JP6970739B2 - A method for producing a titanium-containing silicon oxide, a method for producing an epoxide, and a titanium-containing silicon oxide. - Google Patents

Description

The present invention relates to a method for producing a titanium-containing silicon oxide, a method for producing an epoxide from an olefin using the titanium-containing silicon oxide produced by the method as a catalyst, and a titanium-containing silicon oxide.

Methods for producing epoxides from hydroperoxides and olefins in the presence of catalysts are known. As a catalyst used in this method, for example, Patent Document 1 describes in a first step of obtaining a solid containing a catalyst component and a mold by mixing a silica source, a titanium source and a mold in a liquid state, and in the first step. The second step of removing the mold from the obtained solid by a solvent extraction operation and the extraction solvent contained in the solid after removing the mold obtained in the second step are substantially the same as those of the silylating agent used in the following fourth step. Titanium-containing obtained by a production method including a third step of substituting with a substantially inert solvent and a fourth step of obtaining a silylated catalyst by subjecting the solid obtained in the third step to a silylation treatment. Silicon oxide solvents are described.

Japanese Patent Publication No. 2004-195379 (Published July 15, 2004)

However, the catalyst described in Patent Document 1 is not sufficient in terms of catalyst life.

The problem to be solved by the present invention is to provide a method for producing a titanium-containing silicon oxide capable of maintaining high catalytic activity for a long period of time when used as a catalyst in a reaction for producing an epoxide from an olefin and a hydroperoxide. There is a point to do.

One aspect of the present invention is the following step:
Step A: The mold, the silicon source, and the solvent are mixed to obtain a solid containing the mold and the silicon oxide. Step B: The mold is removed from the solid obtained through the step A to obtain a solid. Step C: A treatment agent containing 0.01 to 20% by mass of water is brought into contact with the solid obtained through Step B to obtain a solid. Step D: The solid obtained through Step C is used as a silylating agent. Has a step of contacting to obtain a solid,
At least selected from the group consisting of in process A, in process B, in process C, in process D, between process A and process B, between process B and process C, and between process C and process D. In one or more, it relates to a titanium-containing silicon oxide that introduces titanium into a solid.

According to one aspect of the present invention, there is provided a titanium-containing silicon oxide capable of maintaining high catalytic activity for a long period of time when used as a catalyst in a reaction for producing an epoxide from an olefin and a hydroperoxide.

The method for producing a titanium-containing silicon oxide according to one aspect of the present invention includes steps A to D.

The titanium-containing silicon oxide refers to a compound having a bond represented by —Si—O—Ti.

<Process A>
Step A is a step of mixing a mold, a silicon source, and a solvent to obtain a solid containing a mold and a silicon oxide, and is sometimes referred to as a raw material mixing step.

"Silicon source" refers to silicon oxides and silicon oxide precursors. The silicon oxide precursor refers to a compound in which a part or all of the silicon oxide precursor becomes silicon oxide by mixing the silicon oxide precursor and water.

Examples of the silicon oxide as a silicon source include amorphous silica. Examples of the silicon oxide precursor as a silicon source include alkoxysilanes, alkyltrialkoxysilanes, dialkyldialkoxysilanes, and 1,2-bis (trialkoxysilyl) alkanes. Alkoxysilanes include tetramethyl orthosilicates, tetraethyl orthosilicates, and tetrapropyl orthosilicates. Examples of the alkyltrialkoxysilane include trimethoxy (methyl) silane. Examples of the dialkyldialkoxysilane include dimethoxydimethylsilane. As the silicon source, a single one may be used, or several kinds may be used in combination.

When a silicon oxide precursor is used as the silicon source, water is used as part or all of the solvent in the step. When the silicon oxide precursor is mixed with water, the silicon oxide precursor is partially or wholly changed to silicon oxide.

