JP2001058817A - Binderless crystalline aluminosilicate formed product, its production and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molded product without substantially any Al present on the outside of the crystal lattice by providing an aluminosilicate with a ZSM-5 type crystal structure and regulating the compositional ratio of Si and Al constituting the crystal structure within a specific range and further the Al content on the outside of the crystal lattice within a specified range. SOLUTION: An aluminosilicate in a molded product has a ZSM-5 type crystal structure. The compositional ratio (atomic ratio) of Si to Al constituting the crystal structure is 1:(0.0001-0.5) of Si:A1. The content of Al on the outside of the crystal structure in the molded product is extremely small such as <=3 mass % of the total A.1 in the molded product which has preferably 300-550 m2/g specific surface area according to the BET method. Furthermore, the molded product preferably has macropores having >=4 nm pore diameter determined by a mercury intrusion method, 2-150 m2/g surface area of the pores and 0.15-1.5 mL/g pore volume of the pores.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binderless crystalline aluminosilicate molded product of the ZSM-5 type, a method for producing the same and a use thereof. More specifically, the present invention relates to a ZSM-5 type binderless crystalline aluminosilicate molded product, a method for producing the same, a catalyst for an amination reaction, and a method for producing an alkyleneamine using the catalyst.

[0002]

2. Description of the Related Art ZSM-5 type aluminosilicate is disclosed in U.S. Pat. No. 3,702,886.
It is a zeolite having 0-membered ring pores.

As a method for synthesizing a ZSM-5 type aluminosilicate, a hydrothermal synthesis method using an aqueous reaction slurry using tetra-n-propylammonium ion as a template agent as a raw material is conventionally known.

However, in the conventional hydrothermal synthesis reaction,
Since a part of the raw material components are dissolved in water during heating, not only does the ratio of the component converted into the target crystal necessarily decrease, but also the crystallization time becomes extremely long due to the low concentration of the alkali component. In such a slow crystallization method,
Since the large crystals are easy to grow and the foreign metal ions other than silicon are easily removed out of the crystal lattice, the Si / Al atomic ratios of the aqueous slurry as the raw material and the synthesized ZSM-5 type zeolite are compared. They did not always match. Further, industrially, since the aqueous slurry is heated, a large-volume closed container is required relatively to the mass of the generated crystals, or a large amount of expensive template agent is required, Furthermore, there are problems such as generation of a large amount of waste liquid, filtration of the zeolite powder, and complicated firing steps.

In the case of producing a zeolite molded body, it is necessary to first synthesize a zeolite powder by a hydrothermal synthesis method and then to mold using an inorganic binder, because the moldability of zeolite alone is poor. Was. In this method, it is necessary to select a binder so as not to adversely affect the use of the obtained zeolite, and in order to achieve a sufficient strength, a large amount of an inorganic binder is required. Not only does the zeolite content decrease, but also the zeolite is buried in the binder and cannot be used effectively.

[0006] In order to solve such problems, there has been proposed a method for producing a zeolite molded article substantially containing no binder. For example, Japanese Unexamined Patent Publication No. Sho 59-162952
Japanese Patent Application Laid-Open No. Sho 61-61 discloses a TSZ type aluminosilicate.
JP-A-72620 describes a MOR-type aluminosilicate, and JP-A-62-138320 describes a crystal-type binderless aluminosilicate molding such as an FAU-type aluminosilicate. In these methods, a pre-synthesized zeolite powder is used as a secondary material, which is molded with an inorganic binder such as a clay mineral or silica-alumina, and the binder is converted into zeolite by reacting with an alkaline solution. Substantially two hydrothermal synthesis steps are required. For this reason, there are problems in that the manufacturing process is lengthened and the amount of waste liquid is increased. Furthermore, in this method, the Si / Al ratio of the secondary raw material zeolite and the inorganic binder Si / Al
It is necessary to match the Al ratio, and if the content of aluminum in the inorganic binder is low, the moldability deteriorates. Therefore, a binderless crystalline aluminosilicate molded body having a high silica content could not be produced. In addition, since the crystallization is performed twice by the hydrothermal synthesis method, aluminum is hardly taken into the zeolite lattice, and there is a problem that such aluminum is included in the product as an impurity.

As described above, heretofore, there has been no known ZSM-5 type binderless aluminosilicate molded body in which aluminum does not substantially exist outside the crystal lattice.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention has been made in view of the above-mentioned problems, and is directed to a ZSM-5 type binderless crystalline alumino in which aluminum is substantially not present outside the crystal lattice. An object of the present invention is to provide a silicate molded body, a method for producing the same, and a use as an amination catalyst.

[0009]

Means for Solving the Problems The present inventors have developed ZSM-5.
About the mold binderless aluminosilicate molded body,
As a result of intensive studies, for example, after supporting an aluminum component, an alkali metal component, and a tetraalkylammonium component on a silica molded body, by contacting with saturated steam under specific conditions, the total amount of aluminum and silica is contained in the lattice. ZS which can be converted into the incorporated ZSM-5 type aluminosilicate and which maintains the shape of the raw silica molded product and which is substantially free of aluminum outside the crystal lattice
The inventors have found that an M-5 type binderless crystalline aluminosilicate molded body can be produced, and have completed the present invention.

That is, the present invention relates to a binderless crystalline aluminosilicate molded article, wherein the aluminosilicate has a ZSM-5 type crystal structure, and a composition ratio (atomic ratio) of silicon and aluminum constituting the crystal structure. ) Is based on silicon and aluminum is 0.0001 to 0.5.
Wherein the content of aluminum outside the crystal lattice is 3% or less of the total aluminum contained in the molded body, and a binderless crystalline aluminosilicate molded body.

The binderless crystalline aluminosilicate molded article of the present invention preferably has a specific surface area of 300 to 550 m ² / g determined by nitrogen adsorption measurement by the BET method.

The binderless crystalline aluminosilicate molded article of the present invention has a pore diameter of 4 determined by a mercury intrusion method.
nm or more, and the surface area of the pores is 2 to 150 m
² / g and the pore volume of the pores is 0.15 to
It is preferably 1.5 ml / g.

