SAPO, and the like under the limited conditions. It is considered that by combining these features, a synergistic effect was exhibited, and an effect that could not be achieved by itself was exhibited. Synthesis of Zeolite by Hydrothermal Synthesis An aqueous gel is prepared by mixing the above-mentioned silicon source, aluminum source, phosphorus source, template and water. The order of mixing is not limited and may be appropriately selected depending on the conditions used.
Usually, first, a phosphorus source and an aluminum source are mixed with water, and then a silicon source and a template are mixed therewith.

The composition of the aqueous gel is such that when the silicon source, the aluminum source and the phosphorus source are expressed by the molar ratio of oxides,
The value of O ₂ / Al ₂ O ₃ is usually larger than 0 and 0.5 or less, preferably 0.4 or less, more preferably 0.
It is 3 or less. The ratio of P ₂ O ₅ / Al ₂ O ₃ is usually 0.6.
Or more, preferably 0.7 or more, more preferably 0.8
It is above, usually 1.3 or less, preferably 1.2 or less,
More preferably, it is 1.1 or less.

The composition of the zeolite obtained by hydrothermal synthesis has a correlation with the composition of the aqueous gel, and the composition of the aqueous gel may be appropriately set in order to obtain zeolite having a desired composition. The total amount of the template is usually 0.2 or more, preferably 0.5 or more, more preferably 1 or more, and usually 4 or less, preferably 3 or less, and more preferably a molar ratio of the template to Al ₂ O ₃ . It is 2.5 or less.
The mixing ratio of two or more templates needs to be appropriately selected according to the conditions. For example, when morpholine and triethylamine are used, the morpholine / triethylamine molar ratio is 0.05 to 20, preferably 0.1 to 1
It is 0, more preferably 0.2 to 9. The order of mixing one or more templates selected from the two or more groups for each group is not particularly limited, and the template may be mixed with other substances after preparation, or each template may be mixed with other substances. May be mixed with.

The ratio of water to Al ₂ O ₃ is usually 3 or more, preferably 5 or more, more preferably 10 or more and usually 200 or less, preferably 150.
Or less, more preferably 120 or less. The pH of the aqueous gel is usually 5 or higher, preferably 6 or higher, more preferably 6.5 or higher, and usually 10 or lower, preferably 9 or lower, more preferably 8.5 or lower.

If desired, components other than those mentioned above may coexist in the aqueous gel. Such components include alkali metal and alkaline earth metal hydroxides and salts,
Examples include hydrophilic organic solvents such as alcohol. In the case of a hydroxide or salt of an alkali metal or an alkaline earth metal, the ratio of coexistence is usually 0.2 or less, preferably 0.1 or less in terms of a molar ratio with respect to Al ₂ O ₃ , and the ratio of alcohol or the like is In the case of a hydrophilic organic solvent, the molar ratio to water is usually 0.5 or less, preferably 0.3 or less.

The aqueous gel is placed in a pressure resistant vessel and hydrothermally synthesized by maintaining a predetermined temperature under a self-generated pressure or under a gas pressure that does not inhibit crystallization, while stirring or standing. The reaction temperature for hydrothermal synthesis is usually 100 ° C or higher, preferably 120 ° C or higher, more preferably 150 ° C or higher, and usually 300 ° C or lower, preferably 250 ° C or lower, more preferably 220 ° C or lower. Reaction time is usually 2
Time or more, preferably 3 hours or more, more preferably 5
It is not less than 30 hours, usually not more than 30 days, preferably not more than 10 days, more preferably not more than 4 days. The reaction temperature may be constant during the reaction or may be changed stepwise. Although the product is separated after the hydrothermal synthesis of the zeolite containing the template, the method for separating the product is not particularly limited. Usually, the product is separated by filtration or decantation, washed with water, and dried at a temperature from room temperature to 150 ° C. or lower to obtain a product-containing template-containing zeolite. Zeolite obtained by the production method of the present invention and the template is removed from the zeolite containing the template, but the method is not particularly limited. Usually, it is contained by a method such as firing at a temperature of 400 ° C. to 700 ° C. in an inert gas containing air or oxygen, or an atmosphere of an inert gas, or extraction with an extractant such as an ethanol aqueous solution or HCl-containing ether. Organic matter can be removed.