The mold refers to a substance that can form a pore structure in a titanium-containing silicon oxide. As the mold, a surfactant is preferable. Examples of the surfactant include a cationic surfactant, an anionic surfactant, and a nonionic surfactant. Examples of the cationic surfactant include a quaternary ammonium compound containing a quaternary ammonium ion and an alkylamine salt. Examples of the quaternary ammonium compound containing a quaternary ammonium ion include tetraalkylammonium hydrochloride, tetraalkylammonium acetate, and tetraalkylammonium hydroxide. Examples of the alkylamine salt include monoalkylamine hydrochloride, monoalkylamine acetate, dialkylamine hydrochloride, dialkylamine acetate, trialkylamine hydrochloride, and trialkylamine acetate. Examples of the anionic surfactant include alkylbenzene sulfonic acid and its salt, α-olefin sulfonic acid sodium salt, alkyl sulfate ester salt, alkyl ether sulfuric acid ester salt, methyl tauric acid, alaninate and its salt, ether carboxylic acid and its salt, and sulfosuccinate. Examples thereof include acid salts, sulfated oils, polyoxyalkylene ether sulfate ester salts, and soaps. Nonionic surfactants include polyalkylene oxides or block copolymers of polyalkylene oxides, and alkylamines.

Among the surfactants, cationic surfactants and nonionic surfactants are preferable. The cationic surfactant is preferably a salt containing a quaternary ammonium ion represented by the following formula (I). The nonionic surfactant is preferably an amine represented by the following formula (II).

[NR ¹ R ² R ³ R ⁴ ] + (I)
(In the formula (I), R ¹ represents a linear or branched hydrocarbon group having ^{2 to 36 carbon atoms, and R 2 to} R ⁴ are independent hydrocarbon groups having 1 to 6 carbon atoms, respectively. Represents.)
NR ⁵ R ⁶ R ⁷ (II)
(In formula (II), R ⁵ represents a linear or branched hydrocarbon group having 2 to 36 carbon atoms, and R ⁶ and R ⁷ independently have hydrogen atoms or carbon atoms 1 to 6 respectively. Represents a hydrocarbon group.)
In the formula (I), R ¹ is a linear or branched hydrocarbon group having 2 to 36 carbon atoms, preferably a hydrocarbon group having 10 to 22 carbon atoms. It is preferable that R ^{2 to} R ⁴ are each independently a hydrocarbon group having 1 to 6 carbon atoms, and ^{all of R 2 to} R ⁴ are methyl groups.

Specific examples of the quaternary ammonium ion represented by the formula (I) include tetraethylammonium, tetrapropylammonium, tetrabutylammonium, decyltrimethylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, and eicosyltrimethyl. Examples thereof include cations such as ammonium, behenyltrimethylammonium, benzyltrimethylammonium, dimethyldidodecylammonium, and hexadecylpyridinium.

Specific examples of the salt containing the quaternary ammonium ion represented by the formula (I) include tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, decyltrimethylammonium hydroxide, and decyltrimethylammonium chloride. Decyltrimethylammonium bromide, dodecyltrimethylammonium hydroxide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium hydroxide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium hydroxide, octadecyltrimethylammonium chloride , Octadecyltrimethylammonium bromide, eicosyltrimethylammonium hydroxide, eicosyltrimethylammonium chloride, eicosyltrimethylammonium bromide, behenyltrimethylammonium hydroxide, behenyltrimethylammonium chloride, and behenyltrimethylammonium bromide, and their quaternary ammonium ions. Examples thereof include dimethyldialkylammonium salts and methyltrialkylammonium salts in which at least one methyl group in the salt containing the above is substituted with an alkyl group having 2 to 22 carbon atoms.

In formula (II), ^{R 5} represents a linear or branched hydrocarbon group having 2 to 36 carbon atoms, and preferably from 10 to 22 carbon atoms. It is preferable that R ⁶ and R ⁷ are independently hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, and R ⁶ and R ⁷ are hydrogen atoms.