Further, another invention of the present invention provides the following formula (1)
In represented aluminosilicate _{precursor: Si 1 Al x M y (} SDA) z (1) ( In the formula, M represents an alkali metal, SDA represents a tetraalkylammonium, x is from 0.0001 to 0.
5, y represents the range of 0.0001 to 1, and z represents the range of 0.001 to 1. ) Is contacted with saturated steam to produce a binderless crystalline aluminosilicate molded article.

The aluminosilicate precursor is preferably obtained by supporting a raw material containing an aluminum component, an alkali metal component and a tetraalkylammonium component on a silica molded body.

Still another aspect of the present invention relates to a catalyst for an amination reaction, comprising the binderless crystalline aluminosilicate molded product.

According to another aspect of the present invention, there is provided the use of the above-mentioned catalyst,
The present invention relates to a method for producing an alkylene amine, which comprises aminating an alkylene oxide with ammonia.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The binderless crystalline aluminosilicate molded aluminosilicate precursors used in the production of the present invention has the following formula _{(1): Si 1 Al x} M y (SDA) z (1) ( In the formula, M is an alkali metal, SDA is a tetraalkylammonium, preferably an alkyl group having 1 to 5 carbon atoms, x is 0.0001 to 0.5, and y is 0.0
001 to 1 and z represent a range of 0.001 to 1. ) Is not particularly limited.

Further, in the above formula (1), x is equal to 0.1.
0001 to 0.5, y is 0.0001 to 1, z is 0.0
It is preferably in the range of 02 to 1, and especially x is 0.0
005 to 0.3, y is 0.0005 to 0.5, and z is 0.
It is desirable to be in the range of 003 to 0.8.

The method for preparing the aluminosilicate precursor is not particularly limited, but a method in which a raw material containing an aluminum component, an alkali metal component and a tetraalkylammonium component is supported on a silica molded body is preferred.

In the method of the present invention, a silica molding is used as a silica source of the crystalline aluminosilicate. The silica molded body is not particularly limited, and a commercial product may be used. As the silica molded body, those having a relatively large specific surface area are suitably used, and the specific surface area obtained from the nitrogen adsorption measurement by the BET method is usually 5 to 5.
800 m ² / g, it is desirable that preferably in the range of 20~600m ² / g. If the specific surface area is too small, crystallization takes a long time and the degree of crystallization may be low.

The silica molded body has pores having a pore diameter of, for example, 4 nm or more determined by a mercury intrusion method,
The surface area based on the pores is 5 to 800 m ² / g, preferably 20 to 600 m ² / g, and the pore volume based on the pores is 0.1 to 1.5 ml / g, preferably 0.2 to 1.
It is in the range of 3 ml / g.

Further, the shape is not particularly limited, and examples thereof include a spherical shape, a cylindrical shape, and a ring shape. The size is not limited, but is usually preferably in the range of 0.5 to 10 mm (equivalent to the diameter).

Although the mechanical strength of the silica molded body is not limited, it is usually 9.8 Newton or more, preferably expressed as a value measured by a Kiya type hardness meter (average value of 10 molded bodies). Is preferably in the range of 9.8 to 490 Newtons. Since the mechanical strength of the silica molded product has a correlation with the mechanical strength of the obtained binderless crystalline aluminosilicate molded product, by using a high-strength silica molded product, a binderless material having sufficient strength for practical use can be obtained. A crystalline aluminosilicate molded body can be manufactured.

The tetraalkylammonium component includes tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetraisopropylammonium, tetra-n-butylammonium, tetra-n-pentylammonium, triethylmethylammonium, triethyl-n Halides such as -propylammonium, tri-n-propylmethylammonium, tri-n-butylmethylammonium,
Hydroxides and the like can be exemplified, and a compound having 1 to 5 carbon atoms in the alkyl group of the tetraalkylammonium component is preferable, a compound containing a tetra-n-propylammonium ion is more preferable, and particularly preferable is tetra-n.
-Purpyrlammonium hydroxide. Tetra-
By using an n-propyl ammonium salt, ZS
This is because the M-5 type aluminosilicate can be efficiently synthesized.

As the alkali metal component, lithium, sodium and potassium can be presented, and hydroxides and halides thereof, or alkali metal components in aluminum compounds such as silica carriers and aluminates can be used.

Examples of the aluminum component include aluminates, nitrates, sulfates, halides, hydroxides and the like. Further, it is preferably used in the form of an aqueous solution. Usually, sodium aluminate is preferred.

In the above method for preparing an aluminosilicate precursor, at least one kind selected from the group consisting of boron, titanium, copper, indium, chromium, iron, cobalt, nickel, zinc and gallium is further provided on the silica molded body. By coexisting the element (A), a bi (poly) metallic binderless ZSM-5 type metalloaluminosilicate molded body in which these elements are incorporated in the lattice can be obtained.

The T of these zeolites, such as aluminum,
The metal component to be an atom (metal component constituting the zeolite crystal skeleton) may be in any form as long as it is supported on a silica molded body. For example, you may use the oxide of the said metal contained in a silica molded object. Usually, a water-soluble salt is preferable as the supported metal salt. A precursor supported as a metal oxide can also be used by impregnating with an aqueous solution of a metal salt, drying and baking. In this case,
A metal component and / or an alkali metal component to be a T atom are supported on a silica molded body and fired to obtain a silica molded body supporting the above components. A zeolite precursor is prepared by supporting a tetraalkylammonium component and, if necessary, an alkali metal component. By using such a zeolite precursor, the mechanical strength of the molded zeolite may be increased in some cases.

