JPH11165074A - Production of titanosilicate-carrying catalyst and production of organic compound using the same by hydrogen peroxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a titanosilicate-carrying catalyst exhibiting activity to the epoxidation or the like of an olefin using hydrogen peroxide as an oxidizing agent and excellent in handling property or the like by forming a silica-titania dry gel on a carrier, treating it with pressurized steam to crystallize and firing. SOLUTION: The titanosilicate is crystallized on the carrier by forming the silica-titania dry gel containing a silicon compound, a titanium compound and a tetraalkylammonium compound on the carrier and next, treating it with the pressurized steam and is fired. As the silicon compound, a tetraalkyl orthosilicate or a colloidal silica or the like is used. As the titanium compound, a tetraalkyl orthotitanate or a hydrolyzable halogenated titanium compound or the like is used. As the tetraalkylammonium compound used as a forming material, a tetraalkylammonium hydroxide, tetraalkylammonium halide and the like are mentioned.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for treating epoxidation of olefin compounds and hydroxylation of phenol compounds or ammoximation of ketone compounds using hydrogen peroxide as an oxidizing agent. It relates to the preparation of an excellent titanosilicate catalyst and the use of this catalyst.

[0002]

2. Description of the Related Art Titanosilicate is a ZSM-5 in which the silicon of the crystal lattice is replaced by titanium instead of aluminum.
Is a type of zeolite having the same crystal structure as Titanosilicate is active in the oxidation reaction of various organic compounds using hydrogen peroxide as an oxidizing agent, for example, epoxidation of olefin compounds, hydroxylation of aromatic compounds, production of alcohols and ketones by oxidation of alkane compounds, It is known as a catalyst for the production of ketoxime compounds by ammoximation of ketone compounds.

[0003] A catalyst having a high activity is required because the probability of the reaction substrate approaching the reactive site inside the titanosilicate pores is increased and the distance over which the product diffuses out of the pores is reduced. In order to obtain the catalyst, the smaller the particle size of the catalyst, the better. However, from a practical viewpoint, the smaller the particle size, the more difficult the handling surface as a catalyst, that is, the more difficult the separation and recovery of the catalyst, and the more the advantage as a solid catalyst is lost.

A method for preparing a titanosilicate catalyst is disclosed in JP-A-56-97720 and JP-A-59-5127.
No. 3, JP-A-61-183275, JP-A-62-18
No. 5081, JP-A-6-9592, JP-A-7-100
No. 387, a titanosilicate is obtained by hydrothermally synthesizing a sol containing an oxide of silicon and titanium and a tetraalkylammonium hydroxide as a mold agent in an autoclave. However, the titanosilicate prepared by the above-mentioned method is all fine particles, and has extremely poor handling characteristics. For example, as a process problem, it takes a long time to separate and wash the catalyst due to clogging of the filter cloth. Furthermore, it is very difficult to recover the catalyst adhering to the filter cloth, and unrecovered catalyst accumulates on the filter cloth.For example, in the case of a batch reaction, every time the number of reactions increases, it is necessary to separate and clean the catalyst. The time gets longer.

On the other hand, as a method for preparing a titanosilicate catalyst having improved mechanical strength and handling characteristics, Japanese Patent Application Laid-Open No. 63-103817 discloses a method in which fine particles of titanosilicate obtained by hydrothermal synthesis are mixed with a binder. A method for obtaining a catalyst having an increased particle size by a spray drying method has been proposed. However, the catalyst formed by this method is not practical in terms of ease of filling and discharging into the reactor, good flowability, and insufficient in strength.

Further, Japanese Patent Application Laid-Open No. H8-103659 proposes a method of coating the surface of a carrier with fine particles of titanosilicate by spraying a slurry solution containing fine particles of titanosilicate onto the surface of a spherical carrier. However, the catalyst obtained by this method is not suitable for use in a reaction apparatus such as a stirring tank because the binding strength of the titanosilicate fine particles on the surface of the carrier is insufficient. Further, the carrier is limited to a spherical shape, and a carrier having a more complicated shape cannot be used.

Further, Japanese Patent Publication No. Hei 8-504125 proposes a method in which hydrothermal synthesis is carried out in the presence of a carrier to crystallize titanosilicate on the carrier. However, when silica gel is used as the support, this method can only obtain a catalyst in which the support is finely divided during hydrothermal synthesis.

