JP2001180928A - Mel type binderless zeolitte molding, and its production process and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binderless molding comprising of substantially MEL type zeolite itself. SOLUTION: The binderless zeolite molding and its production process comprises bringing a zeolite precursor of the formula: Sil(TBA)xM1yM2z (TBA is tetrabutylammonium; M1 is an alkali metal; M2 is a metal element incorporated in metallosilicate crystal structure; x is 0.001-1, y is 0.0001-1, z is 0-0.4) into contact with a saturated steam of 80-260 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a "MEL" type binderless zeolite molded product referred to by a code indicating a structure according to the International Zeolite Society, a method for producing a MEL type binderless zeolite molded product, and uses of the molded product.

[0002]

2. Description of the Related Art MEL type zeolites are disclosed in US Pat.
It is a crystalline metallosilicate represented by crystalline aluminosilicate disclosed for the first time in the specification of Japanese Patent Application Laid-Open No. 09,979. Metal component constituting the zeolite crystal skeleton (hereinafter referred to as T
However, in crystalline aluminosilicates composed of silicon and aluminum, it is widely used to replace the Al ³⁺ cation in the crystal lattice with another metal ion mainly for the purpose of controlling its acidity. Generally, it is called MEL-type zeolite, including silicalite having the same structure but not containing aluminum and crystalline metallosilicate in which aluminum is substituted with another metal ion. ME
L-type zeolite is a tetragonal zeolite characterized in that two kinds of intersecting pores formed by a 10-membered oxygen ring are both straight channels and their pore openings have the same elliptical shape. is there.

As a method for synthesizing MEL-type metallosilicate, a so-called hydrothermal reaction method using an aqueous reaction slurry using tetra-n-butylammonium ion as a template as a raw material is conventionally known. For example, as disclosed such as in JP-B-53-23280, the SiO ₂ concentration in the feed aqueous slurry 10
An aqueous slurry of about mass% capable of uniform stirring and mixing was prepared, and reacted under hydrothermal conditions (100 ° C., autogenous pressure) for 23 days to crystallize the MEL-type crystalline metallosilicate.

[0004] However, in the conventional hydrothermal synthesis method, since a part of the raw material components are dissolved in water at the time of heating, the ratio of the components converted into crystals is necessarily reduced, and the yield is low.
Further, since the alkali component is diluted, the crystallization time becomes very long. In such a slow crystallization method, the crystal tends to grow in a large size. In addition, since the foreign metal component (M) other than silicon (Si) is easily excluded outside the crystal lattice, the atomic ratio of Si / M (M represents T atom other than silicon) in the aqueous slurry, There is a problem that the atomic ratio of Si / M in the synthesized MEL zeolite does not always match. Further, since the aqueous slurry is industrially heated, a relatively large-volume closed container is required for the mass of the generated crystals, a large amount of expensive template agent must be used, and a large amount of waste liquid is required. There are problems such as the generation of the zeolite powder and the complicated filtration and firing steps of the zeolite powder.

[0005] Further, when a conventional zeolite molded body is manufactured, it is necessary to first synthesize the zeolite by a hydrothermal synthesis method and then mold it using an inorganic binder, since the moldability of zeolite alone is poor. Was. In this method, it is necessary to select a binder that does not adversely affect the intended use, and since a large amount of an inorganic binder is required to obtain sufficient strength, only the zeolite content in the molded body decreases. In addition, there is a problem that zeolite buried in the binder cannot be used effectively.

Further, a method for producing a supported zeolite molded article using an inorganic molded article has been proposed. For example, in Japanese Patent Application Laid-Open No. 11-165074, an aqueous gel composed of tetraethylorthosilicate, tetraethylorthotitanate and tetrapropylammonium hydroxide is supported on a silica carrier, and then subjected to steam treatment under pressure to obtain an MFI-type crystalline titanium. A method for crystallizing nosilicate on a support is described. In this method, it is necessary to use a low-concentration aqueous gel having sufficient fluidity to be carried on the carrier, and thus there is a problem that the amount of the carrier carried on the carrier is extremely low.

For this reason, several methods have been proposed for producing aluminosilicate molded bodies substantially containing no binder. For example, Japanese Unexamined Patent Publication No. Sho 59-162952
(TSZ type aluminosilicate)
Some limited crystal-type binderless aluminosilicate moldings such as 72620 (MOR type aluminosilicate) and JP-A-62-138320 (FAU type aluminosilicate) are known. However, a binderless MEL type aluminosilicate molded body has not been known at all.