That is, it is possible to synthesize a zeolite having a framework structure in which the molar ratios of aluminum, phosphorus, and silicon are as follows. The abundance ratios of aluminum, phosphorus and silicon atoms in the zeolite are calculated by the following formulas (I), (II) and (II
I) 0.001 ≦ x ≦ 0.3 (I) (In the formula, x represents a molar ratio of silicon to the total of silicon, aluminum and phosphorus in the skeleton structure) 0.3 ≦ y ≦ 0.6 (II) (In the formula, y represents the molar ratio of aluminum to the total of silicon, aluminum and phosphorus of the skeleton structure) 0.3 ≦ z ≦ 0.6 (III) (wherein z Indicates the molar ratio of phosphorus to the total of silicon, aluminum and phosphorus of the skeletal structure) According to the production method of the present invention described above, the molar ratio of silicon to the total of aluminum, phosphorus and silicon of the skeletal structure is 30%. It can be controlled by the following, and the molar ratio of silicon, which has been difficult so far with templates of amines, is 9% or less, preferably 8.7% or less, more preferably 8.5.
% Or less of zeolite can also be synthesized.

That is, the zeolite in which the abundance ratio of silicon is represented by the following formula (IV) 0.001 ≦ x ≦ 0.09 (IV) (wherein x has the same meaning as above) Among them, a zeolite represented by the following formula (V) 0.005 ≦ x ≦ 0.087 (V) (wherein x has the same meaning as above), among which the following formula (VI) 0. 01 ≦ x ≦ 0.085 (VI) (wherein x is as defined above) can be produced, which is particularly preferably used in the water vapor adsorbent described later. .

That is, as shown in the present invention, a combination of amines was used as a template, and S in the starting gel was used.
By controlling the amount of i as described, the desired Si
The content of SAPO can be synthesized. The above atomic ratio is determined by elemental analysis, but in the elemental analysis in the present invention, the sample is heated and dissolved in an aqueous hydrochloric acid solution, and is determined by ICP analysis.

Further, when the zeolite of the present invention is used as a water vapor adsorbent, among the zeolites produced by the above production method, those having the following structure and framework density are preferable. The structure of zeolite is determined by XRD.
The code specified by (IZA) shows AEI, AFR, AF
S, AFT, AFX, AFY, AHT, CHA, DF
O, ERI, FAU, GIS, LEV, LTA, VFI
And AEI, AFX, GIS, CHA, VFI, A
FS, LTA, FAU and AFY are preferred, and zeolite having a CHA structure is most preferred. The framework density is a parameter that reflects the crystal structure.
ZA is ATLAS OF ZEOLITE FRAMEWORK TYPES Fifth Revis
The value shown in ed Edition 2001 is preferably 10.0 T / 1000Å ³ or more, and usually 16.0.
T / 1000Å ³ or less, preferably 15.0 T / 100
0 Å ³ or less. Water vapor adsorbent containing zeolite of the present invention Zeolite having the above structure produced by the present invention shows excellent performance as a water vapor adsorbent, when used as a water vapor adsorbent silica, alumina, metals such as titania It can be used together with a binder component such as an oxide or clay, or a component having high thermal conductivity. At this time,
The content of zeolite is 60% by weight or more of the whole water vapor adsorbent, preferably 70% or more, and more preferably 80% or more.

Further, according to the production method of the present invention, it is possible to produce a zeolite exhibiting excellent adsorption / desorption characteristics. That is, the use of the present invention makes it possible to control the Si content, which makes it possible to manufacture those having adsorption / desorption characteristics under various conditions. this is,
Of course, depending on the conditions, it is generally possible to adsorb from a low temperature to a high temperature region where normal adsorption becomes difficult, and from a high humidity state to a low humidity region where normal adsorption becomes difficult, and at a relatively low temperature. It shows that desorption is possible at 100 ° C or lower.

When such excellent adsorption / desorption characteristics are evaluated by an adsorption isotherm, for example, in the steam adsorption isotherm at 40 ° C., the adsorption amount at a relative vapor pressure of 0.05 is 0.1 g / g or less, And a zeolite having a relative vapor pressure range in which the amount of water adsorbed changes by 0.15 g / g or more when the relative vapor pressure changes by 0.15 in the relative vapor pressure range of 0.05 or more and 0.25 or less, 55 The adsorption amount at a relative vapor pressure of 0.03 is 0.1 g / g or less in the water vapor adsorption isotherm at 0 ° C., and the relative vapor pressure is 0.15 in the range of 0.03 or more and 0.20 or less. When it changes, the change in water adsorption will be 0.1
It is a zeolite having a relative vapor pressure range of 5 g / g or more.

