JP3442348B2 - Binderless crystalline aluminosilicate molded body, method for producing the same and use thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Prior Art ZSM-5 type aluminosilicates are the oxygen 1 disclosed in U.S. Pat. No. 3,702,886.
It is a zeolite having 0-membered ring pores.

As a method for synthesizing ZSM-5 type aluminosilicate, a hydrothermal synthesis method using an aqueous reaction slurry containing tetra-n-propylammonium ion as a template agent has been known.

However, in the conventional hydrothermal synthesis reaction,
Since a part of the raw material components is dissolved in water during heating, the ratio of the components converted into the desired crystals is necessarily reduced, and the concentration of the alkaline component is low, so that the crystallization time becomes extremely long. In such a slow crystallization method,
Since large crystals grow easily and foreign metal ions other than silicon are easily excluded outside the crystal lattice, comparing the Si / Al atomic ratios in the aqueous slurry as a raw material and the synthesized ZSM-5 type zeolite Not necessarily a match. Furthermore, industrially, since the aqueous slurry is heated, it requires a relatively large-capacity closed container with respect to the mass of the produced crystals, or requires a large amount of expensive template agent, Furthermore, there are problems that a large amount of waste liquid is generated, zeolite powder is filtered, and the firing process is complicated.

Further, in the case of producing a zeolite molded body, it is necessary to first synthesize zeolite powder by a hydrothermal synthesis method and then to mold it using an inorganic binder, since the zeolite alone has poor moldability. It was In this method, it is necessary to select a binder so as not to adversely affect the intended use of the obtained zeolite, and since a large amount of an inorganic binder is required to achieve sufficient strength, the resulting molded product is There is a problem that not only the zeolite content of the above-mentioned decreases but also the zeolite is buried in the binder and cannot be effectively used.

In order to solve such a problem, a method of producing a zeolite molded body substantially containing no binder has been proposed. For example, JP-A-59-162952
In the publication, TSZ type aluminosilicate is disclosed in
-72620 discloses a MOR type aluminosilicate, and JP-A-62-138320 describes a crystalline binderless aluminosilicate molded article such as a FAU type aluminosilicate. In these methods, a zeolite powder pre-synthesized is used as a secondary raw material, which is molded with an inorganic binder such as a clay mineral or silica-alumina, and the binder is converted to zeolite by reacting with an alkaline solution. Substantially two hydrothermal synthesis steps are required. Therefore, there are problems in that the manufacturing process becomes long and the amount of waste liquid increases. Further, in this method, the Si / Al ratio of the secondary raw material zeolite and the Si / Al ratio of the inorganic binder are
It is necessary to match the Al ratio, and when the content of aluminum in the inorganic binder is low, the moldability is deteriorated, so that it was not possible to manufacture a binderless crystalline aluminosilicate molded body having a high silica content. Further, since the crystallization is carried out by the hydrothermal synthesis method twice, it is difficult for aluminum to be taken into the zeolite lattice, and such aluminum is contained in the product as an impurity.

As described above, a ZSM-5 type binderless aluminosilicate molded body in which aluminum does not substantially exist outside the crystal lattice has not been heretofore known.

[0008]

Therefore, the object of the present invention was made in view of the above-mentioned problems, and a ZSM-5 type binderless crystalline alumino in which aluminum does not substantially exist outside the crystal lattice. It is intended to provide a silicate molded body, a method for producing the same, and a use as an amination catalyst.

[0009]

The inventors of the present invention have developed ZSM-5.
Type binderless aluminosilicate moldings,
As a result of diligent study, for example, a silica molded body, after supporting an aluminum component, an alkali metal component and a tetraalkylammonium component, by a method of contacting with saturated steam under specific conditions, the total amount of aluminum and silica in the lattice ZS that can be converted into the incorporated ZSM-5 type aluminosilicate and maintains the shape of the silica molded body that is the raw material, and that does not substantially contain aluminum outside the crystal lattice
The inventors have found that an M-5 type binderless crystalline aluminosilicate molded article can be produced, and completed the present invention.