In these methods, a crystalline aluminosilicate powder synthesized in advance is used as a secondary raw material, and molded using an inorganic binder such as a clay mineral or silica alumina sol, is brought into contact with an alkali solution. Substantially twice hydrothermal synthesis is required to convert the binder to crystalline aluminosilicate. Therefore, there are problems in that the manufacturing process becomes longer and the amount of waste liquid increases.

Further, there is known a method for synthesizing a binderless silicalite molded article in which the metal component constituting the crystal skeleton is substantially composed of only silicon or a binderless crystalline metallosilicate molded article composed of T atoms other than aluminum. Had not been.

As described above, a MEL type binderless zeolite molded article substantially containing no binder and a simple and efficient production method thereof have not been known yet.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide a MEL-type binderless resin comprising substantially only a zeolite crystal without containing an inorganic binder. An object of the present invention is to provide a zeolite molded body.

Another object of the present invention is to provide a simple and efficient method for producing a MEL-type zeolite molded body without using a binder.

It is a further object of the present invention to provide a use of a MEL type binderless zeolite molded article.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies on a MEL type binderless zeolite molded product, and found that, for example, a tetrabutylammonium component, an alkali metal component, and other metal components were supported on a silica molded product. After that, by a method of contacting with saturated steam under a specific condition, the entire amount of the silica component is crystallized while maintaining the shape of the silica molded product, and at the same time, the metal component is incorporated as T atoms. The inventors have found that a MEL-type binderless zeolite molded body containing no binder can be produced easily and with high yield, and have completed the present invention.

That is, an object of the present invention is to provide a binderless zeolite molded article, wherein the zeolite is a MEL
Or a binderless zeolite molded body that is a metallosilicate having a crystal structure of an MFI-type / MEL-type composite.

The object of the present invention is to provide the following formula (1): Si ₁ (TBA) _x M ¹ _y M ² _z (1) (where TBA is tetrabutylammonium,
M ¹ represents an alkali metal, M ² represents a metal element incorporated in the metallosilicate crystal skeleton, x is 0.001-1, y
Represents a range of 0.0001 to 1, and z represents a range of 0 to 0.4. )
The method for producing a MEL-type binderless zeolite molded body, characterized by contacting the zeolite precursor represented by the formula (1) with saturated steam.

Further, the object of the present invention is attained by a catalyst for an amination reaction, comprising the binderless zeolite molded product according to any one of claims 1 to 3.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below.

In the MEL type binderless zeolite molded article of the present invention, the MEL type refers to the MEL type and ME
A substance containing a complex of L type and MFI type.

MEL type binderless zeolite of the present invention
Zeolite precursor used in the method of manufacturing a molded article,
The following formula (1) Si₁(TBA)_xM¹ _yM^Two _z (1) (where TBA is tetrabutylammonium,
M¹Is an alkali metal, M ^TwoIs a metallosilicate crystal skeleton
X represents 0.001 to 1, y represents a metal element to be incorporated.
Represents a range of 0.0001 to 1, and z represents a range of 0 to 0.4. )
There is no particular limitation as long as the composition is represented by The formula
In (1), x is 0.002 to 1, and y is 0.0001.
Preferably, the composition is such that １1 and z are in the range of 0 to 0.3.
More preferably, x is 0.003-0.8 and y is 0.00
02-0.5, wherein z is in the range of 0-0.2
It is even more desirable.

The method for preparing the zeolite precursor is not particularly limited, but a raw material containing a tetrabutylammonium component, an alkali metal component, and, if desired, one or more metal components incorporated into a supported metallosilicate crystal skeleton is used. It is preferable to use a method in which the particles are supported on a silica molded body.

In the case where the above-mentioned tetrabutylammonium component and alkali metal component are carried on the above-mentioned silica molding, a binderless MEL comprising only T atoms of silicon is used.
Molded silicalite molded body can be manufactured, in addition to the two components, boron, aluminum, titanium, chromium, iron,
When carrying one or more components selected from the group consisting of cobalt, nickel, copper, zinc, gallium, and indium, it is possible to produce a MEL-type binderless crystalline metallosilicate molded body in which this is incorporated as a T atom. it can.