The method of supporting a raw material containing an aluminum component, an alkali metal component and a tetraalkylammonium component on the silica molded body is not particularly limited, but the raw material is uniformly dispersed in the silica molded body. In order to be supported on a silica material, it is desirable to include a method in which an aqueous solution of the raw material is included in a silica molded body and then dried. As an example, a predetermined amount of each component is made into a uniform aqueous solution, and is prepared and impregnated so as to have an aqueous solution amount corresponding to the water absorption amount of the silica molded body. At this time, each component may be supported at the same time, or each component or a uniform mixed solution may be supported by dividing it into several times. Even if the support is divided, the order of loading does not affect the product. Thereafter, the water content in the precursor is reduced by a drying step. The water content of the precursor is usually 30% by mass or less, based on the total mass of the precursor after drying, from the viewpoint that the supported component is not eluted during crystallization and the yield of zeolite is good. The range of 20 to 0.1% by mass is preferred.

The drying temperature after the impregnation with the aqueous solution is not particularly limited, but is usually from 20 to 120 ° C., preferably from 50 to 120 ° C., since the decomposition of the tetraalkylammonium salt is small.
It is in the range of 120 ° C.

The method of drying is not particularly limited, and may be any of reduced pressure and normal pressure. Drying under an air stream at normal pressure is preferred for convenience.

The production method of the present invention is characterized in that the aluminosilicate precursor is brought into contact with saturated steam.

The temperature of the saturated steam is not particularly limited as long as the aluminosilicate precursor is converted into zeolite, but the decomposition of the tetraalkylammonium component contained therein is small, and the ZSM-5 type binderless zeolite molding having high crystallinity is formed. Usually 80-260 to get body
C, preferably in the range of 100 to 230C.

The contact time between the aluminosilicate precursor and saturated steam is usually 2 hours or more, preferably 2 to 2 hours.
The range is 150 hours. If the crystallization time is too short, the degree of crystallinity will decrease, and if it is too long, mixed crystals with other zeolites may be formed.

The method and apparatus for bringing the aluminosilicate precursor into contact with saturated steam are not particularly limited as long as the aluminosilicate precursor is converted to zeolite. For example, it can be carried out by placing a precursor in the hollow of a pressure-resistant container, filling water corresponding to the amount of saturated steam determined by the reaction temperature and the volume of the container in the lower part of the container, and then heating in a constant temperature bath. Also, put this precursor in a container,
A closed vessel containing water on the outside thereof may be used, or may be continuously synthesized by a moving bed reactor.

In the method of the present invention, the aluminosilicate precursor is dispersed in water without performing a hydrothermal reaction,
Crystallization can be performed. In the method of the present invention, almost the entire amount of the raw material can be converted into zeolite, and the silica molded body as the raw material is entirely converted into zeolite while maintaining the shape. Will not be included. Thus, a binderless crystalline aluminosilicate molded body can be obtained by a simple method.

Since no binder is used in the method of the present invention, the synthesized binderless crystalline aluminosilicate molded article has a very high crystallinity with a zeolite content of almost 100%. The degree of crystallinity can be controlled by appropriately selecting the composition ratio of the precursor, the crystallization temperature and the crystallization time from the above conditions. The crystallinity of the molded body is usually 95% or more, preferably 98% or more. The crushing strength can be controlled by the crystallinity. For example, as measured by a Kiya hardness tester, it is desirably 1 Newton or more, preferably 5 Newton or more.
The pore volume in the range of 150 nm, including the average pore diameter,
It has a sharp pore distribution of 60% or more, preferably 70% or more of the total macropore volume of 4 nm or more in pore diameter.

Further, according to the production method of the present invention, a silica molded article having an arbitrary shape such as a sphere, a cylinder and a ring can be used as a raw material. By converting a precursor prepared from a silica molded article having an arbitrary shape into zeolite by the method of the present invention, a binderless crystalline aluminosilicate molded article can be obtained as it is.

Further, in the production method of the present invention, not only the appearance of the raw silica molded body is maintained, but also the crushing strength, macropore distribution, and the like are reflected. For this reason, the physical properties of the binderless crystalline aluminosilicate molded article can be easily controlled by controlling the physical properties of the silica molded article used as a raw material.

Specifically, the following binderless crystalline aluminosilicate molded product is obtained.

An aluminum component, tetra-n-propylammonium as a tetraalkylammonium component, and an alkali metal component are supported on a silica molded body as an aluminosilicate precursor. In this case, binderless ZSM-5 containing silicon and aluminum as T atoms
A shaped aluminosilicate molded body is obtained. Here, the composition ratio (atomic ratio) of each component is the silica molding (as Si)
Assuming that 1, the ratio of the aluminum component, the tetraalkylammonium component, and the alkali metal component is usually 0.0
001-0.5: 0.001-1: 0.0001-1,
Preferably 0.0001 to 0.5: 0.002 to 1:
0.0001 to 1, more preferably 0.0005 to
The range of 0.3: 0.003 to 0.8: 0.0005 to 0.5 is desirable. Examples of the tetraalkylammonium component include tetra-n-propylammonium halide and hydroxide. Particularly, tetra-n-propyl ammonium hydroxide is preferred. As the aluminum component, a water-soluble salt is preferable. Aluminates, nitrates, sulfates, halides and the like can be exemplified, but sodium aluminate is preferred. Further, in addition to the three components, boron, titanium, chromium, iron, cobalt,
It can carry at least one metal component selected from the group consisting of nickel, copper, zinc, gallium and indium. In this case, a binderless ZSM-5 type metalloaluminosilicate molded body (the framework topology code by the International Zeolite Society is MFI type) in which this component is incorporated as a T atom can be produced.

The binderless crystalline aluminosilicate molded article of the present invention has the following features (i) to (iii).

(I) The aluminosilicate has a ZSM-5 type crystal structure.

(Ii) The composition ratio (atomic ratio) between silicon and aluminum constituting the aluminosilicate crystal structure is such that aluminum is 0.0001 to 0.5 with respect to silicon 1;
Preferably, the range is 0.0005 to 0.3.

(Iii) The content of aluminum outside the crystal lattice is 3% or less of the total aluminum contained in the molded body.

The aluminosilicate in the molded article of the present invention has a ZSM-5 type crystal structure. This is powder X
It can be confirmed by measurement of line diffraction.