That is, the present invention is a binderless crystalline aluminosilicate molding, wherein the aluminosilicate has a ZSM-5 type crystal structure, and the composition ratio (atomic ratio) of silicon and aluminum constituting the crystal structure. ) Is 0.0001 to 0.5 of aluminum with respect to 1 of silicon.
And the content of aluminum outside the crystal lattice is 3% or less of the total aluminum contained in the molded body, the present invention relates to a binderless crystalline aluminosilicate molded body.

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

The binderless crystalline aluminosilicate molding of the present invention has a pore size of 4 as determined by the mercury penetration method.
having pores of 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.

Another aspect of the present invention is aluminum
Ingredients and alkali metal ingredients and tetraalkylammonium
Supporting the raw material containing the components on the silica molded body
Aluminosilicate precursor represented by the following formula (1) obtained _{by: Si 1 Al x M y (} SDA) z (1) ( In the formula, M represents an alkali metal, SDA represents tetraalkyl ammonium, 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 brought into contact with saturated steam, and a method for producing a ZSM-5 type binderless crystalline aluminosilicate molded article is characterized.

[0014]

Further, another invention of the present invention relates to a catalyst for an amination reaction, which comprises the binderless crystalline aluminosilicate molding.

Another aspect of the present invention is the use of the above catalyst,
It relates to a method for producing an alkanolamine , which comprises aminating alkylene oxide with ammonia.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

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 the alkyl group has 1 to 5 carbon atoms, x is 0.0001 to 0.5, and y is 0.0.
001-1 and z represent the range of 0.001-1. The composition is not particularly limited as long as it is represented by ().

Further, in the above formula (1), x is 0.
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 particularly x is 0.0
005 to 0.3, y is 0.0005 to 0.5, and z is 0.
It is desirable that the range is 003 to 0.8.

The method of preparing the aluminosilicate precursor is not particularly limited, but a method of supporting a raw material containing an aluminum component, an alkali metal component and a tetraalkylammonium component on a silica molded body is preferable.

In the method of the present invention, a silica molded body is used as the silica source of the crystalline aluminosilicate. The silica molded body is not particularly limited, and a commercially available product may be used. As the silica molded body, one having a relatively large specific surface area is preferably 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. This is because if the specific surface area is too small, it may take a long time to crystallize and the crystallinity may decrease.

Further, the silica molded body has pores having a pore size of, for example, 4 nm or more as determined by the mercury penetration 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 thereof is not particularly limited, but examples thereof include a spherical shape, a cylinder type and a ring type. Although the size is not limited, it is usually preferably in the range of 0.5 to 10 mm (corresponding to the diameter).

The mechanical strength of the silica molded body is not limited, but is usually 9.8 newtons or more, preferably represented by 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 body has a correlation with the mechanical strength of the obtained binderless crystalline aluminosilicate molded body, by using a high strength silica molded body, a binderless material with strength that can withstand practical use is obtained. A crystalline aluminosilicate molding can be manufactured.

Examples of the tetraalkylammonium component include tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetraisopropylammonium, tetra-n-butylammonium, tetra-n-pentylammonium, triethylmethylammonium, triethyl-n. -Propyl ammonium, tri-n-propyl methyl ammonium, tri-n-butyl methyl ammonium and other halides,
Examples thereof include hydroxides, compounds having an alkyl group of a tetraalkylammonium component having 1 to 5 carbon atoms are preferable, compounds containing a tetra-n-propylammonium ion are more preferable, and tetra-n is particularly preferable.
-Purpylammonium hydroxide. Tetra
By using the n-propyl ammonium salt, ZS
This is because M-5 type aluminosilicate can be efficiently synthesized.

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

Examples of the aluminum component include aluminate, nitrate, sulfate, halide, hydroxide and the like. Furthermore, it is preferably used in the form of an aqueous solution. Generally, sodium aluminate is preferred.

In the method for preparing an aluminosilicate precursor, at least one 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 with the element (A), a bi (poly) metallic binderless ZSM-5 type metalloaluminosilicate molded product in which these elements are incorporated in the lattice can also be obtained.