The silica molded body is not particularly limited, but a commercial product can be used. As the silica molded body, a molded body having a relatively large specific surface area is suitably used. Usually, the specific surface area determined by the nitrogen adsorption measurement by the BET method is, for example, 5 to 1000 m ² / g, preferably ² m ² / g.
Those having a range of 0 to 800 m ² / g are used. If the specific surface area is too small, crystallization requires a long time, and the degree of crystallization may be deteriorated.

The silica molded body has pores having a pore diameter of 4 nm or more determined by, for example, a mercury intrusion method, and the surface area and the pore volume of the pores are 5 to 1000, respectively.
m is ^{2 /g,0.10~1.5ml/g,} preferably in the range of 20~800m ² /g,0.15~1.3ml/g.

Examples of the tetrabutylammonium component include halides and hydroxides of tetra-n-butylammonium. Usually, tetra-n-butylammonium hydroxide is used to form a MEL type. Zeolite can be efficiently synthesized.

As the alkali metal component, lithium,
Examples thereof include sodium and potassium, and their hydroxides and halides, or silica moldings and / or
Alternatively, an alkali metal component in a metal salt compound can be used.

In the case of synthesizing a MEL type binderless crystalline metallosilicate molded body, a salt of a metal which simultaneously becomes a T atom is supported on the silica molded body together with the tetrabutylalkylammonium component and the alkali metal component. I do. These metal salts include boron, aluminum, titanium, chromium, iron, cobalt, nickel,
Copper, zinc, gallium, indium and the like, preferably boron, aluminum, chromium, iron, zinc, gallium nitrate,
Examples thereof include sulfates, halides, oxoacid salts, and hydroxides, and these are preferably used in the form of an aqueous solution. Further, the metal salt is at least one metal selected from the group consisting of boron, aluminum, chromium, iron, zinc and gallium, preferably at least one metal selected from the group consisting of boron, aluminum, iron and gallium The use of the metal salt is preferred because the crystallization time can be significantly reduced. These metal components are converted into binderless metallosilicate by being incorporated into the zeolite framework during crystallization.

The metal component serving as a T atom incorporated in the crystal skeleton may be in any form as long as it is supported on a silica molded body, and for example, an oxide of the metal contained in the silica molded body can be used.

Usually, a water-soluble salt is suitably used as the supported metal salt, but a precursor supported as a metal oxide by impregnating with an aqueous solution of the metal salt, drying and calcining can also be used. . In this case, the zeolite precursor is supported by supporting a metal component and / or an alkali metal component to be a T atom on a silica molded body and calcining, and then supporting and drying a tetrabutylammonium component and / or an alkali metal component. obtain. Thereby, the strength of the obtained zeolite molded body may be able to be increased.

The method of supporting a raw material containing a tetrabutylammonium component, an alkali metal component, and one or more metal components incorporated into a metallosilicate crystal skeleton to be supported as required on the silica molded body is not particularly limited. However, since it is desirable that the raw material is uniformly supported in the silica molded body, it is usually dried by impregnating with an aqueous solution. As an example, a predetermined amount of each component is made into a uniform aqueous solution, which 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. Has no effect.

The drying temperature after the impregnation with the aqueous solution is not particularly limited, but is preferably from 20 to 120 ° C., more preferably from 50 to 120 ° C., since the decomposition of the tetrabutylammonium salt is small, and the water content is suppressed efficiently. Carried out at １１０110 ° C. The water content of the precursor is preferably 30% or less, more preferably 20 to 0.1%, in that the supported components are not eluted during crystallization and the yield is high.

The drying method is not particularly limited, and the drying can be performed under reduced pressure or normal pressure. Drying under an air stream at normal pressure is preferred because it is simple.

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

The temperature of the saturated steam is not particularly limited, and the crystallization rate is high, the decomposition of the contained tetrabutylammonium component is small, and a MEL type binderless zeolite molded article having a high crystallinity can be obtained. 80-2
A range of 60 ° C is preferred, and 100 to 230 ° C is more preferred. If the crystallization temperature is too high, mixed crystals with other minerals may be formed.