As a method of synthesizing a zeolite membrane other than hydrothermal synthesis, Japanese Patent Application Laid-Open No. Hei 7-89714 discloses a method in which a sol solution or a gel suspension is applied to a porous ceramic substrate, dried and dried. An example is disclosed in which a zeolite membrane is synthesized by exposure to steam containing water and used for a separation membrane.

[0009]

DISCLOSURE OF THE INVENTION The present invention relates to a method for treating epoxidation of olefin compounds, hydroxylation of phenol compounds, or ammoximation of ketone compounds using hydrogen peroxide as an oxidizing agent. An object of the present invention is to provide a method for producing a titanosilicate-supported catalyst having excellent strength. Another object of the present invention is to provide a method for producing an epoxy compound and / or a derivative thereof by selective epoxidation of an olefin compound using this catalyst, and a divalent compound by selective hydroxylation of a monohydric phenol compound. An object of the present invention is to provide a method for producing a phenol compound or a method for producing a ketoxime compound by selective ammoximation reaction of a ketone compound.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, first, a silica-titania dry gel containing a silicon compound, a titanium compound and a tetraalkylammonium compound was formed on a carrier. After forming the titanosilicate on the carrier by steaming it under pressure and then sintering it, the above object is achieved by firing, and the titanosilicate carrier having excellent handling characteristics and mechanical strength A catalyst was found to be obtained. The present invention has been completed based on such findings.

[0011] That is, the present invention relates to a carrier comprising a silicon compound,
A sol or gel suspension containing a titanium compound and a tetraalkylammonium compound is applied and dried to form a gel, which is then subjected to steam treatment under pressure to crystallize the titanosilicate on the carrier. And a method for producing a titanosilicate-supported catalyst characterized by firing. Further, a method for producing an epoxy compound and / or a derivative thereof by selective epoxidation of an olefin compound using the titanosilicate-supported catalyst, and a method for producing a dihydric phenol compound by selectively hydroxylating a monohydric phenol compound And a method for producing a ketoxime compound by a selective ammoximation reaction of a ketone compound.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION A suspension of a sol or a gel to be applied to a carrier of the present invention is prepared from a solution comprising a silicon compound, a titanium compound, a tetraalkylammonium compound as a template and water. A gel suspension is one in which the gel exhibits fluidity in the presence of a solvent.

As the silicon compound that can be used here, tetraalkyl orthosilicate (Si (OR
₁ ) ₄ ; wherein R ₁ represents an alkyl group having 1 to 5 carbon atoms) or colloidal silica or the like. As the tetraalkyl orthosilicate, tetraethyl orthosilicate is preferably used.

Examples of the titanium compound include tetraalkyl orthotitanate (Ti (OR ₂ ) ₄ ; R ₂ represents an alkyl group having 1 to 5 carbon atoms) or a hydrolyzable halogenated titanium compound exemplified by TiOCl ₂ . Etc. can be used. As the tetraalkyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate and tetrabutyl orthotitanate are preferably used.

Examples of the tetraalkylammonium compound used as the mold include tetraalkylammonium hydroxide and tetraalkylammonium halide. Among these compounds, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapropylammonium bromide and the like are preferably used. It is particularly preferred to use tetrapropylammonium hydroxide to form titanosilicate crystals having a ZSM-5 structure.

When preparing a suspension of a sol or gel, the charge ratio of the raw materials is as follows.
i / Ti atomic ratio is 5-500, and tetraalkylammonium compound and silicon compound have N / Si atomic ratio of 0.2.
The molar ratio of water to the silicon compound (water / silicon compound) is 10 to 100. Further, from the reaction mixture obtained by mixing the raw materials in the charged molar ratio, alcohols and the like are produced along with the hydrolysis of the silicon compound and the titanium compound, and these hydrolysis products are sol or gel. The suspension may or may not be removed before applying the suspension to the carrier.

The carrier is not particularly limited as long as it has a certain strength and is stable against a certain amount of heat. For example, silica gel, alumina gel, various zeolites and the like are suitable. Examples of the above zeolite include ZS
Zeolite having an MFI structure including various metallosilicates such as M-5, silicalite, tin silicate, vanadosilicate, germanosilicate, and gallosilicate; and a MEL structure including ZSM-11 and silicalite 2. Zeolite having a MOR structure such as zeolite, mordenite, zeolite having a BEA structure such as beta zeolite, MC
Zeolites having mesopore pores such as M-41 and MCM-48 are exemplified.