The T of these zeolites, such as aluminum
The metal component serving as an atom (metal component constituting the zeolite crystal skeleton) may be in any form as long as it is supported on the 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 firing. In this case,
A metal component and / or an alkali metal component to be a T atom is supported on a silica molded product and fired to obtain a silica molded product carrying the above components. A tetraalkylammonium component and, if necessary, an alkali metal component are carried on this to prepare a zeolite precursor. By using such a zeolite precursor, it may be possible to increase the mechanical strength of the zeolite molded body.

The method of supporting the raw material containing the aluminum component, the alkali metal component and the 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 support it on the substrate, it is preferable to include a solution of the raw material substance in a silica molded body and then dry it. As an example, a predetermined amount of each component is made into a uniform aqueous solution, which is prepared and impregnated so that the amount of the aqueous solution corresponds to the amount of water absorption of the silica molded body. At this time, each component may be loaded simultaneously, or each component or a homogeneous mixed solution may be loaded several times. Even if they are loaded in a divided manner, the order of loading does not affect the products. Then, the water content in the precursor is reduced by a drying process. The water content of the precursor is usually 30% by mass or less, based on the total mass of the precursor after drying, because the supported component does not elute during crystallization and the zeolite yield is good, and further, The range of 20 to 0.1 mass% is preferable.

The drying temperature after impregnation with the aqueous solution is not particularly limited, but is usually 20 to 120 ° C., preferably 50 to 10 from the viewpoint of less decomposition of the tetraalkylammonium salt.
It is in the range of 120 ° C.

The method of drying is not particularly limited, and any conditions of reduced pressure and normal pressure may be used. Drying under a stream of air at normal pressure is preferable because it is simple and easy.

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 contained tetraalkylammonium component is small and the ZSM-5 type binderless zeolite molding having high crystallinity is formed. 80-260 to get body
C., preferably in the range of 100 to 230.degree.

The contact time between the aluminosilicate precursor and saturated steam is usually 2 hours or more, preferably 2 to
It is in the range of 150 hours. This is because if the crystallization time is too short, the crystallinity decreases, and if it is too long, mixed crystals with other zeolites may form.

The method and apparatus for contacting the aluminosilicate precursor 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 the precursor in the hollow of the pressure-resistant container, filling the lower part of the container with water corresponding to the amount of saturated steam determined by the reaction temperature and the volume 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 may be used, or the synthesis may be continuously carried out by a moving bed reactor.

In the method of the present invention, the aluminosilicate precursor is dispersed in water and hydrothermal reaction is not carried out.
Crystallization can be carried out. In the method of the present invention, almost the entire amount of the raw material can be converted to zeolite, the silica molded body as the raw material, while maintaining the shape, since the total amount is converted to zeolite, essentially the binder is in the produced zeolite. It will not be included. Thus, a binderless crystalline aluminosilicate molding can be obtained by a simple method.

Since no binder is used in the method of the present invention, the synthesized binderless crystalline aluminosilicate molding has an extremely high crystallinity with a zeolite content of approximately 100%. The 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. Further, the crush strength can be controlled by the crystallinity. For example, as measured by a Kiya type hardness meter, it is desirable that it is 1 newton or more, preferably 5 newtons or more.
The pore volume in the range of 150 nm including the average pore diameter is
It has a sharp pore distribution of 60% or more, preferably 70% or more of the total macropore volume of 4 nm or more.

Further, according to the production method of the present invention, it is possible to use, as a raw material, a silica molded body having an arbitrary shape such as a spherical shape, a cylinder shape, a ring shape or the like. By converting a precursor prepared from a silica molded body having an arbitrary shape into zeolite by the method of the present invention, a binderless crystalline aluminosilicate molded body can be formed as it is.

Furthermore, in the production method of the present invention, not only the appearance of the raw silica molding is retained, but also the crushing strength, the macropore distribution, etc. are reflected. Therefore, the physical properties of the binderless crystalline aluminosilicate molded product can be easily controlled by controlling the physical properties of the silica molded product used as the raw material.