It is also known that MFI-type zeolites and MEL-type zeolites may form a composite because they are easily bonded (intergrowth) in a crystal.
The MEL-type binderless zeolite molded article of the present invention also includes
The complex can be formed by specific preparation conditions. For example, the composite ratio of the MEL type and the MFI type can be arbitrarily controlled by the amount of the alkali metal component in the precursor, the crystallization temperature, and the like. The compounding ratio of the MFI type zeolite is 3 or less, preferably 1 or less, more preferably 0.2 or less, with respect to MEL type.

The contact time with the saturated steam may be short, usually in the range of 2 to 100 hours, preferably in the range of 3 to 72 hours. If the crystallization time is too short, the degree of crystallinity will decrease, and if it is too long, a mixed crystal with other minerals may be formed.

The method and apparatus for heating the zeolite precursor by contacting it with saturated steam are not particularly limited. For example, the precursor is installed in the hollow of the pressure vessel,
The method can be carried out by sealing the lower part of the vessel with water corresponding to the amount of saturated steam determined by the reaction temperature and the volume of the vessel, and then heating it in a thermostat, but the embodiment is not limited to this. This precursor may be placed in a vessel, and a closed vessel containing water outside may be used, or the precursor is continuously synthesized by a fixed-bed reactor or a moving-bed reactor in contact with saturated steam. You can also.

By using the production method of the present invention, crystallization can be carried out by contacting the zeolite precursor with saturated steam without dispersing the zeolite precursor in water and causing a hydrothermal reaction. And, if necessary, the supported metal component can be converted to a MEL zeolite having T atoms. As a result, the silica molded body as a raw material is entirely converted into zeolite while maintaining its shape, and thus the zeolite to be produced contains essentially no binder, so that a MEL-type binderless zeolite molded body can be easily produced. It is inferred.

Since no binder is used in the production method of the present invention, the MEL-type zeolite molded body synthesized by the production method of the present invention has a very high crystallinity with a zeolite content of almost 100%. A suitable precursor composition ratio,
By selecting the crystallization temperature and the crystallization time from the above conditions, the crystallinity of the molded product can be controlled, and is, for example, 95% or more, preferably 98% or more.
The crushing strength can be controlled by the crystallinity.

In the production method of the present invention, the silica molded body is molded into an arbitrary shape such as a sphere, a cylinder, a ring, or a honeycomb by a conventional method, and then converted into zeolite by the method of the present invention. Spherical, cylindrical,
A binderless zeolite molded article having an arbitrary shape such as a ring shape or a honeycomb shape can be manufactured. Since the raw silica carrier itself is converted into the zeolite as it is, a binderless zeolite molded body can be obtained while maintaining the shape of the silica molded body.

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, by controlling the physical properties of the silica molded product used as the raw material in a conventional manner, the physical properties of the binderless zeolite molded product can be easily controlled.

Further, the binderless zeolite molded article of the present invention is characterized in that (1) the zeolite has a MEL type crystal structure, and (2) the composition ratio (atomic ratio) between silicon and the metal constituting the zeolite crystal structure is as follows. , Silicon, and the metal is in a range of 0 to 0.4.

The zeolite in the molded article of the present invention is MEL
It has a type crystal structure. This can be confirmed by powder X-ray diffraction measurement or the like. The structure of the MEL-type zeolite is such that a TO ₄ tetrahedron in which four oxygen atoms are coordinated at the apexes with a T atom as the center is bonded three-dimensionally to form a zeolite crystal skeleton. For this reason, silicalite in which T atoms consist only of silicon is electrically neutral and does not exhibit solid acidity. Replacing Si ⁴⁺ with another valence metal gives TO
It is well known that cations such as protons are present in the crystal to electrically neutralize the ₄ anions, which causes solid acidity. These cations can be easily exchanged by ordinary operations. Also,
The amount and type of solid acidic acid expressed can be controlled by the amount and type of the element introduced as the T atom. The solid acidity can be evaluated by a thermal desorption (TPD) method of ammonia.

In the molded article of the present invention, the composition ratio (atomic ratio) of the metal component constituting the zeolite crystal structure in the molded article is as follows:
In the range of 0 to 0.4, preferably 0.0
005 to 0.2.

Further, the molded body of the present invention has a specific surface area of, for example, 250 to 55 determined by nitrogen adsorption measurement by the BET method.
A 0 m ² / g, preferably in the range of 270~525m ² / g.