The structure of the ZSM-5 type aluminosilicate is a three-dimensionally bonded SiO ₄ and AlO ₄ tetrahedron composed of silicon atoms or aluminum atoms and four oxygen atoms coordinated at the apexes. are doing. For this reason,
It is well known that all aluminum atoms entering the zeolite framework are tetracoordinated, while aluminum atoms outside the lattice that are off the framework are usually hexacoordinated. These two types of aluminum atoms are, for example, Al
^It can be easily distinguished or quantified by ²⁷ MAS-NMR measurement. Chemical shift (σ) 5 attributed to tetracoordinate aluminum
The area of the peak measured in the range of 0 to 70 ppm and the area of the peak observed in the range of σ = 0 to 10 ppm belonging to hexacoordinate aluminum were determined, and based on the area ratio, the molding obtained in the present invention was used. The percentage of off-lattice aluminum relative to the total amount of aluminum contained in the body is determined.

The molded article of the present invention is characterized in that the aluminum component outside the zeolite lattice is extremely small. A
The off-lattice aluminum abundance calculated by measurement of l ²⁷ MAS-NMR was 3% by mass of the total aluminum in the molded body
Or less, preferably 2% by mass or less, more preferably substantially not contained (not detected). In addition, the degree of non-crystallinity of the molded article is presumed to be derived from a silica component which is not converted into zeolite.

In the molded product of the present invention, the composition ratio (atomic ratio) of silicon and aluminum constituting the aluminosilicate crystal structure in the molded product is generally 0.0001 to 0 with respect to silicon. .5, preferably 0.00
The range is from 0.5 to 0.3.

Further, the specific surface area of the molded body obtained from the nitrogen adsorption measurement by the BET method is, for example, 300 to 55.
0 m ² / g, preferably in the range of 315~500m ² / g.

Further, the molded article has macropores having a pore diameter of 4 nm or more determined by a mercury intrusion method. The surface area of the pores is usually in the range of ^{2 to} 150 m ² / g, preferably 4 to 100 m ² / g. The pore volume of the pores is usually in the range of 0.15 to 1.5 ml / g, preferably 0.2 to 1.3 ml / g.

Since the binderless crystalline aluminosilicate molded article of the present invention can easily control the shape, size, macropore distribution, etc., in various chemical processes, it can be used as an adsorbent, a catalyst for a chemical reaction, or a catalyst. It can be used as a carrier. For example, it is suitably used as a catalyst for an alkylation reaction, a catalyst for an isomerization reaction, a catalyst for a cracking reaction, a catalyst for a Beckmann rearrangement reaction, a catalyst for a hydration reaction, a catalyst for an alcohol addition reaction, and the like.

When a zeolite molded body using a conventional inorganic binder is used as a catalyst, the catalyst activity is lower than that of the original zeolite catalyst, the strength of the catalyst molded body is weak, and various impurities are produced as by-products. There are problems such as points to do. The binderless crystalline aluminosilicate molded article of the present invention does not have these problems, and is excellent because the intrinsic catalytic performance of zeolite can be exhibited.

Further, in various amination reactions, the adverse effect of the inorganic binder is large, and therefore, it is preferable to use the binderless crystalline aluminosilicate molded article of the present invention, which does not use a binder, as a catalyst. Examples of the amination reaction include a reaction of aminating an alkylene oxide with ammonia to synthesize alkanolamines, an ammonia addition reaction to an olefin, an N-alkylation reaction with an alcohol represented by the synthesis of methylamines, and a ring of ethanolamines. A dehydration reaction and a synthesis reaction of ethylenediamine from monoethanolamine and ammonia can be exemplified. Conventional conditions can be employed for the reaction conditions for aminating the alkylene oxide with ammonia to synthesize alkanolamines. Preferably, the following conditions are satisfied.

The molar ratio of ammonia to alkylene oxide is usually in the range of 1 to 50: 1, preferably 2 to 40: 1. The reaction temperature is usually 20 to 300 ° C,
Preferably it is in the range of 30 to 200 ° C. The reaction pressure is usually 2 to 30 MPa, preferably 4 to 20 MPa.
Range. LHSV (hr ^-1 ) is usually 0.1 to
50, preferably in the range of 0.5 to 30.

In the alkanolamine synthesis reaction, for example, a process for producing ethanolamines using ethylene oxide and ammonia can be mentioned. Usually, when a zeolite catalyst molded with an inorganic binder is used, the activity decreases, generation of impurities such as diglycolamines,
There are problems such as a point that the strength of the molded body is weak and a decrease in diethanolamine selectivity. This is attributable to the effect of diluting the catalyst component due to the addition of the inorganic binder and the chemical properties of the inorganic binder. Therefore, it is particularly preferable to use the binderless zeolite molded article of the present invention which does not contain an inorganic binder and has sufficient strength as a catalyst or a catalyst carrier. In this case, it is preferable that the crystalline structure of the crystalline aluminosilicate be ZSM-5 type (the framework topology is MFI type according to the International Zeolite Society) because it shows high diethanolamine selectivity.

[0058]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.

In the examples, the following measuring methods were used.

Measurement method of mechanical strength Measured using a Kiya type hardness tester. It was represented by the average value of 10 molded bodies.

Method for measuring the content of zeolite Confirmed by powder X-ray diffraction. It is measured as the ratio of the sum of the peak areas attributed to zeolite to the sum of all the peak areas that are present in the CuKα X-ray diffraction measured at 2θ = 5 to 140 °. A zeolite content of almost 100% means that no peak other than zeolite is observed as a result of the measurement under the above conditions.

Measurement of crystallinity : Confirmed by powder X-ray diffraction method. It is measured as the ratio of the area belonging to zeolite to the area of halo derived from amorphous. In this analysis method, since the analysis result may greatly vary depending on the characteristics of the measurement device, a reference catalyst provided by the Catalysis Society of Japan is usually used as a standard substance.