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

An aluminum component, a tetraalkylammonium component, tetra-n-propylammonium, 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 type aluminosilicate molded body is obtained. Here, the composition ratio (atomic ratio) of each component is the silica molding (as Si)
The ratio of aluminum component, tetraalkylammonium component and alkali metal component is usually 0.0
001 to 0.5: 0.001 to 1: 0.0001 to 1,
Preferably 0.0001-0.5: 0.002-1:
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-propylammonium hydroxide is preferable. The aluminum component is preferably a water-soluble salt. Examples include aluminate, nitrate, sulfate, and halide, but sodium aluminate is preferable. Furthermore, 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 product (framework topology code by the International Zeolite Association is MFI type) in which this component is incorporated as a T atom can be produced.

The binderless crystalline aluminosilicate molding of the present invention has the following characteristics (i) to (iii).

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

(Ii) The composition ratio (atomic ratio) of silicon and aluminum constituting the aluminosilicate crystal structure is 0.0001 to 0.5 of aluminum to 1 of silicon,
The range of 0.0005 to 0.3 is preferable.

(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 product of the present invention has a ZSM-5 type crystal structure. This is powder X
It can be confirmed by measuring line diffraction.

The structure of the ZSM-5 type aluminosilicate has three-dimensionally bonded SiO ₄ and AlO ₄ tetrahedra composed of silicon atoms or aluminum atoms and four oxygen atoms coordinated at the vertices. is doing. For this reason,
It is well known that all aluminum atoms entering the zeolite skeleton are tetra-coordinated, while aluminum atoms outside the lattice outside the skeleton are usually hexa-coordinated. These two types of aluminum atoms are, for example, Al
²⁷ MAS-NMR measurement makes it easy to distinguish or quantify. Chemical shift (σ) 5 attributed to tetracoordinated aluminum
The peaks measured in the range of 0 to 70 ppm and the peaks observed in the range of σ = 0 to 10 ppm belonging to hexacoordinated aluminum were determined, and the molding obtained in the present invention was based on this area ratio. The abundance ratio of aluminum outside the lattice is calculated with respect to the total amount of aluminum contained in the body.

The molded article of the present invention is characterized in that the aluminum component outside the zeolite lattice is very small. A
The amount of aluminum present outside the lattice calculated by the measurement of l ²⁷ MAS-NMR is 3% by mass of the total aluminum in the molded body.
Below, preferably not more than 2% by mass, more preferably substantially not contained (not detected). The non-crystallinity of the molded product is presumed to be derived from the silica component that 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 usually 0.0001 to 0 for aluminum relative to 1 for silicon. .5, preferably 0.00
It is in the range of 05 to 0.3.

Further, in the molded body, the specific surface area determined by 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 product has macropores having a pore diameter of 4 nm or more as determined by the mercury porosimetry method. The surface area due to 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 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., it can be used as an adsorbent, a catalyst for a chemical reaction, or a catalyst in various chemical processes. It can be used as a carrier. For example, it is preferably used as an alkylation reaction catalyst, an isomerization reaction catalyst, a cracking reaction catalyst, a Beckmann rearrangement reaction catalyst, a hydration reaction catalyst, an alcohol addition reaction catalyst, and the like.

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

Further, in various amination reactions, the adverse effect of the inorganic binder is great, so that it is preferable to use the binderless crystalline aluminosilicate molding of the present invention which does not use a binder as a catalyst. As the amination reaction, a reaction of aminating alkylene oxide with ammonia to synthesize an alkanolamine, an ammonia addition reaction to an olefin, an N-alkylation reaction with an alcohol represented by the synthesis of methylamines, a ring of ethanolamines. Examples thereof include chemical dehydration reaction and ethylenediamine synthesis reaction from monoethanolamine and ammonia. Conventional reaction conditions can be adopted as the reaction conditions for aminating alkylene oxide with ammonia to synthesize alkanolamines. The following conditions are preferable.