The molded article of the present invention has secondary pores having a pore diameter of, for example, 4 nm or more determined by a mercury intrusion method, and the surface area and pore volume of the pores are each 2 to 150 m.
A ^{2 /g,0.10~1.5ml/g,} preferably in the range of 3~130m ² /g,0.13~1.3ml/g.

The molded article of the present invention can be produced simply and efficiently by the above-mentioned method for producing a binderless zeolite molded article. Examples of the shape of the molded article of the present invention include a sphere, a cylinder, a ring, and a honeycomb, but are not particularly limited.

The size of the binderless zeolite molded product of the present invention depends on the size of the silica molded product to be used, but is usually 0.1 to 30 mm in the case of a spherical, cylindrical, or ring type. Is in the range of 0.2 to 20 mm. In the case of a honeycomb form, there is no particular limitation.

The binderless zeolite molded article of the present invention can easily control the shape, size, macropore distribution, etc., and thus can be used as a catalyst or a catalyst carrier for adsorbents or chemical reactions in various chemical processes. Available, amination reaction catalyst, alkylation reaction catalyst, isomerization reaction catalyst,
It is suitably used as a cracking reaction catalyst, a Beckmann rearrangement reaction catalyst, a hydration reaction catalyst, an alcohol addition reaction catalyst, and the like.

When a conventional zeolite molded body using an inorganic binder is used as a catalyst, the catalyst activity is lower than the original zeolite catalyst, the strength of the catalyst molded body is weak, and various impurities are produced as by-products. However, the binderless zeolite molded article of the present invention does not have these problems, and is excellent because the catalyst performance inherent in zeolite can be exhibited. Furthermore, since various amination reactions have a large adverse effect of the inorganic binder, it is preferable to use the binderless zeolite molded article of the present invention as a catalyst. Examples of the amination reaction include a synthesis reaction of alkanolamines by amination of ammonia with an alkylene oxide, an ammonia addition reaction to an olefin, an N-alkylation reaction with an alcohol represented by synthesis of methylamines, and a reaction of ethanolamines. Examples include a cyclization dehydration reaction and an ethylenediamine synthesis reaction from monoethanolamine and ammonia.

The above-mentioned alkanolamine synthesis reaction includes, for example, a process for producing ethanolamines using ethylene oxide and ammonia. Usually, when a zeolite catalyst molded using an inorganic binder is used, the catalytic activity is reduced, and diglycolamines are reduced. However, there are problems such as generation of impurities such as the above, a point that the strength of the molded body is weak, and a decrease in diethanolamine selectivity. Since this is due to the effect of diluting the catalyst component and the chemical properties of the inorganic binder due to the addition of the inorganic binder, the binder-less zeolite molded article of the present invention containing no inorganic binder and having sufficient strength is used as a catalyst or a catalyst carrier. It is particularly preferred to use. Further, in this case, the crystal structure of the zeolite is preferably an MEL type or a complex of the MFI type and the MEL type in view of exhibiting high reaction activity and diethanolamine selectivity.

[0052]

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

(Example 1) Sodium aluminate 0.2
6 g was dissolved in distilled water to make 12 ml. At 120 ° C
Silica beads dried one day and night (Fuji Silysia Chemical
7. "Carrieract Q-10", 10-20 mesh)
After impregnating 25 g with the total amount of the aqueous solution for one hour, 8 g
Dry on a 0 ° C water bath and place sodium aluminate on silica beads.
Thorium was loaded. In addition, dry at 120 ° C all day and night.
After that, 40% by mass of tetrabutylammonium hydroxide
8.91 g of an aqueous solution of sodium (abbreviated as TBA) in distilled water
In the aqueous solution diluted to 12 ml, add the sodium aluminate
The entire amount of thorium-supported silica beads was impregnated for one hour. Pull
Successively, it is dried on a water bath at 80 ° C.
Supported sodium aluminate and TBA. Composition ratio
Is Si₁TBA_0.100Na _0.026Al_0.020It is.

The obtained precursor was placed in a basket made of a stainless steel net and placed in a hollow Teflon (registered trademark) crucible with a capacity of 100 ml. 1 at the bottom of the crucible
g of distilled water, sealed, and heated at 170 ° C. for 30 hours. After cooling the crucible to room temperature, the product was taken out and calcined at 550 ° C. for 6 hours in an air stream to remove organic components derived from TBA, thereby obtaining 8.30 g of a white product. This is designated as product A.