The shape of the carrier is not particularly limited, and a carrier having a more complicated structure such as a honeycomb structure in addition to a spherical or granular shape can be used.

The size of the carrier is such that the particle size distribution median (particle size in which 50% by weight of the smaller particles are 50% by weight in the particle size distribution) suitable for use in industrial equipment is 0.1 mm.
The above is preferred.

The application of the sol or gel suspension to the carrier can be carried out by a dipping method, a spin coating method, or a spray method. If the carrier is likely to be destroyed due to rapid adsorption of water, such as silica gel, a sol or gel suspension is applied after humidifying treatment with water vapor or the like in advance.

Gelation from the sol or drying of the gel suspension by drying can be performed by heating, vacuum evaporation, air blowing, or the like. Drying may be performed in an atmosphere of an inert gas such as nitrogen in addition to air. In the case of heating and drying, the temperature is preferably from 50 to 150C. When the drying temperature is higher than 150 ° C., coloring of the gel and thermal decomposition of the mold agent are caused.

The steam treatment of the carrier containing the dried gel is performed in a pressure vessel such as an autoclave. When the carrier comes into contact with water in a liquid state, the dried gel on the carrier flows out into the water. In order to prevent this, in the pressure vessel, it is necessary to isolate water and carrier as a water vapor source, and to avoid contact between water droplets generated by condensation of water vapor and the carrier.

The steam treatment temperature is 120 to 300 ° C, more preferably 180 to 250 ° C. Heating temperature is 120
When the temperature is lower than ℃, it takes a long time to crystallize the titanosilicate, and when the temperature is higher than 300 ° C, the thermal decomposition of the mold proceeds and the crystallization of the titanosilicate occurs. Has a negative effect. The time required for crystallization of the titanosilicate depends on the steam treatment temperature, the thickness of the dried gel, and the like, but is usually 1 hour to 30 days.

The titanosilicate-supported catalyst can be produced by calcining the support obtained by crystallizing titanosilicate by steam treatment at 450 to 650 ° C. for 1 to 100 hours. At this time, a more preferable firing temperature is 500 to 600 ° C, and a more preferable firing time is 2 to
20 hours.

The catalyst of the present invention is suitably used for producing an epoxy compound from hydrogen peroxide and an olefin compound,
An epoxy compound and / or a derivative thereof is obtained by selective epoxidation. The derivative of the epoxy compound refers to a glycol compound, an ether compound, or the like generated by further subjecting the epoxy compound to solvolysis.

The olefin compounds to be epoxidized are acyclic and cyclic organic compounds having at least one ethylenically unsaturated double bond. Two or more carbon-carbon double bonds may be present in the olefin compound. Further, the olefin compound may contain various substituents, for example, halogen, carboxylic acid, ester, ketone, hydroxyl, acyl, ether, thiol, nitro, cyano, amino, acid anhydride and the like. Preferred olefin compounds are those containing 2 to 20 carbon atoms.
Examples of the olefin compound include ethylene, propylene, 1-butene, 2-butene, isobutene, isoprene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, allyl chloride, allyl alcohol, and acryl. Examples include acid, methacrylic acid, methyl methacrylate, allyl acrylate, allyl methacrylate, styrene and the like.

As the hydrogen peroxide, a product having a concentration of 30 to 90% by weight can be used. Hydrogen peroxide may be added to the reaction system in its entirety at once, or may be added stepwise in parallel with the progress of the reaction.

The use ratio of the olefin compound to hydrogen peroxide is 0.5 mol or more, more preferably 0.7 to 10 mol.
It is 5 times mol. If the molar ratio is less than 0.5 times, the side reaction increases, and if it exceeds 5 times, the recovery energy of the unreacted olefin increases.