The molar ratio of ammonia to alkylene oxide is usually in the range 1 to 50: 1, preferably 2 to 40: 1. The reaction temperature is usually 20 to 300 ° C,
It is preferably in the range of 30 to 200 ° C. The reaction pressure is usually 2 to 30 MPa, preferably 4 to 20 MPa.
Is the range. LHSV (hr ^-1 ) is usually 0.1 to
It is in the range of 50, preferably 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, the formation of impurities such as diglycolamines,
There are problems that the strength of the molded body is weak and the selectivity of diethanolamine is lowered. This is due to the effect of diluting the catalyst component by adding the inorganic binder and the chemical properties of the inorganic binder. Therefore, it is particularly preferable to use the binderless zeolite molded product of the present invention having no inorganic binder and having sufficient strength as a catalyst or a catalyst carrier. In this case, it is preferable that the crystalline structure of the crystalline aluminosilicate is ZSM-5 type (framework topology according to the International Zeolite Association is MFI type) since it exhibits 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.

Measuring Method of Mechanical Strength The mechanical strength was measured using a Kiya type hardness meter. The average value of 10 molded articles was used.

Method for Measuring Zeolite Content It is confirmed by powder X-ray diffraction. It is measured as a ratio of the sum of peak areas belonging to zeolite to the sum of all peak areas found to exist in CuKα X-ray diffraction measured at 2θ = 5 to 140 °. The zeolite content of almost 100% means that no peak other than zeolite is observed as a result of measurement under the above-mentioned conditions.

Crystallinity measurement method Confirmed by powder X-ray diffraction method. It is measured as the ratio of the area attributed to zeolite and the area of the halo of amorphous origin. In this analysis method, since the analysis result may vary greatly depending on the characteristics of the measuring device, the reference catalyst provided by the Catalysis Society is usually used as a standard substance.

In the case of ZSM-5 type zeolite, "J
RC-Z5-90H (1) "is used, and amorphous silica (for example, Caractact Q-5 manufactured by Fuji Silysia Chemical Ltd.
A standard curve is prepared by using a sample prepared by mixing (0 crushed 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 created.

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

This was transferred onto an evaporation dish. After drying on a hot water bath at 100 ° C., it was dried at 80 ° C. in an air stream of nitrogen for 5 hours. The obtained precursor was placed in a Teflon cup and placed in the hollow Teflon (registered trademark) crucible with a jacket having a volume of 100 ml. The bottom of the crucible container was charged with 1.00 g of distilled water and heated at 180 ° C. for 8 hours. The crucible was cooled to room temperature, the product taken out was packed in a column, washed with 500 ml of distilled water, and heated at 120 ° C. for 5 minutes.
Dried for hours. The white solid obtained was calcined in an air stream at 540 ° C. for 3.5 hours 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 to 20
It was a mesh size bead. After pulverizing 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 originating from aluminum outside the zeolite lattice. Furthermore, when the side band peaks were excluded, only a signal at σ54.7 ppm attributable to aluminum in the lattice was observed. From this, it can be seen that the entire amount of aluminum supported on the silica beads is incorporated in the skeleton of the zeolite crystal. That is, the product A is a ZSM-5 type aluminosilicate.

BET 3-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. As a result of measuring the pore distribution by the mercury porosimetry, the pore distribution curve shown in FIG. 3 was obtained. In FIG. 3, for example, 1E-1 is 1 × 10 ⁻¹ , 3
E-3 means 3 × 10 ⁻³ . The total macropore volume of 4 nm or more 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 the pore distribution is extremely sharp, accounting for 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 concentration TPAOH aqueous solution. 120
Silica beads dried at ℃ for 1 day ("Carrieract Q-50", 10-20 mesh manufactured by Fuji Silysia Chemical Ltd.) 2
After 5.05 g was impregnated in the above aqueous solution for 1 hour, it was evaporated to dryness with stirring to uniformly support sodium aluminate and TPAOH on silica beads.
The composition ratio was Si ₁ Al _0.03 Na _0.04 TPA _0.20 . This is carried out in the same way as in Example 1 to give the white product 25.
44 g was obtained. This is referred to as product B.

The shape of the product B retained the appearance of the silica beads used as a raw material and was a bead having a size of 10 to 20 mesh. Powder X after crushing product B
As a result of measurement by line diffraction, it is essentially the same as that of 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 measured by the 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 porosimetry, the total macropore volume of 4 nm or more was 1.0 ml / g, and the surface area of the macropore was 2
It was 0 m ² / g.