The shape of the product A was 10 to 20 mesh size beads while maintaining the appearance of the silica beads used as the raw material. As a result of powder X-ray diffraction measurement after pulverizing the product A, as shown in FIGS. 1 and 2, it was a MEL-type crystalline aluminosilicate. 2 shown in FIG.
Since the diffraction at θ = 44.86 ° is singlet, it can be seen that the product A is not the MFI type but the MEL type.

The BET three-point method for nitrogen at 77K (P /
(P0 = 0.01, 0.05, 0.10), the specific surface area was 476 m ² / g. Further, as a result of measuring the pore distribution by the mercury intrusion method, a pore distribution curve shown in FIG. 3 was obtained, and the total macropore volume of 4 nm or more was 0.64.
ml / g, and the macropore volume was 40 m ² / g. Pore diameter 30-100 nm (average pore diameter 50 nm)
Is 0.38 ml / g and 4n
It has a sharp pore distribution occupying about 60% of the total macropore volume of m or more.

Example 2 Sodium aluminate 6.6
8 g was dissolved in distilled water to make 140 ml. 120 ° C
Beads dried all day and night at
"Carrierct Q-10", 10-20 mesh) 10
0 g was impregnated with the entire amount of the aqueous solution for 2 hours.
Dry at 80 ° C in a nitrogen stream using a reevaporator
To support sodium aluminate on silica beads.
Was. Furthermore, after drying at 120 ° C. for one day, 40 mass
% Aqueous solution of tetrabutylammonium hydroxide 10
7.97 g in an aqueous solution diluted with distilled water to 140 ml
The total amount of the sodium aluminate-supported silica beads
For 2 hours. Dry at 80 ° C in the same way
Sodium aluminate and TBA on silica beads
Carried. The composition ratio is Si ₁TBA_0.100Na_0.053Al
_0.042It is.

The obtained precursor was placed in a basket made of a stainless steel net and placed in the hollow of a stainless steel autoclave having a capacity of 3300 ml. 30 at the bottom of the autoclave
g of distilled water was added and heated at 170 ° C. for 32 hours. After cooling the autoclave to room temperature, the product was taken out and calcined at 550 ° C. for 6 hours in an air stream to remove organic components derived from TBA, thereby obtaining 106 g of a white product.
This is designated as product B.

The shape of the product B was 10 to 20 mesh size beads while maintaining the appearance of the silica beads used as the raw material. As a result of powder X-ray diffraction measurement after pulverizing the product B, the same diffraction pattern as that of the product A was given, and it was a MEL type crystalline aluminosilicate.

The BET three-point method for nitrogen at 77K (P /
(P = 0.02, 0.06, 0.10), the specific surface area was 376 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, and the total macropore volume of 4 nm or more was 0.45 ml /
g, and the specific surface area of the macropores was 44 m ² / g.

The following examples show production examples of ethanolamines mainly from ethylene oxide and ammonia. The examples are intended for illustrative purposes of the present invention and are not intended to limit the invention.

The LHSV, the conversion of ethylene oxide and the selectivity of diethanolamine are defined as follows. In addition, almost no products other than ethanolamines were produced, and therefore, the conversion of ethylene oxide (mol%)
Is approximately equal to the overall yield (mol%) of (mono, di, tri) ethanolamine based on ethylene oxide.

LHSV = A1 / B1 A1: Volume of liquid raw material passing through the reactor every hour (cm ³ /
Hr), B1: catalyst volume (cm ³ ) in the reaction vessel.

Conversion of ethylene oxide (mol%) =
(A2 / B2) × 100 A2: mole number of ethylene oxide consumed in the reaction, B2: mole number of ethylene oxide subjected to the reaction.

The selectivity of diethanolamine (% by mass) =
(A3 / B3) × 100 A3: mass of diethanolamine in the product, B3: mass of total ethanolamine in the product.