Since the zeolite having this characteristic can desorb the adsorbate at 100 ° C. or lower, it can be used as a water vapor adsorbent having excellent adsorption / desorption characteristics. With such characteristics, it is possible to adsorb under a wide range of conditions from low temperature to high temperature, from low humidity to high humidity, and it is possible to desorb at a relatively low temperature, such as heat pump, desiccant, dehumidification, etc. Available as a drug.

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.

[0030]

Example 1 To 30 g of water, 12.9 g of 85% phosphoric acid and 9.52 g of pseudo-boehmite (containing 25% water, manufactured by Condea) were slowly added and stirred. This was designated as solution A. Fu separately from A liquid
A liquid was prepared by mixing 0.84 g of med silica (Aerosil 200), 6.1 g of morpholine, 7.1 g of triethylamine, and 40 g of water. This was slowly added to Solution A and stirred for 3 hours to obtain an aqueous gel having the following composition. _{0.2SiO 2: Al 2 O 3:} 0.8P 2 O 5: 1 Morpholine:
1 Triethylamine: 60H ₂ O The aqueous gel was charged into a 200 cc stainless autoclave containing a fluororesin inner cylinder, and reacted at 200 ° C. for 24 hours while rotating. After the reaction, the mixture was cooled and the supernatant was removed by decantation to collect the precipitate. The precipitate was washed with water three times, filtered, and dried at 120 ° C. After that, baking was performed at 560 ° C. under an air stream to remove the template.

The XRD of the thus obtained zeolite was measured, and it was found that the CHA structure (framework density = 1
It was 4.6 T / 1,000 Å ³ ). The XRD result is shown in FIG. In addition, when it was heated and dissolved in a hydrochloric acid aqueous solution and subjected to elemental analysis by ICP analysis, the constituent ratio (molar ratio) of each component to the total of skeleton-structure silicon, aluminum, and phosphorus was 6.6% for silicon and aluminum for Four
7.4% phosphorus was 46.1%. Example 2 87.1 g of 85% phosphoric acid was added to 180 g of water, and 57.2 g of pseudo-boehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. This was designated as solution A.
Fumed silica (Aerosil 200) separately from solution A
A liquid was prepared by mixing 5.04 g, morpholine 36.6 g, and water 240 g. This was added slowly to solution A. Further, 47.0 g of triethylamine was added, and this was stirred for 3 hours to obtain an aqueous gel having the following composition. 0.2Si
O ₂ : Al ₂ O ₃ : 0.9P ₂ O ₅ : 1 morpholine: 1.1 triethylamine: 60H ₂ O The mixture thus obtained was charged into a 1 liter stainless steel autoclave containing a fluororesin inner cylinder, and stirred at 100 rpm with 190. The reaction was carried out at 60 ° C for 60 hours. After the reaction, the mixture was cooled and the supernatant was removed by decantation to collect the precipitate. The precipitate was washed with water three times, filtered, and dried at 120 ° C.

When the XRD of the thus obtained zeolite was measured, it had a CHA structure. The measurement result of XRD is shown in FIG. Thereafter, the zeolite from which the template had been removed was calcined in an air stream at 560 ° C. to be dissolved by heating in a hydrochloric acid aqueous solution, and elemental analysis was carried out by ICP analysis. As a result, the composition ratio (molar ratio) of each component to the total of silicon, aluminum and phosphorus was 7.9% for silicon, 48.7% for aluminum and 43.3% for phosphorus.

Further, FIG. 3 shows the water vapor adsorption isotherm at 40 ° C. measured by the zeolite adsorption isotherm measuring device (Belsorb 18: Nippon Bell Co., Ltd.). In addition,
The measurement of the adsorption isotherm is as follows: high temperature air temperature 50 ° C., adsorption temperature 40 ° C., initial introduction pressure 5.0 torr, introduction pressure set point 0, saturated vapor pressure 55.34 mmHg, equilibration time 500.
Went in seconds. Example 3 To 30 g of water, 16.1 g of 85% phosphoric acid and 9.52 g of pseudo-boehmite (containing 25% water, manufactured by Condea) were slowly added and stirred. This was designated as solution A. Fu separately from A liquid
A liquid was prepared by mixing 2.52 g of med silica (Aerosil 200), 6.1 g of morpholine, 7.1 g of triethylamine, and 40 g of water. This was slowly added to Solution A and stirred for 3 hours to obtain an aqueous gel having the following composition. 0.6SiO ₂ : Al ₂ O ₃ : 1P ₂ O ₅ : 1morpholine: 1 triethylamine: 60H ₂ O The aqueous gel was charged into a 200 cc stainless steel autoclave containing a fluororesin inner cylinder, and while rotating, 1
After reacting at 90 ° C. for 24 hours, the temperature is raised to 200 ° C. and 24
Reacted for hours. After the reaction, the mixture was cooled and the supernatant was removed by decantation to collect the precipitate. Precipitate with water 3
After washing twice, it was filtered and dried at 120 ° C. When the XRD of this zeolite was measured, it had a CHA structure.
The result of XRD is shown in FIG.