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

The shape of the product C retained the appearance of the silica beads used as a raw material and was a bead having a size of 10 to 20 mesh. Powder X after crushing product C
As a result of line diffraction, the crystallinity is slightly low.
The diffraction pattern obtained was essentially the same as that of 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 nitrogen at 77 K measured by the BET three-point method (P / P0 = 0.01, 0.03, 0.06) was 400 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 is 1.1 ml / g, and the surface area of the macropore is 2
It was 7 m ² / g.

Example 4 Using 6.54 g of sodium aluminate, change the loading composition ratio
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.
26.60 g of white product was obtained. This is product D
Called.

The shape of the product D retained the appearance of the silica beads used as a raw material, and was a bead having a size of 10 to 20 mesh. Powder X after crushing product D
As a result of line diffraction, the crystallinity is slightly low.
Which was essentially 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 measured by the BET three-point method (P / P0 = 0.01, 0.03, 0.06) was 410 m ² / g. As a result of measuring the pore size distribution by the mercury porosimetry, 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 20.70 g of a white product was obtained in the same manner as in Example 1 except that the crystallization condition was changed to 160 ° C. for 8 hours. This is referred to as product E.

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

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 measured by the 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 is 1.0 ml / g, and the surface area of the macropores is 4
It was 0 m ² / g.

Example 6 0.3 ml of a 4 mol / L sodium hydroxide aqueous solution and 9.14 g of TP were added to 5.00 g of a colloidal silica solution (Snowtex S: SiO ₂ 30% by mass, manufactured by Nissan Kagaku).
Aqueous AOH solution (concentration 1 mol / L) was added with stirring. After stirring at room temperature for 30 minutes, 0.31 g of an aqueous solution of aluminum nitrate nonahydrate dissolved in 5 g of distilled water was gradually added dropwise. The raw material mixture of this aqueous slurry was stirred for 2 hours. Then, silica beads were dried at 120 ° C. for one day (“Carrieract Q-50” manufactured by Fuji Silysia Chemical Ltd., 1
13.0Og (0-20 mesh) was impregnated for 1 hour.
The composition ratio was Si ₁ Al _0.003 Na _0.005 TPA _0.04 . This is carried out in the same way as in Example 1 to give the white product 16.
20 g was obtained. This is referred to as product F.

The shape of the product F retained the appearance of silica beads used as a raw material, and was a bead having a size of 10 to 20 mesh. Powder X after crushing product F
As a result of measurement by line diffraction, it is essentially the same as that of 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 77 K measured by the BET three-point method (P / P0 = 0.01, 0.03, 0.06) was 330 m ² / g. As a result of measuring the pore size distribution by the mercury porosimetry, 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 ("Carriact Q" manufactured by Fuji Silysia Chemical Ltd.)
-10 ", 10 to 20 mesh, average pore size 10 nm,
22.93 g of mechanical strength (29.4 Newton) was used. Other than this, it carried out similarly to Example 1, and obtained 21.00 g of white products. This is referred to as product G.

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

BET 3-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. As a result of measuring the pore distribution by the mercury porosimetry, the pore distribution curve shown in FIG. 4 was obtained. The total macropore volume of 4 nm or more is 0.67 ml / g
And the surface area of the same macropore was 30 m ² / g. The pore volume in the range of 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 that occupies about 85% of the total macropore volume of m or more.

Example 8 Silica beads ("Carriact Q" manufactured by Fuji Silysia Chemical Ltd.)
-50 ", 5-10 mesh, average pore size 50 nm, mechanical strength 59 Newton) 22.93 g. Otherwise in the same manner as in Example 1, white product 22.0 was obtained.
0 g was obtained. This is referred to as product H.

The shape of the product H retained the appearance of silica beads used as a raw material, and was a 5 to 10 mesh size bead. The product H was pulverized and then measured by powder X-ray diffraction to find that it was essentially the same as that of 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.
Had a crystallinity of 100%.