Example 3 8.08 g of aluminum nitrate 9-hydrate was dissolved in distilled water to make a total volume of 38 ml. Silica beads dried at 120 ° C. for one day and night (“Carrierct Q-6”, manufactured by Fuji Silysia Chemical Ltd., 16
31.04 g) was impregnated with the aqueous solution at room temperature for 1 hour, and subsequently dried on a 100 ° C. water bath. This was calcined at 550 ° C. for 3 hours in an air stream, and was supported on silica beads as aluminum oxide. After cooling, 7.6 ml of a 4 mol / l aqueous sodium hydroxide solution and 33.5 g of a 40 mass% aqueous tetrabutylammonium hydroxide solution were mixed, and the total amount was adjusted to 3 with distilled water.
8 ml of the solution was impregnated for 1 hour, followed by 100
The resultant was dried in a hot water bath at ℃, and further dried in an oven at 80 ° C. under a nitrogen stream for 5 hours. The composition ratio is Si ₁ Al _0.042 Na
_0.063 TBA was _0.10 .

The obtained precursor was placed in a Teflon cup,
It was installed in the hollow of a stainless steel autoclave having a capacity of 3300 ml. 30 g of distilled water was put in the bottom of the autoclave vessel and heated at 170 ° C. for 32 hours to crystallize. After cooling to room temperature, the product taken out was packed in a jacketed column and ion-exchanged by flowing a 1 mol / liter ammonium nitrate aqueous solution at 60 ° C. and a flow rate of 0.4 ml / min for 24 hours. Distilled water 500
After washing with water, dry at 120 ° C for 5 hours.
By calcining at 50 ° C. for 6 hours to remove excess organic components, 29 g of a white product was obtained. This is designated as product C.

The shape of the product C was 16 to 32 mesh size beads while maintaining the appearance of the silica beads used as the raw material. As a result of powder X-ray diffraction measurement after pulverizing the product C, the result was essentially the same as in FIGS. 1 and 2,
It was a MEL type zeolite.

The BET three-point method for nitrogen at 77K (P /
(P = 0.02, 0.06, 0.10), the specific surface area was 410 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, and the total macropore volume of 4 nm or more was 0.6 ml / g.
Met.

(Catalyst Preparation Example 1) MEL zeolite beads (proton type, 16 to 32 mesh) prepared in Example 3 were added to a solution prepared by dissolving 0.8383 g of lanthanum nitrate hexahydrate in distilled water to make 38 ml. 29 g at room temperature
Impregnated for hours and subsequently dried on a 100 ° C. water bath. This was calcined at 550 ° C. for 3 hours in an air stream to obtain a lanthanum-containing MEL zeolite bead catalyst. This is designated as catalyst A.

(Catalyst Preparation Example 2) (Comparative Example) 100 g of MEL type zeolite (Si / Al atomic ratio 39, proton type) prepared by the method described in Example 8 of US Pat. No. 3,709,979 was used. A solution prepared by dissolving 2.50 g 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 was calcined at 550 ° C. for 3 hours in the air to obtain a lanthanum-containing MEL zeolite.

The lanthanum-containing ME obtained as described above
70 g of L-type zeolite and alumina sol (alumina sol 520 manufactured by Nissan Chemical Co., alumina content 20.7% by mass) 14
5 g (30 g as alumina) was kneaded, and the slurry was concentrated. After adjusting the water content to 40% by mass, it was extruded with a diameter of 0.7 mm and molded. This is placed in an air stream at 650 ° C3
By calcining for a period of time, a lanthanum-containing MEL catalyst molded with an alumina binder was obtained. This is called catalyst B
And

Example 4 Using the catalyst A obtained in the catalyst preparation example 1, a reaction for synthesizing ethanolamines from ethylene oxide and ammonia was carried out. Using the apparatus shown in FIG. 5, the reaction tube 1 was kept warm by wrapping a stainless steel tube having an inner diameter of 10 mm and a length of 400 mm with a heater for compensating heat radiation. A protective tube into which a thermocouple can be inserted for measuring the temperature profile of the catalyst layer was provided inside the reactor. This reactor was charged with 20 ml of catalyst A, and heated to 70 ° C. in preheater 2 (molar ratio of ammonia / ethylene oxide: 1).
5) was passed through LHSV 10 hr ^-1 to react.

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 solution was collected and analyzed by gas chromatography. Table 1 shows the results of the reaction 24 hours after the start of the reaction.