Further, after baking at 560 ° C. under air flow to remove the template, the template was dissolved by heating with an aqueous hydrochloric acid solution, and ICP analysis was carried out. Constituent ratio (molar ratio) of each component to the total of silicon, aluminum and phosphorus in the skeletal structure
As a result of elemental analysis, silicon was 11.6%, aluminum was 49.0%, and phosphorus was 39.4%. Example 4 To 15 g of water, 6.46 g of 85% phosphoric acid and 4.76 g of pseudo-boehmite (containing 25% water, manufactured by Condea) were slowly added and stirred. This was designated as solution A. Fu separately from A liquid
A mixture of 0.63 g of med silica (Aerosil 200), 5.18 g of morpholine, 1.04 g of cyclohexylamine, and 20 g of water was slowly added to the solution A and stirred for 3 hours to have the following composition. An aqueous gel was prepared. _{0.3SiO 2: Al 2 O 3:} 0.8P 2 O 5: 1.7 morpholine: 0.
3 Cyclohexylamine: 60H ₂ O The aqueous gel was charged into a 200 cc stainless steel autoclave containing a fluororesin inner cylinder, and was rotated while rotating.
The reaction was carried out at 0 ° C for 72 hours. After the reaction, the mixture was cooled and the supernatant was removed by decantation to collect the precipitate. The precipitate was washed with water three times, filtered, and dried at 120 ° C. to obtain zeolite. When the XRD of this zeolite was measured, it had a CHA structure. The result of XRD is shown in FIG.

Further, after firing at 560 ° C. in an air stream to remove the template, the template was dissolved by heating in an aqueous solution of hydrochloric acid and subjected to elemental analysis by ICP analysis. As a result of elemental analysis, the composition ratio (molar ratio) of the components is that silicon is 7.4%, aluminum is 49.1%, and phosphorus is 43.5%.
%Met. For elemental analysis, the sample was heated and dissolved in an aqueous hydrochloric acid solution, and ICP analysis was performed. Comparative Example 1 57.7 g of 85% phosphoric acid was added to 105.8 g of water, and pseudo boehmite (containing 25% water, manufactured by Condea) 34.0 was added thereto.
g was added slowly and stirred for 3 hours. This was designated as solution A. Separated from liquid A, fumed silica (Aerosil 20
0) 3.01 g, morpholine 48.6 g, water 147.4
Make a liquid mixed with g and add it slowly to liquid A,
After stirring for 7 hours, an aqueous gel having the following composition was obtained. _{0.3SiO 2: Al 2 O 3:} 0.8P 2 O 5: 2 Morpholine: 60H
₂ O The aqueous gel was charged into a 0.5 l stainless steel autoclave containing a fluororesin inner cylinder, and reacted at 190 ° C. for 48 hours while stirring at 100 rpm. After the reaction, the mixture was cooled and the supernatant was removed by decantation to collect the precipitate. The precipitate thus obtained is washed with water and then filtered off,
It was dried at 120 ° C. When the XRD of this zeolite was measured, it was a mixture of the CHA structure and the tridymite phase which is the dense component. The result of XRD is shown in FIG. Comparative Example 2 8.07 g of 85% phosphoric acid was added to 15 g of water, and 4.76 g of pseudo-boehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 2 hours. This was designated as solution A. A
Separated from the liquid, fumed silica (Aerosil 200) 0.
A liquid was prepared by mixing 42 g, triethylamine 7.14 g and water 20 g, and this was slowly added to the liquid A and stirred for 3 hours to obtain an aqueous gel having the following composition. 0.2SiO ₂ : Al ₂ O ₃ : 1P ₂ O ₅ : 2 triethylamine:
60H ₂ O The aqueous gel was placed in a 200 cc stainless autoclave containing a fluororesin inner cylinder and reacted at 200 ° C. for 24 hours. After the reaction, the mixture was cooled and the supernatant was removed by decantation to collect the precipitate. The precipitate was washed with water, filtered, and dried at 120 ° C. X of this zeolite
When RD was measured, most of them had an AFI structure with a large framework density (framework density = 17.3T).
It was / 1,000Å3). The XRD result is shown in FIG. Comparative Example 3 8.07 g of 85% phosphoric acid was added to 15 g of water, and 4.76 g of pseudo-boehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 2 hours. This was designated as solution A. A
Separated from the liquid, fumed silica (Aerosil 200) 0.
A liquid was prepared by mixing 84 g, cyclohexylamine 6.9 g and water 20 g, and this was slowly added to the liquid A and stirred for 3 hours to obtain a gel mixture having the following composition. 0.4SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 2 cyclohexylamine: 60H ₂ O The mixture was charged into a 0.2 l stainless steel autoclave containing a fluororesin inner cylinder and allowed to react at 200 ° C. for 24 hours while rotating. It was After the reaction, the mixture was cooled and the supernatant was removed by decantation to collect the precipitate. The precipitate thus obtained was washed with water, filtered, and dried at 120 ° C. When the XRD of this zeolite was measured, it showed an XRD pattern in the form of a layered material and no CHA structure was observed. The XRD result is shown in FIG. Example 5 7.25 g of 85% phosphoric acid was added to 15 g of water, and 4.76 g of pseudo-boehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. This was designated as solution A. A
Separated from the liquid, fumed silica (Aerosil 200) 0.
A liquid was prepared by mixing 63 g and 20 g of water. This was added slowly to solution A. Further, 4.5 g of diisopropylethylamine was added, and further 3.0 g of morpholine was added.
This was stirred for 3 hours to obtain an aqueous gel having the following composition. 0.3SiO ₂ : Al ₂ O ₃ : 0.9P ₂ O ₅ : 1 morpholine: 1 diisopropylethylamine: 60H ₂ O
It was charged in a 1 liter stainless steel autoclave and allowed to react at 170 ° C. for 7 days in a stationary state. After the reaction, the mixture was cooled and the supernatant was removed by decantation to collect the precipitate.
The precipitate was washed with water three times, filtered, and dried at 120 ° C.