In the case of ZSM-5 type zeolite, "J
RC-Z5-90H (1) "and use amorphous silica (for example, Caractact Q-5 manufactured by Fuji Silysia Chemical Ltd.)
A standard curve is prepared using a sample obtained by mixing the pulverized product (0 pulverized product) at an arbitrary ratio as a standard substance. The crystallinity of the ZSM-5 type zeolite molded body is measured by measuring the crystallinity under the same conditions as when the calibration curve was prepared.

Example 1 1.09 g of sodium aluminate was dissolved in 22.93 g of a 1 mol / L (liter) aqueous solution of tetra-n-propylammonium hydroxide (hereinafter referred to as TPAOH). The total volume was made up to 30 ml with distilled water. Silica beads (Fuji Silysia Chemical Ltd. "Caractact Q-50", 10-20 mesh, average pore diameter 50 nm, mechanical strength 29.4 Newton) dried at 120 ° C. for 1 day and 2
0.42 g was impregnated with 30 ml of the aqueous solution for 1 hour. Sodium aluminate and TPAO on silica beads
H was carried. The composition ratio is Si ₁ Al _0.03 Na _0.04 TP
A was _0.07 .

This was transferred onto an evaporating dish. After drying on a 100 ° C. water bath, it was dried in an 80 ° C. oven under a stream of nitrogen for 5 hours. The obtained precursor was placed in a Teflon cup and placed in a hollow Teflon (registered trademark) crucible with a volume of 100 ml. 1.00 g of distilled water was put in the bottom of the crucible container and heated at 180 ° C. for 8 hours. The crucible was cooled to room temperature, and the product taken out was packed in a column, washed with 500 ml of distilled water,
Dried for hours. The obtained white solid was calcined at 540 ° C. for 3.5 hours in a stream of air to remove excess organic components, thereby obtaining 20.75 g of a white product. This is designated as product A.

The shape of the product A retained the appearance of the silica beads used as the raw material. That is, 10-20
The beads were of mesh size. After grinding the product A, it was measured by powder X-ray diffraction. As a result, as shown in FIG. 1, it was a ZSM-5 type zeolite. The zeolite content was almost 100%.

As a result of measuring the crystallinity using "JRC-Z5-90H (1)" as a standard sample, the crystallinity of the product A was 100%.

The product A was measured by Al ²⁷ MAS-NMR, and the results are shown in FIG. There was no signal from aluminum outside the zeolite lattice. Furthermore, excluding the side band peak, only a signal at σ54.7 ppm attributed to aluminum in the lattice was observed. This indicates that the entire amount of aluminum supported on the silica beads has been incorporated into the framework of the zeolite crystal. That is, the product A is a ZSM-5 type aluminosilicate.

The BET three-point method for nitrogen at 77K (P /
The specific surface area according to P0 = 0.01, 0.03, 0.06) was 360 m ² / g. Further, as a result of measuring the pore distribution by a mercury intrusion method, a pore distribution curve shown in FIG. 3 was obtained. In FIG. 3, for example, 1E-1 is 1 × 10 ^-1 and 3E-1
E-3 means 3 × 10 ^-3 . The total macropore volume above 4 nm was 0.85 ml / g, and the surface area of the same macropore was 28 m ² / g. Pore size 100-250
The pore volume in the range of nm (average pore diameter 150 nm) was 0.68 ml / g. It can be seen that it has a very sharp pore distribution, occupying about 80% of the total macropore volume of 4 nm or more.

The mechanical strength of the obtained molded body was 9.8 Newton.

Example 2 1.35 g of sodium aluminate was dissolved in 84.29 g of a 1 mol / L aqueous TPAOH solution. 120
Silica beads ("Carrierct Q-50", manufactured by Fuji Silysia Chemical Ltd., 10 to 20 mesh) dried at ℃ for 1 day and 2 days
After impregnating 5.05 g in the aqueous solution for 1 hour, the mixture was evaporated to dryness with stirring to uniformly support sodium aluminate and TPAOH on the silica beads.
The composition ratio was Si ₁ Al _0.03 Na _0.04 TPA _0.20 . This was carried out in the same manner as in Example 1 to obtain a white product.
44 g were obtained. This is called product B.

The shape of the product B retained the appearance of the silica beads used as the raw material and was 10 to 20 mesh size beads. Powder X after grinding product B
As a result of measurement by X-ray diffraction, it is essentially the same as FIG.
It was an SM-5 type aluminosilicate.

As a result of measuring the product B by Al ²⁷ MAS-NMR, there was no signal derived from aluminum outside the zeolite lattice. The specific surface area of nitrogen at 77 K by a BET three-point method (P / P0 = 0.01, 0.03, 0.06) was 422 m ² / g. As a result of measuring the pore distribution by the mercury intrusion method, the total macropore volume of 4 nm or more was 1.0 ml / g, and the surface area of the macropore was 2 ml / g.
It was 0 m ² / g.

Example 3 Instead of a 1 mol / L aqueous TPAOH solution, 6.91 g of a 10 mass% TPAOH concentration was used, the loading composition ratio was changed to Si ₁ Al _0.03 Na _0.04 TPA _0.01 , and the crystallization conditions were set to 180 ° C. Example 1 except that the time was changed to 30 hours.
In the same manner as described above, 20.70 g of a white product was obtained. This is called product C.

The shape of the product C retained the appearance of the silica beads used as the raw material, and was beads of 10 to 20 mesh size. Powder X after grinding product C
As a result of measurement by X-ray diffraction, although the crystallinity was somewhat low,
The diffraction pattern was essentially the same as the above, and was a ZSM-5 type aluminosilicate.

As a result of measuring the product C by Al ²⁷ MAS-NMR, there was no signal derived from aluminum outside the zeolite lattice. The specific surface area of the nitrogen at 77 K by the BET three-point method (P / P0 = 0.01, 0.03, 0.06) was 400 m ² / g. As a result of measuring the pore distribution by the mercury intrusion method, the total macropore volume of 4 nm or more was 1.1 ml / g, and the surface area of the macropore was 2 ml / g.
It was 7 m ² / g.