The solvent used in the reaction is preferably a polar solvent such as alcohol, ketone and water. As the alcohol, an aliphatic alcohol having 5 or less carbon atoms is preferable, and specific examples thereof include methanol, ethanol, propanol, t-butanol and the like, and methanol is most preferable. On the other hand, the ketone is preferably an aliphatic ketone having 3 to 6 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, and ethyl isopropyl ketone. Particularly preferred are acetone and methyl ethyl ketone. These solvents may be used alone or as a mixture of two or more. The amount of the solvent used is not limited, but is preferably 5 to 80 wt%, more preferably 10 to 70 wt% based on the total amount of the reaction solution.
%. If the amount is less than 5 wt%, the yield decreases and 8
If it is more than 0 wt%, the recovery energy of the solvent increases.

The reaction can be carried out in a liquid phase at atmospheric pressure. When the olefin compound is gaseous, it is preferable to maintain a pressure sufficient to dissolve it in the liquid phase. The reaction temperature is preferably in the range of 30 to 120C, more preferably in the range of 40 to 80C. When the reaction temperature is lower than 30 ° C., the reaction rate is low, and when the reaction temperature is higher than 120 ° C., side reactions increase.

In addition, in the epoxidation reaction of an olefin compound with hydrogen peroxide using the catalyst of the present invention,
The epoxy compound produced under the reaction conditions is further subjected to solvolysis to give a glycol compound or an ether compound. Therefore, by selecting appropriate reaction conditions, the catalyst of the present invention can be suitably used for the selective production of glycol compounds and ether compounds.

The catalyst of the present invention is also suitably used for the production of a dihydric phenol compound using hydrogen peroxide and a monohydric phenol compound to give a specific dihydric phenol compound by selective hydroxylation.

As the monohydric phenol compound, phenol, cresol, xylenol and the like can be used, and phenol is particularly preferably used.

The use ratio of the monohydric phenol compound to hydrogen peroxide is at least twice as much as possible to suppress side reactions.
More preferably, it is at least 3 moles.

As the solvent used in the reaction, polar solvents such as alcohols, ketones and water are preferred, and water is most preferred. The amount of the solvent used is not limited, but is preferably 10 to 50% by weight, more preferably 20 to 40% by weight based on the total amount of the reaction solution.
%. Further, it is preferable to add dioxane to the reaction solution for paraselective hydroxylation.

The reaction temperature ranges from 50 to 150 ° C., preferably from 60 to 120 ° C. When the reaction temperature is lower than 50 ° C, the reaction rate is low, and when the reaction temperature is higher than 150 ° C, side reactions increase.

The catalyst of the present invention is further suitably used for producing a ketoxime compound from hydrogen peroxide, a ketone compound and ammonia, and gives a specific ketoxime compound by ammoximation.

As the ketone compound, cyclohexanone, methyl ethyl ketone and the like are preferably used.

The use ratio of the ketone compound to hydrogen peroxide is 0.5 to 1.5 moles, more preferably 0.5 to 1.5 moles.
1.2 times mol. The use ratio of ammonia to the ketone compound is at least 1 mol, and more preferably at least 1.5 mol. When the use ratio of ammonia to the ketone compound is less than 1 mole, side reactions increase.

As the solvent used in the reaction, a polar solvent such as alcohol, ketone, water and the like is preferable, and t-butyl alcohol is particularly preferable. The amount of the solvent used is not limited, but is 10 to 50% by weight based on the total amount of the reaction solution. 10
If the amount is less than 50% by weight, the yield decreases.

The reaction temperature ranges from 30 to 120 ° C., preferably from 60 to 100 ° C. The reaction is carried out under normal pressure or under pressure so that the ammonia concentration in the solution does not become too low.

[0042]

EXAMPLES The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the scope of the invention.