When the XRD of the thus obtained zeolite was measured, it had a CHA structure. After that, 560 ℃
FIG. 9 shows an XRD diagram of the zeolite from which the template was removed by firing in an air stream at. This was heated and dissolved in an aqueous hydrochloric acid solution, and elemental analysis was performed by ICP analysis. As a result, the composition ratio (molar ratio) of each component to the total of silicon, aluminum, and phosphorus was 7.7% for silicon, 49.8% for aluminum, and 42.4% for phosphorus.

Further, FIG. 10 shows the water vapor adsorption isotherm at 55 ° C. measured by the zeolite adsorption isotherm measuring device (Belsorb 18: Nippon Bell Co., Ltd.). The adsorption isotherm was measured at an air high temperature tank temperature of 60 ° C., an adsorption temperature of 55 ° C., an initial introduction pressure of 5.0 torr, an introduction pressure set point of 0, a saturated vapor pressure of 118.11 mmHg, and an equilibration time of 500 seconds.

[0038]

According to the present invention, it becomes possible to produce a silicoaluminophosphate whose Si content can be controlled by using an inexpensive template. Such zeolite can be widely used for industrially desired catalysts and adsorbents. For example, a water adsorbent that exhibits special adsorption performance can be manufactured at low cost.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction diagram showing a crystal structure of zeolite obtained in Example 1.

FIG. 2 is an X-ray diffraction diagram showing a crystal structure of zeolite obtained in Example 2.

FIG. 3 is a steam adsorption isotherm of the zeolite obtained in Example 2.

FIG. 4 is an X-ray diffraction diagram showing a crystal structure of zeolite obtained in Example 3.

5 is an X-ray diffraction diagram showing a crystal structure of the zeolite obtained in Example 4. FIG.

FIG. 6 is an X-ray diffraction diagram showing a crystal structure of zeolite obtained in Comparative Example 1.

FIG. 7 is an X-ray diffraction diagram showing a crystal structure of zeolite obtained in Comparative Example 2.

8 is an X-ray diffraction diagram showing a crystal structure of zeolite obtained in Comparative Example 3. FIG.

9 is an X-ray diffraction pattern showing the crystal structure of the zeolite obtained in Example 5. FIG.