BET 3-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. Further, as a result of measuring the pore distribution by the mercury intrusion method, the total macropore volume of 4 nm or more is 0.94 ml / g, and the surface area of the same macropore is 2
It was 5 m ² / g.

The mechanical strength of the obtained molded product was 39 Newtons.

Example 9 8.08 g of aluminum nitrate nonahydrate was dissolved in distilled water to a total amount of 38 ml. Silica beads dried at 120 ° C for 1 day ("Carrieract Q-" manufactured by Fuji Silysia Chemical Ltd.)
6 ", 16 to 32 mesh) 31.04 g was impregnated with the aqueous solution at room temperature for 1 hour. Subsequently, it was dried in a hot water bath at 100 ° C, and this was dried at 550 ° C in a stream of air.
It was baked for 3 hours. It was supported as aluminum oxide on silica beads. Then, it cooled. 7.6 ml of 4 mol / L concentration sodium hydroxide aqueous solution and 22.84 g of 23 mass% concentration TPAOH aqueous solution were mixed. The solution was made up to a total volume of 38 ml with distilled water and impregnated for 1 hour, then 10
It was dried on a water bath at 0 ° C. Further, it was dried 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 _0.05 .

The obtained precursor was put in a Teflon cup. It was placed in the hollow of a stainless steel autoclave with a volume of 3300 ml. 30 at the bottom of the autoclave container
Crystallized by adding 180 g of distilled water and heating at 180 ° C. for 20 hours. After cooling to room temperature, the product taken out was packed into a jacketed column. 60 ° C, 0.4 ml / m
A 1 mol / L concentration ammonium nitrate aqueous solution was circulated for 24 hours at a flow rate of in to perform ion exchange. Distilled water 5
After washing with 00 ml of water, it was dried at 120 ° C. for 5 hours. It was calcined at 550 ° C. for 6 hours under a stream of air. By removing the excess organic components, 29 g of a white product was obtained. This is designated as Product J.

The shape of the product J was 16 to 32 mesh while maintaining the appearance of the silica beads used as a raw material. The product J was pulverized and then measured by powder X-ray diffraction. As a result, it was essentially the same as in FIG. 1 and was a ZSM-5 type zeolite.

BET 3-point method of nitrogen at 77K (P /
The specific surface area according to P0 = 0.01, 0.03, 0.06) was 360 m ² / g. As a result of measuring the pore distribution by the mercury porosimetry, 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 the silica carrier and a precursor containing no sodium component was used. Immediately after being taken out from the autoclave, the molded body was crushed and powder X-ray diffraction measurement was performed. As a result, it was amorphous.

Comparative Example 2 An experiment was carried out in the same manner as in Example 9 except that TPAOH was not supported on the silica carrier and a precursor in which no tetraalkylammonium component was present was used. Immediately after being taken out from the autoclave, the molded body was crushed and powder X-ray diffraction measurement was performed. As a result, it was amorphous.

The examples which follow are examples of the production of ethanolamines mainly from ethylene oxide and ammonia. This example is intended for purposes of illustrating the invention and is not intended to limit the invention.

The LHSV, ethylene oxide conversion and monoethanolamine selectivity are defined as follows. In addition, almost no products other than ethanolamines are produced. Therefore, the conversion rate (mol%) of ethylene oxide is (mono,
It is almost 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 per hour (cm ³ /
hr) AC: catalyst volume (cm ³ ) in the reaction vessel.

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

Selectivity of diethanolamine (% 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 type zeolite beads (proton type, 16 to 32 mesh) were impregnated at room temperature for 1 hour. Continue to 100
Dried on a water bath at ℃. 5 under the air flow
The mixture was calcined at 50 ° C. for 3 hours to obtain lanthanum-containing MFI type zeolite beads. This is referred to as catalyst CA.

Catalyst Preparation Example 2 (Comparative Example) Commercially available ZSM-5 zeolite (manufactured by Zeorist, Si / A)
1 atomic ratio = 28, proton type) 100 g, 2.50 g
A solution of lanthanum nitrate hexahydrate in Example 1 dissolved 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 3 at 550 ℃ under air flow
It was calcined for an hour to obtain a lanthanum-containing ZSM-5 zeolite.