Example 4 The loading composition ratio was determined using 6.54 g of sodium aluminate.
Si₁Al_0.20Na_{0.2 6}TPA_0.07And the crystallization conditions
Same as Example 1 except that the temperature was changed to 180 ° C for 3 hours.
This gave 26.60 g of a white product. This is the product D
Called.

The shape of the product D retained the appearance of the silica beads used as the raw material, and was 10 to 20 mesh size beads. Powder X after grinding product D
As a result of measurement by X-ray diffraction, although the crystallinity was somewhat low,
This gave essentially the same diffraction pattern as that of ASM, and was a ZSM-5 type aluminosilicate.

As a result of measuring the product D by Al ²⁷ MAS-NMR, there was no signal derived from aluminum outside the zeolite lattice. The specific surface area of nitrogen at 77 K by a BET three-point method (P / P0 = 0.01, 0.03, 0.06) was 410 m ² / g. Further, as a result of measuring the pore distribution by the mercury intrusion method, the total macropore volume of 4 nm or more was 0.79 ml / g, and the surface area of the macropores was 15 m ² / g.

Example 5 A white product (20.70 g) was obtained in the same manner as in Example 1 except that the crystallization conditions were changed to 160 ° C. for 8 hours. This is called product E.

The shape of the product E retained the appearance of the silica beads used as the raw material, and was 10 to 20 mesh size beads. Powder X after grinding product E
As a result of measurement by line diffraction, the diffraction pattern was essentially the same as that shown in FIG. 1, and it was a ZSM-5 type aluminosilicate.

As a result of measuring the product E by Al ²⁷ MAS-NMR, there was no signal derived from aluminum outside the zeolite lattice. The specific surface area of nitrogen at 77 K by a BET three-point method (P / P0 = 0.01, 0.03, 0.06) was 450 m ² / g. Further, as a result of measuring the pore distribution by the mercury intrusion method, the total macropore volume of 4 nm or more was 1.0 ml / g, and the surface area of the macropore was 4 ml / g.
It was 0 m ² / g.

Example 6 0.3 ml of a 4 mol / L aqueous sodium hydroxide solution and 9.14 g of TP were added to 5.00 g of a colloidal silica solution (Nissan Chemical's Snowtex S: 30% by mass of SiO ₂ ).
An AOH aqueous solution (concentration: 1 mol / L) was added with stirring. After stirring at room temperature for 30 minutes, an aqueous solution of 0.31 g of aluminum nitrate nonahydrate dissolved in 5 g of distilled water was gradually added dropwise. The raw mixture of this aqueous slurry was stirred for 2 hours. Thereafter, silica beads ("Carrieract Q-50" manufactured by Fuji Silysia Chemical Ltd.)
(0-20 mesh) 13.50 g for 1 hour.
The composition ratio was Si ₁ Al _0.003 Na _0.005 TPA _0.04 . This was performed in the same manner as in Example 1 to obtain a white product.
20 g were obtained. This is called product F.

The shape of the product F retained the appearance of the silica beads used as the raw material, and was 10 to 20 mesh size beads. After crushing product F, powder X
As a result of measurement by X-ray diffraction, it is essentially the same as FIG.
It was an SM-5 type aluminosilicate.

As a result of measuring the product F by Al ²⁷ MAS-NMR, there was no signal derived from aluminum outside the zeolite lattice. The specific surface area of nitrogen at 77K by a BET three-point method (P / P0 = 0.01, 0.03, 0.06) was 330 m ² / g. As a result of measuring the pore distribution by the mercury intrusion method, the total macropore volume of 4 nm or more was 0.81 ml / g, and the surface area of the macropores was 14 m ² / g.

Example 7 Silica beads ("Carrierct Q" manufactured by Fuji Silysia Chemical Ltd.)
-10 ", 10-20 mesh, average pore diameter 10 nm,
22.93 g of mechanical strength (29.4 Newtons) was used. Otherwise in the same manner as in Example 1, 21.00 g of a white product was obtained. This is called product G.

The shape of the product G retained the appearance of the silica beads used as the raw material, and was beads of 10 to 20 mesh size. After grinding the product G, the powder X
As a result of measurement by X-ray diffraction, it is essentially the same as FIG.
It was an SM-5 type aluminosilicate.

The BET three-point method for nitrogen at 77K (P /
The specific surface area according to P0 = 0.01, 0.03, 0.06) was 370 m ² / g. Further, as a result of measuring the pore distribution by the mercury intrusion method, a pore distribution curve shown in FIG. 4 was obtained. Total macropore volume of 4 nm or more is 0.67 ml / g
And the surface area of the same macropores was 30 m ² / g. The pore volume in the range of pore diameter 30 to 130 nm (average pore diameter 45 nm) was 0.57 ml / g. 4n
It can be seen that it has a very sharp pore distribution occupying about 85% of the total macropore volume of m or more.

Example 8 Silica beads ("Carrierct Q" manufactured by Fuji Silysia Chemical Ltd.)
-50 ", 5 to 10 mesh, average pore diameter of 50 nm, mechanical strength of 59 Newton). Except for this, the white product 22.0 was treated in the same manner as in Example 1.
0 g was obtained. This is referred to as product H.

The shape of the product H retained the appearance of the silica beads used as the raw material, and was 5 to 10 mesh size beads. The product H was ground and measured by powder X-ray diffraction, which was essentially the same as FIG.
It was an M-5 type aluminosilicate. The zeolite content was almost 100%.

As a result of measuring the crystallinity using “JRC-Z5-90H (1)” as a standard sample, the product C1 was obtained.
Has a crystallinity of 100%.

The BET three-point method for nitrogen at 77K (P /
The specific surface area according to P0 = 0.01, 0.03, 0.06) was 365 m ² / g. Also, as a result of measuring the pore distribution by the mercury intrusion method, the total macropore volume of 4 nm or more was 0.94 ml / g, and the surface area of the same macropore was 2.
It was 5 m ² / g.

The mechanical strength of the obtained molded body was 39 Newton.