Example 1 563 g of tetraethylorthosilicate and 12.3 g of tetraethylorthotitanate were placed in a 3 liter flask, and 811 g of a 20% by weight aqueous solution of tetrapropylammonium hydroxide was added dropwise over 2 hours under a nitrogen stream. During the dropwise addition, the temperature of the reaction solution was adjusted to be constant at 20 ° C.
After the addition was completed, stirring was continued for a while to promote hydrolysis, and then the reaction solution was heated to 80 ° C., and ethanol generated by hydrolysis was distilled off from the reaction solution to prepare 752 g of a sol. Next, 20 g of Carract 30 (10 to 20 mesh) of spherical silica gel manufactured by Fuji Silysia Chemical Ltd. was humidified, added to 65 g of the above sol, heated to 90 ° C., and left overnight at room temperature. After filtering off the silica gel 75
Drying at 6 ° C. for 6 hours gave a dried gel-supported silica gel. This was placed in a Teflon beaker, placed in a 3 liter autoclave, on a support attached to isolate from the water of the steam source, steamed at 220 ° C for 6 days, and the titanosilicate layer was placed on the carrier. Was crystallized.
After cooling the inside of the autoclave to room temperature, take out the catalyst,
Baking was performed at 550 ° C. for 6 hours. A catalyst having a titanosilicate content of about 23 wt% was obtained (hereinafter, referred to as "catalyst A"). The particle size of catalyst A was almost the same as that of the silica gel carrier. FIG. 1 shows the distribution of titanium atoms in catalyst A by EPMA (X-ray microanalyzer) analysis. FIG. 1 shows that titanium atoms are almost uniformly distributed in catalyst A. On the other hand, powder X-ray diffraction and diffuse reflection IR measurement confirmed that the supported compound had a titanosilicate structure. Therefore, it was found that the titanosilicate particles were almost uniformly distributed in the catalyst A.

Example 2 The procedure of Example 1 was repeated except that Carrieract 50 (10 to 20 mesh) of spherical silica gel manufactured by Fuji Silysia Chemical Ltd. was used as the carrier to form a dry gel and titanosilicate crystals by steam treatment. , And a catalyst having a titanosilicate content of about 30 wt% was obtained (hereinafter, referred to as “catalyst”).
"Catalyst B"). The particle size of catalyst B was almost the same as that of the silica gel carrier. In addition, EPMA analysis, powder X-ray diffraction and diffuse reflection IR measurement confirmed that titanosilicate particles were almost uniformly distributed in catalyst B.

Example 3 Gallosilicate (Si / G manufactured by NE Chemcat)
a = 25, extruded product, diameter 1.6 mm) was crushed and sieved to collect particles of 1.0 to 1.4 mm. Except that this was used as a carrier, formation of a dried gel, crystallization of titanosilicate by steam treatment, and calcination were carried out in the same manner as in Example 1 to obtain a catalyst having a titanosilicate content of about 17 wt% ( Hereinafter, referred to as “catalyst C”).

Example 4 The carrier was ZSM-11 (Si, manufactured by NE Chemcat).
/ Al = 25, extruded product, diameter 1.6 mm), in the same manner as in Example 3, to form a dry gel, crystallize titanosilicate by steam treatment, and calcinate to obtain a titanosilicate content. Was obtained (hereinafter, referred to as "catalyst D").

Example 5 A mordenite made by NE Chemcat (Si
/ Al = 15, extruded product, diameter 1.6 mm) except that a dry gel was formed, titanosilicate was crystallized by steam treatment, and calcined in the same manner as in Example 3 to obtain a titanosilicate content. Was obtained (hereinafter, referred to as "catalyst E").

Example 6 In a 200 ml flask equipped with a thermometer, a reflux condenser and a stirrer, 66 g (0.52 mol) of allyl methacrylate, 10 g of methanol as a reaction solvent and 10 g of methyl ethyl ketone, the catalyst prepared in Example 1 A7.
8 g each were weighed and heated to 60 ° C. When the temperature becomes constant, 11.9 g of 60 wt% hydrogen peroxide solution
(0.21 mol) was added dropwise over 1.5 hours. Further 60
After stirring for minutes, the flask was removed from the oil bath to terminate the reaction. After filtering off the catalyst, the organic components and residual hydrogen peroxide were quantified by gas chromatography and iodine titration. The conversion of hydrogen peroxide was 96%, and the selectivity for glycidyl methacrylate was 87%. In addition, the separated catalyst was 1
Washed with 0 g of methanol. Table 1 shows the catalyst filtration time required for separating the catalyst from the reaction solution and washing with methanol.

Example 7 An epoxidation reaction of allyl methacrylate was carried out in the same manner as in Example 6 except that 13.0 g of catalyst C was used instead of catalyst A. The conversion of hydrogen peroxide was 99%, and the selectivity for epoxy (the total of the selectivity for glycidyl methacrylate and the selectivity for the glycol product as a hydrolysis product thereof) was 75%.
Table 1 shows the catalyst filtration time required for separating the catalyst from the reaction solution and washing with methanol.