The lanthanum-containing ZSM-5 thus obtained
70 g of zeolite and 145 g of alumina sol (alumina sol 520 manufactured by Nissan Chemical Industries, alumina content 20.7% by mass)
(30 g of alumina) was kneaded and the slurry was concentrated. After the water content was adjusted to 40% by mass, it was extruded to a diameter of 0.7 mm. This was calcined in an air stream at 650 ° C. for 3 hours to obtain a lanthanum-containing ZSM-5 catalyst molded with an alumina binder. This is referred to as 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.
A mm tube made of stainless steel was wrapped with a heater that compensates for heat dissipation and kept warm. In order to measure the temperature profile of the catalyst layer, a protective tube capable of inserting a thermocouple was provided inside the reactor. The reactor was filled 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 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 circulated through the LHSV at 10 hr ⁻¹ , and the reactor 3
Supplied to. 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 the ammonia flash tower 7 and analyzed by gas chromatography. Unreacted source gas,
Ammonia was mainly cooled via the heat exchanger 9 and recovered in the recovered ammonia tank 8. Recovery ammonia tank 8
Was recycled as raw material ammonia through the high pressure pump 6.

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 based on the area ratio of the FID detector (the reaction solution after ammonia flush was diluted to 0.25 mass%,
10 μL was injected).

Table 1 shows the reaction results when 24 hours had elapsed from the start of the reaction. Impurities other than ethanolamines were not detected by this analysis.

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

The results are shown in Table 1.

[0115]

[Table 1]

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

[0117]

The binderless crystalline aluminosilicate molded product of the present invention contains essentially no binder, so that the zeolite content in the molded product is extremely high,
Moreover, the zeolite is not buried in the inorganic binder, and the zeolite can be efficiently used. Furthermore, it is not necessary to consider the adverse effects caused by impurities such as the inorganic binder and extralattice aluminum.

When the binderless ZSM-5 type aluminosilicate molded article of the present invention is used as a catalyst, the activity is lowered, the generation of impurities can be suppressed, and the shape selectivity which is the original 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, the molded precursor and saturated water vapor are brought into contact with each other for crystallization, so that a 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 are not eluted into water, so that the metal ions are efficiently taken into the crystal lattice. The composition of the raw material and the composition of the product are in good agreement with each other, and there is no extralattice aluminum
The 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 silica molded product, so that the physical properties such as the pore structure can be easily controlled. , The scope of application can be expanded. In addition, since the amount of expensive tetraalkylammonium used can be reduced and almost no waste liquid is generated,
It is an economical manufacturing method that does not require consideration of recovery and waste liquid treatment.

[Brief description of drawings]

1 shows the CuKα X-ray diffractogram of product A. FIG.

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

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

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

FIG. 5 is a drawing showing a reactor 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)

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C01B 39/00 B01J 29/00 JISC file (JOIS)

Claims (6)

(57) [Claims] 1. A binderless crystalline aluminosilicate molding, wherein the aluminosilicate is ZSM-5.
Has a type crystal structure, and the composition ratio (atomic ratio) of silicon and aluminum forming the crystal structure is as follows:
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. Binderless crystalline aluminosilicate molding. body. 2. The molded product 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 measured by mercury porosimetry 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 product according to claim 1 or 2, which has a volume of ml / g. 4. An aluminum component and an alkali metal component
A raw material containing a tetraalkylammonium component,
Aluminosilicate precursor represented by the following formula obtained by supporting silica molded body _{(1): Si 1 Al x} M y (SDA) z (1) ( In the formula, M is an alkali metal, SDA Represents tetraalkylammonium, and x represents 0.0001-0.
5, y represents the range of 0.0001 to 1, and z represents the range of 0.001 to 1. ) Is brought into contact with saturated steam, and a method for producing a ZSM-5 type binderless crystalline aluminosilicate molding. 5. A catalyst for amination reaction, comprising the binderless crystalline aluminosilicate molding according to any one of claims 1 to 3. 6. A method for producing an alkanolamine , which comprises aminating an alkylene oxide with ammonia using the catalyst according to claim 5 .