Example 9 8.08 g of aluminum nitrate nonahydrate was dissolved in distilled water to make a total volume of 38 ml. Silica beads dried at 120 ° C for one day and night (“Carrier Q-
6 ", 16 to 32 mesh) was impregnated with 31.04 g of the aqueous solution at room temperature for 1 hour. Subsequently, it was dried on a hot water bath at 100 ° C., and dried at 550 ° C. under a stream of air.
For 3 hours. It was supported on silica beads as aluminum oxide. Then, it cooled. 7.6 ml of a 4 mol / L aqueous sodium hydroxide solution and 22.84 g of a 23 mass% aqueous TPAOH solution were mixed. The solution was adjusted to 38 ml with distilled water for 1 hour, and then
Dry on a 0 ° C. water bath. Further, drying was performed in an oven at 80 ° C. under a stream of nitrogen for 5 hours. The composition ratio is Si
₁ Al _0.042 Na _0.059 TPA was _0.05 .

The obtained precursor was placed in a Teflon cup. It was placed in the hollow of a stainless steel autoclave having a capacity of 3300 ml. 30 at the bottom of the autoclave container
g of distilled water was added and heated at 180 ° C. for 20 hours to crystallize. After cooling to room temperature, the product removed was packed in a jacketed column. 60 ° C, 0.4ml / m
At a flow rate of in, a 1 mol / L aqueous ammonium nitrate solution was passed for 24 hours to perform ion exchange. Distilled water 5
After washing with 00 ml of water, it was dried at 120 ° C. for 5 hours. Calcination was performed at 550 ° C. for 6 hours under a stream of air. Removal of excess organic components gave 29 g of a white product. This is referred to as product J.

The shape of the product J was 16 to 32 mesh while keeping the appearance of the silica beads used as the raw material. As a result of powder X-ray diffraction measurement after pulverizing the product J, the result was essentially the same as that of FIG. 1 and was a ZSM-5 type zeolite.

The BET three-point method for nitrogen at 77K (P /
The specific surface area according to P0 = 0.01, 0.03, 0.06) was 360 m ² / g. Moreover, as a result of measuring the pore distribution by the mercury intrusion method, the total macropore volume of 4 nm or more was 0.6 ml / g.

Comparative Example 1 An experiment was conducted in the same manner as in Example 9 except that sodium hydroxide was not supported on a silica carrier and a precursor containing no sodium component was used. The molded body immediately after being extracted from the autoclave was pulverized, and as a result of powder X-ray diffraction measurement, it was found to be amorphous.

Comparative Example 2 An experiment was carried out in the same manner as in Example 9 except that TPAOH was not supported on a silica carrier and a precursor containing no tetraalkylammonium component was used. The molded body immediately after being extracted from the autoclave was pulverized, and as a result of powder X-ray diffraction measurement, it was found to be amorphous.

The examples that follow show production examples of ethanolamines mainly from ethylene oxide and ammonia. This example is intended for the purpose of illustration of the invention and does not limit the invention.

The LHSV, the conversion of ethylene oxide and the selectivity of monoethanolamine are defined as follows. In addition, products other than ethanolamines are hardly produced. Therefore, the conversion (mol%) of ethylene oxide is (mono,
It is approximately equal to the overall yield (mol%) of di, tri) ethanolamine.

LHSV (hr ⁻¹ ) = (AB) / (AC) where, AB: volume of liquid raw material passing through the reactor every hour (cm ³ /
hr) AC: catalyst volume (cm ³ ) in the reaction vessel.

Conversion of ethylene oxide (mol%) = 1
00 (BC) / (BD) where, BC: moles of ethylene oxide consumed in the reaction BD: moles of ethylene oxide used in the reaction.

Diethanolamine selectivity (% by mass) =
100 (CD) / (CE) where CD: mass of diethanolamine in the product CE: mass of total ethanolamine in the product

Catalyst Preparation Example 1 0.8383 g of lanthanum nitrate hexahydrate was dissolved in distilled water to make 38 ml. In addition, the MFI prepared in Example 9
29 g of zeolite type beads (proton type, 16 to 32 mesh) were impregnated at room temperature for 1 hour. Continue to 100
And dried on a hot water bath. This is 5
By baking at 50 ° C. for 3 hours, lanthanum-containing MFI zeolite beads were obtained. This is called catalyst CA.

Catalyst Preparation Example 2 (Comparative Example) Commercially available ZSM-5 zeolite (Si / A, manufactured by Zeolist)
l atomic ratio = 28, proton type)
Of lanthanum nitrate hexahydrate in 250 ml of distilled water was impregnated for 1 hour. Subsequently, it was dried on a hot water bath at 100 ° C. This is heated at 550 ° C. under air current for 3 hours.
After calcination for a time, a lanthanum-containing ZSM-5 zeolite was obtained.

The lanthanum-containing ZSM-5 thus obtained was obtained.
70 g of zeolite and 145 g of alumina sol (alumina sol 520 manufactured by Nissan Chemical Co., alumina content 20.7% by mass)
(30 g as alumina) was kneaded, and the slurry was concentrated. After adjusting the water content to 40% by mass, it was extruded to a diameter of 0.7 mm. This was calcined at 650 ° C. for 3 hours in a stream of air to obtain a lanthanum-containing ZSM-5 catalyst molded with an alumina binder. This is called catalyst CB.

Example 10 Using the catalyst CA obtained in Catalyst Preparation Example 1, a reaction for synthesizing ethanolamines from ethylene oxide and ammonia was carried out.

FIG. 5 shows the reactor used. In FIG. 5, the reaction tube 1 has an inner diameter of 10 mm and a length of 400 mm.
A stainless steel tube with a heater for compensating heat radiation wound around a mm stainless steel tube was used. In order to measure the temperature profile of the catalyst layer, a protective tube into which a thermocouple can be inserted was provided inside the reactor. The reactor was charged with 20 ml of catalyst CA.