Example 8 The epoxidation reaction of allyl methacrylate was carried out in the same manner as in Example 6, except that 10.4 g of catalyst D was used instead of catalyst A. The conversion of hydrogen peroxide was 99%, and the selectivity of epoxy (total of the selectivity of glycidyl methacrylate and the selectivity of the glycol product as a hydrolysis product thereof) was 70%.
Table 1 shows the catalyst filtration time required for separating the catalyst from the reaction solution and washing with methanol.

Example 9 An epoxidation reaction of allyl methacrylate was carried out in the same manner as in Example 6 except that 13.0 g of Catalyst E was used instead of Catalyst A. The conversion rate of hydrogen peroxide was 99%, and the selectivity for epoxy (the total of the selectivity for glycidyl methacrylate and the selectivity for the glycol product as a hydrolysis product thereof) was 62%.
Table 1 shows the catalyst filtration time required for separating the catalyst from the reaction solution and washing with methanol.

Example 10 A 200 ml flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 25 g (0.33 mol) of allyl chloride, 25 g of methanol as a reaction solvent and 2 g of methyl ethyl ketone.
5 g and 9.6 g of the catalyst A prepared in Example 1 were each weighed and heated to 50 ° C. When the temperature became constant, 4.0 g (0.07 mol) of a 60 wt% aqueous hydrogen peroxide solution was added dropwise over 40 minutes. After stirring was continued for another 10 minutes, the flask was removed from the oil bath to terminate the reaction. After filtering off the catalyst, the organic components and residual hydrogen peroxide were quantified by gas chromatography and iodine titration. The conversion of hydrogen peroxide was 82%, and the selectivity for epichlorohydrin was 97%.

Example 11 In a 200 ml flask equipped with a thermometer, a reflux condenser and a stirrer, 50 g (0.30 mol) of 1-dodecene, 50 g of methanol as a reaction solvent and 50 g of methyl ethyl ketone, the catalyst prepared in Example 2 10.0 g of B was weighed and heated to 60 ° C. When the temperature becomes constant, 3.5 g of 60 wt% hydrogen peroxide solution (0.0 g
6 mol) was added dropwise in 35 minutes. After stirring was continued for another 30 minutes, the flask was removed from the oil bath to terminate the reaction. After filtering off the catalyst, the organic components and residual hydrogen peroxide were quantified by gas chromatography and iodine titration. Hydrogen peroxide conversion 69%, 1-epoxide decane selectivity 88
%Met.

Example 12 In a 200 ml flask equipped with a thermometer, a reflux condenser and a stirrer, 50 g (0.53 mol) of phenol, 1,
8.4 g of 4-dioxane, 30 g of water and 6.3 g of the catalyst A prepared in Example 1 were weighed out,
Heated to ° C. When the temperature becomes constant, 31 wt%
14.4 g (0.13 mol) of aqueous hydrogen peroxide was added dropwise.
As a result of analyzing the solution after the reaction for 3 hours, the yield of dihydric phenol based on hydrogen peroxide was 76%, the molar ratio of produced hydroquinone / catechol was 5.6, and hydroquinone was selectively obtained.

Example 13 In a 300 ml SUS316 autoclave, 38.3 g (0.39 mol) of cyclohexanone, 39.6 g (0.58 mol) of a 25 wt% aqueous ammonia solution, 59 g of t-butanol, and the mixture prepared in Example 1 were prepared. Catalyst A1
Each 9.3 g was weighed and heated to 80 ° C. When the temperature becomes constant, 31 wt% hydrogen peroxide water.
7 g (0.41 mol) were fed in one hour and stirring was continued for a further 30 minutes. After filtering off the catalyst from the reaction solution and adding acetone to make a homogeneous solution, the organic components and residual hydrogen peroxide were quantified by gas chromatography and iodine titration. The yield based on hydrogen peroxide of cyclohexanone oxime was 82%.

Comparative Example 1 93 g of the sol solution synthesized in Example 1 and 157 g of water were placed in a 500 ml shaking autoclave, and 25 g of Carract 30 (10 to 20 mesh) as a carrier was added after humidification. After the gas in the autoclave was replaced with nitrogen, the autoclave was closed, heated to 170 ° C for 96 hours, heated to 210 ° C, kept at 210 ° C for another 48 hours, and then cooled to room temperature. The silica gel support was dissolved during the hydrothermal synthesis, and a white clay-like solid was deposited in the autoclave. After the white solid is centrifuged, washed and dried with distilled water,
As a result, all of the white solid passed through the sieve and became fine particles. The powder was fired in an electric furnace at 550 ° C. for 6 hours in the air to obtain a fine powdery titanosilicate catalyst.