FIG. 10 is a steam adsorption isotherm of the zeolite obtained in Example 5.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Watanabe Exhibition             1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa             Within Mitsubishi Chemical Corporation (72) Inventor Masanori Yamazaki             1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa             Within Mitsubishi Chemical Corporation F-term (reference) 4G066 AA61A AA61B BA36 CA43                       DA01 EA20 FA03 FA20 FA21                       GA06                 4G073 BB12 BB41 BB44 BB47 BB70                       CZ59 FB01 FB02 FB50 UA06

Claims (16)

[Claims] 1. When producing a zeolite containing aluminum, phosphorus and silicon in the skeletal structure by hydrothermally synthesizing a silicon source, an aluminum source, a phosphorus source and a template, (1) nitrogen as a hetero atom is used as a template. An alicyclic heterocyclic compound containing, a (2) cycloalkylamine, and (3) an alkylamine, using a template in which one or more compounds are selected from each of two or more groups. A method for producing zeolite, which is characterized. 2. The method for producing a zeolite according to claim 1, wherein the template contains an alicyclic heterocyclic compound containing nitrogen as a hetero atom. 3. The method for producing a zeolite according to claim 1, wherein the template contains (1) an alicyclic heterocyclic compound containing nitrogen as a hetero atom and (2) a cycloalkylamine. 4. The method for producing a zeolite according to claim 1, wherein the alicyclic heterocyclic compound containing nitrogen as a hetero atom is morpholine. 5. The method for producing a zeolite according to claim 1, wherein the cycloalkylamine is cyclohexylamine. 6. The method for producing a zeolite according to claim 1, wherein the alkylamine is triethylamine. 7. A mixing ratio of a silicon source, an aluminum source and a phosphorus source is a molar ratio of oxides of the aluminum source, the silicon source and the phosphorus source in the composition of the aqueous gel, and SiO.
₂ / Al ₂ O ₃ value is 0.5 or less, P ₂ O ₅ / Al ₂ O
_The method for producing a zeolite according to claim 1, wherein the value of ₃ is 0.6 or more. 8. A zeolite obtained by the method according to claim 1. 9. The zeolite according to claim 8, wherein the zeolite is a zeolite in which the abundance ratios of atoms of silicon, aluminum and phosphorus are represented by the following formulas (I), (II) and (III). 0.001 ≦ x ≦ 0.3 (I) (wherein x represents a molar ratio of silicon to the total of aluminum, phosphorus, and silicon of the skeleton structure) 0.3 ≦ y ≦ 0.6 .. (II) (In the formula, y represents a molar ratio of aluminum to the total of aluminum, phosphorus, and silicon of the skeleton structure) 0.3 ≦ z ≦ 0.6 (III) (wherein, z Indicates the molar ratio of phosphorus to the total of skeletal structure aluminum, phosphorus, and silicon) 10. The zeolite according to claim 9, wherein the zeolite has a silicon content represented by the following formula (IV). 0.001 ≦ x ≦ 0.09 (IV) (In the formula, x represents the molar ratio of silicon to the total of aluminum, phosphorus, and silicon in the skeleton structure) 11. Zeolite is International
al Zeolite Association (IZ
The zeolite structure according to any one of claims 8 to 10, wherein the framework structure has a framework density of 10.0 or more and 16.0 T / 1000 A ³ or less in the zeolite structure defined by A). 12. Zeolite is International
al Zeolite Association (IZ
The zeolite according to claim 11, which is CHA in the zeolite structure defined by A). 13. A water vapor adsorbent containing the zeolite according to any one of claims 8 to 12. 14. The water vapor adsorbent according to claim 13, wherein the content of zeolite is 60% by weight or more based on the whole water vapor adsorbent. 15. Zeolite has an adsorption amount of 0.1 g / at a relative vapor pressure of 0.05 on a water vapor adsorption isotherm at 40 ° C.
g or less and relative vapor pressure of 0.05 or more, 0.25
The water vapor adsorbent according to claim 13 or 14, which has a relative vapor pressure range in which a change in the amount of water adsorbed when the relative vapor pressure changes by 0.15 in the following range is 0.15 g / g or more. 16. The amount of zeolite adsorbed at a relative vapor pressure of 0.03 on a water vapor adsorption isotherm at 55 ° C. of 0.1 g /
g or less and relative vapor pressure of 0.03 or more and 0.20
The water vapor adsorbent according to claim 13 or 14, which has a relative vapor pressure range in which a change in the amount of water adsorbed when the relative vapor pressure changes by 0.15 in the following range is 0.15 g / g or more.