Ethylene oxide was supplied to the preheater 2 from the raw material tank 10 for ethylene oxide via the high-pressure pump 4, and ammonia was supplied from the raw material tank 11 for ammonia via the high-pressure pump 5. The raw material (ammonia / ethylene oxide = 15 (molar ratio)) heated to 70 ° C. in the preheater 2 was passed through the LHSV at 10 hr ⁻¹ ,
Supplied. Ammonia and ethylene oxide were fed into the reaction vessel at a constant rate using a high-pressure pump, and the reaction pressure was maintained at 14 MPa. The reaction inlet temperature was 70 ° C. The reaction solution was collected by an ammonia flash tower 7 and analyzed by gas chromatography. Unreacted source gas,
Ammonia was mainly cooled through the heat exchanger 9 and recovered in the recovered ammonia tank 8. Recovery ammonia tank 8
Was recycled through the high-pressure pump 6 as raw material ammonia.

The impurities of the obtained ethanolamines were measured by gas chromatography (FUSED SIL).
ICA capillary column (30m, 0.53mm,
0.5 μm film thickness). Quantitative analysis of ethanolamines was performed by the area ratio of the FID detector (the reaction solution after the ammonia flush was diluted to 0.25% by mass,
10 μL was injected).

Table 1 shows the results of the reaction 24 hours after the start of the reaction. By this analysis, no impurities other than ethanolamines were detected.

Comparative Example 3 A reaction was carried out in the same manner as in Example 10 except that catalyst CB was used instead of catalyst CA. By gas chromatography analysis, diglycolamine (abbreviated as DGA), 1 mole of ethylene oxide adduct to diethanolamine terminal hydroxyl group (abbreviated as DEA + EO), 1 mole of ethylene oxide adduct to triethanolamine terminal hydroxyl group (T
(Abbreviated as EA + EO).

Table 1 shows the results.

[0115]

[Table 1]

From Table 1, the products obtained using the catalysts CA and CB were analyzed under the same conditions. As a result, in the case of the catalyst CB, impurities DGA, DEA + E, and TEA + EO were detected.

[0117]

The binderless crystalline aluminosilicate molded article of the present invention contains essentially no binder, so that the zeolite content in the molded article is extremely high.
In addition, zeolite can be efficiently used without burying zeolite in the inorganic binder. Further, there is no need to consider the adverse effects caused by impurities such as inorganic binders and off-lattice aluminum.

When the binderless ZSM-5 type aluminosilicate molded article of the present invention is used as a catalyst, the activity can be reduced, the generation of impurities can be suppressed, and the shape selectivity, which is the intrinsic property of zeolite, can be maintained. It is excellent in having sufficient mechanical strength to withstand. Thereby, dialkanolamine can be efficiently and selectively synthesized from various amination reactions, for example, ammonia and alkylene oxide.

According to the method of the present invention, since the crystallization is carried out by bringing the molded precursor into contact with saturated steam, the binderless ZSM-5 type aluminosilicate molded body can be easily produced.

Further, according to the method of the present invention, the time required for crystallization is short, and the raw material components do not elute into water, so that metal ions are efficiently incorporated into the crystal lattice. The raw material charge composition and the product composition are in good agreement, and Z is free from off-lattice aluminum.
SM-5 type binderless crystalline aluminosilicate can be produced in high yield.

Further, according to the method of the present invention, the obtained ZSM-5 type binderless crystalline aluminosilicate molded product reflects the properties of the raw material silica molded product, so that the physical properties such as the pore structure can be easily controlled. , Can expand the scope of application. In addition, since the amount of expensive tetraalkylammonium can be reduced and almost no waste liquid is generated,
It is an economical production method that does not require consideration of recovery and waste liquid treatment.

[Brief description of the drawings]

FIG. 1 shows a CuKα X-ray diffraction diagram of product A.

FIG. 2 shows an Al ²⁷ MAS-NMR spectrum of product A.

FIG. 3 shows a pore distribution curve of a product A by a mercury intrusion method.

FIG. 4 shows a pore distribution curve of a product G by a mercury intrusion method.

FIG. 5 is a drawing showing a reaction apparatus used in Example 10.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Reaction tube 2 ... Preheater 4,5,6 ... High pressure pump 7 ... Ammonia flash tower 8 ... Recovery ammonia tank 10,11 ... Raw material tank (10: ethylene oxide, 1
1: ammonia)

Claims (7)

[Claims] 1. A binderless crystalline aluminosilicate molded article, wherein the aluminosilicate is ZSM-5.
It has a type crystal structure, and the composition ratio (atomic ratio) of silicon and aluminum constituting the crystal structure is:
A binderless crystalline aluminosilicate molding, wherein aluminum is in the range of 0.0001 to 0.5, and the content of aluminum outside the crystal lattice is 3% or less of the total aluminum contained in the molded body. body. 2. The molded article according to claim 1, wherein the specific surface area determined by nitrogen adsorption measurement by the BET method is in the range of 300 to 550 m ² / g. 3. The pore diameter determined by a mercury intrusion method is 4 nm.
It has the above pores, and the surface area of the pores is ² to 150 m ² /
g, and the pore volume of the pores is 0.15 to 1.5.
The molded article according to claim 1 or 2, wherein the molded body is ml / g. 4. aluminosilicate precursor represented by the following formula _{(1): Si 1 Al x} M y (SDA) z (1) ( In the formula, M represents an alkali metal, SDA represents a tetraalkylammonium , X is 0.0001-0.
5, y represents the range of 0.0001 to 1, and z represents the range of 0.001 to 1. ) Is contacted with saturated steam to produce a binderless crystalline aluminosilicate molded article. 5. The method according to claim 4, wherein the aluminosilicate precursor is obtained by supporting a raw material containing an aluminum component, an alkali metal component and a tetraalkylammonium component on a silica molded body. 6. A catalyst for an amination reaction, comprising the binderless crystalline aluminosilicate molded product according to claim 1. Description: 7. A process for producing an alkylene amine, comprising aminating an alkylene oxide with ammonia using the catalyst according to claim 6.