Comparative Example 2 A titanosilicate catalyst was obtained by hydrothermal synthesis according to the examples of JP-A-56-97720 (hereinafter referred to as "catalyst F").
Described). The epoxidation reaction of allyl methacrylate was carried out in the same manner as in Example 6, except that 2.6 g of the catalyst F was used instead of the catalyst A. The conversion of hydrogen peroxide was 99%, and the selectivity for glycidyl methacrylate was 85%. Table 1 shows the catalyst filtration time required for separating the catalyst from the reaction solution and washing with methanol. Since the filter paper was clogged by the fine particles of the catalyst F, the filtration of the catalyst required a considerably long time as compared with the titanosilicate-supported catalyst (Examples 6 to 9). Further, when the epoxidation reaction was repeatedly performed, the catalyst filtration time tended to be further increased.

[0058]

[Table 1] 濾過 Catalyst filtration time (seconds) ──────────触媒 Catalyst separation methanol washing Example 6 12 2 Example 7 13 2 Example 8 12 3 Example 9 14 3 Comparative Example 2 61 78 ─

[0059]

According to the present invention, a titanosilicate-supported catalyst having excellent handling characteristics and mechanical strength is provided. In the production of the catalyst of the present invention, first, a silica-titania dry gel containing a silicon compound, a titanium compound and a tetraalkylammonium compound is formed on a support, and this is subjected to steam treatment under pressure, so that not only a spherical shape but also a spherical shape is obtained. The titanosilicate can be crystallized on a carrier having a more complicated shape. Further, the titanosilicate supported catalyst of the present invention can be used for selective epoxidation of an olefin compound with hydrogen peroxide, selective hydroxylation of a monohydric phenol compound with hydrogen peroxide, or a ketone compound and ammonia and hydrogen peroxide. Has remarkable activity on the selective ammoximation of, and is utilized in organic synthesis.

[Brief description of the drawings]

FIG. 1 is a distribution diagram of titanium atoms in catalyst A by EPMA.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 301/12 C07D 301/12 303/04 303/04

Claims (11)

[Claims] 1. A sol or gel suspension containing a silicon compound, a titanium compound and a tetraalkylammonium compound is applied on a carrier and then dried to form a gel.
Next, the titanosilicate is crystallized on a carrier by steam treatment under pressure, and then calcined, followed by calcining. 2. The method for producing a titanosilicate-supported catalyst according to claim 1, wherein a tetraalkyl orthosilicate or colloidal silica is used as the silicon compound. 3. The method for producing a titanosilicate-supported catalyst according to claim 1, wherein tetraethylorthosilicate is used as the silicon compound. 4. The method for producing a titanosilicate-supported catalyst according to claim 1, wherein a tetraalkyl orthotitanate or a titanium halide compound is used as the titanium compound. 5. The method according to claim 1, wherein the titanium compound is tetraethyl orthotitanate, tetrapropyl orthotitanate or tetrabutyl orthotitanate. 6. The method for producing a titanosilicate-supported catalyst according to claim 1, wherein a tetraalkylammonium hydroxide or a tetraalkylammonium halide is used as the tetraalkylammonium compound. 7. The method for producing a titanosilicate-supported catalyst according to claim 1, wherein tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or tetrapropylammonium bromide is used as the tetraalkylammonium compound. 8. The method for producing a titanosilicate-supported catalyst according to claim 1, wherein the steam temperature is 120 to 300 ° C. 9. A method for producing an epoxy compound and / or a derivative thereof using hydrogen peroxide and an olefin compound, wherein the titanosilicate-supported catalyst according to claim 1 is used. Method. 10. A method for producing a dihydric phenol compound, which comprises using the titanosilicate-supported catalyst according to claim 1 in producing a dihydric phenol compound using hydrogen peroxide and a monohydric phenol compound. 11. A method for producing a ketoxime compound using hydrogen peroxide, a ketone compound and ammonia.
A method for producing a ketoxime compound, comprising using the titanosilicate-supported catalyst according to the above.