For analysis by gas chromatography, a fused silica capillary column (Fused Silica capillary column, 30 m, 0.53 mm, 0.5 μm
Quantitative analysis of ethanolamines was performed from the area ratio of the FID detector using the filmthickness (the reaction solution after the ammonia flush was diluted to 0.25% by mass,
0 μl was injected into the analytical instrument).

From this analysis, no impurities other than ethanolamines were detected.

(Comparative Example 1) A reaction was conducted in the same manner as in Example 4 except that catalyst B was used instead of catalyst A. Gas chromatography analysis showed that diglycolamine (D
Impurities such as GA), ethylene oxide 1 mol adduct to diethanolamine terminal hydroxyl group (abbreviated as DEA + EO), and ethylene oxide 1 mol adduct to triethanolamine terminal hydroxyl group (abbreviated as TEA + EO) were detected.

Table 1 shows the results of the reaction 24 hours after the start of the reaction.

[0079]

[Table 1]

[0080]

The MEL-type binderless zeolite molded article of the present invention essentially contains no binder, so that the zeolite content in the molded article is extremely high, and zeolite is not buried in the inorganic binder. For this reason, zeolite can be used efficiently, and there is a characteristic that there is no adverse effect due to impurities such as an inorganic binder.

According to the method of the present invention, the time required for crystallization is short, and since the raw material components do not elute into water, the metal components are efficiently incorporated into the crystal lattice, and the raw material composition ME having a composition almost identical to
The L-type crystalline metallosilicate can be produced in high yield.

Further, according to the method of the present invention, since the MEL-type binderless zeolite molded body produced reflects the properties of the raw silica molded body as it is, it is easy to control the physical properties such as the secondary pore structure. In addition, the amount of expensive tetraalkylammonium used can be reduced, and almost no waste liquid is generated, so that there is no need for recovery and waste liquid treatment, which is economical.

The binder-less zeolite molded product of the present invention has excellent selectivity and is less likely to generate impurities as compared with a catalyst containing a binder when aminated for amination reaction, particularly for amination of alkylene oxide with ammonia. It is.

[Brief description of the drawings]

FIG. 1. CuKα X-ray diffraction diagram of product A (2θ = 5-6)
0 °).

FIG. 2: CuKα X-ray diffraction diagram of product A (2θ = 40-
50 °).

FIG. 3 is a drawing showing a pore distribution curve of a product A by a mercury intrusion method.

FIG. 4 is a drawing showing a pore distribution curve of a product B by a mercury intrusion method.

FIG. 5 is a schematic diagram of a reaction apparatus used in Example 5.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Reaction tube 2 ... Preheater 3,4,5 ... High pressure pump 6 ... Pressure control valve 7 ... Ammonia flash tower 8 ... Recovery ammonia tank 9 ... Heat exchanger 10,11 ... Raw material tank (10: ethylene oxide, 1
1: ammonia)

Claims (7)

[Claims] 1. A binderless zeolite molded product, wherein the zeolite is of MEL type or MFI type / MEL.
Binderless zeolite molded product which is a metallosilicate having a crystal structure of a composite of the type. 2. Determined from nitrogen adsorption measurement by the BET method.
Specific surface area is 250m ^Two/ G ~ 550m^Two/ G
The molded article according to 1. 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 m ² / g to 150
m ² / g and the pore volume is 0.10 ml
The molded article according to claim 1 or 2, wherein the molded body has a concentration of from 1.5 g / g to 1.5 ml / g. 4. The following formula (1): Si ₁ (TBA) _x M ¹ _y M ² _z (1) (where TBA is tetrabutylammonium,
M ¹ represents an alkali metal, M ² represents a metal element incorporated in the metallosilicate crystal skeleton, x is 0.001-1, y
Represents a range of 0.0001 to 1, and z represents a range of 0 to 0.4. )
A method for producing a MEL-type binderless zeolite molded body, comprising contacting a zeolite precursor represented by the following formula with saturated steam. 5. The zeolite precursor comprises a tetrabutylammonium component, an alkali metal component, and, if desired,
The method of claim 4, wherein the raw material is a zeolite precursor comprising supported on silica molded body comprising a metallic element component represented by M ² in the formula (1). 6. A catalyst for an amination reaction, comprising the binderless zeolite molded product according to any one of claims 1 to 3. 7. A process for producing an alkanolamine, comprising aminating an alkylene oxide with ammonia using the catalyst according to claim 6.