Specific examples of the amine represented by the formula (II) include ethylamine, propylamine, butylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine and hexadecylamine. Examples include amines, heptadecylamines, octadecylamines, nonadesylamines, eicosylamines, and behenylamines, as well as methylalkylamines in which at least one hydrogen atom in these amines is substituted with a methyl group, dimethylalkylamines, and the like. can.

As the mold, a single one may be used, or several kinds may be used in combination.

Mixing of the mold and the silicon source is carried out in the presence of a solvent. Examples of the solvent include water and alcohol. Examples of the alcohol include methanol, ethanol, 1-propanol and 2-propanol.

By going through step A, a solid containing a mold and a silicon oxide is obtained. The solid containing the mold and the silicon oxide obtained in the step A can be taken out by filtration or the like. The mixing of step A is preferably carried out in a temperature range of 20 to 200 ° C. over 2 to 1000 hours. It is also possible to carry out stirring during mixing.

<Process B>
Step B is a step of removing the mold from the solid containing the mold and the silicon oxide obtained through the step A to obtain a solid, and is sometimes referred to as a mold removing step. By carrying out step B, a solid containing no mold or substantially no mold is obtained.

The content of the mold in the solid obtained in step B is preferably 10% by mass or less, and more preferably 1% by mass or less.

Removal of the mold can be achieved by calcining the solid containing the mold in the air at 300-800 ° C. or by extracting with a solvent. It is preferable to remove the mold by extraction.

Techniques for extracting molds with a solvent have been reported by Whitehurst et al. (See US Pat. No. 5,143,879). The solvent may be any one that can dissolve the compound used as the mold, and generally a compound having 1 to 12 carbon atoms that is liquid at room temperature or a mixture of two or more of these compounds can be used. Suitable solvents include alcohols, ketones, acyclic and cyclic ethers and esters. Examples of the alcohol include methanol, ethanol, ethylene glycol, propylene glycol, 1-propanol, 2-propanol, 1-butanol and octanol. Examples of the ketone include acetone, diethyl ketone, methyl ethyl ketone and methyl isobutyl ketone. Examples of the ether include diisobutyl ether and tetrahydrofuran. Examples of the ester include methyl acetate, ethyl acetate, butyl acetate and butyl propionate.

As the solvent, from the viewpoint of the dissolving ability of the mold, for example, when the mold is a salt containing a quaternary ammonium ion, alcohol is preferable, and methanol is more preferable. The mass ratio of the solvent to the solid containing the mold is usually 1 to 1000, preferably 5 to 300. Acids or salts thereof may be added to these solvents to improve the extraction effect. Examples of the acid used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and odorous acid, and organic acids such as formic acid, acetic acid and propionic acid. Examples of these salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. The concentration of the added acid or a salt thereof in the solvent is preferably 30% by mass or less, more preferably 15% by mass or less.

Examples of the method for removing the mold include a method in which the solvent and the solid containing the mold are sufficiently mixed, and then the liquid phase portion is separated by a method such as filtration or decantation. This operation may be repeated a plurality of times. It is also possible to extract the mold by filling a container such as a column with a solid containing the mold and circulating an extraction solvent. The extraction temperature is preferably 0 to 200 ° C, more preferably 20 to 100 ° C. If the boiling point of the extraction solvent is low, the extraction may be performed under pressure.

The mold in the solution obtained by the extraction treatment can be recovered and reused as the mold in step A. Similarly, the extraction solvent can also be purified and reused by a normal distillation operation or the like.

<Process C>
Step C is a step of bringing a treatment agent containing 0.01 to 20% by mass of water into contact with the solid obtained through step B to obtain a solid, and is sometimes referred to as a water treatment step. The water content in the treatment agent is 0.01 to 20% by mass, more preferably 0.02 to 10% by mass, further preferably 0.02 to 5% by mass, and 0.1 to 1% by mass. Most preferably, it is 2% by mass. If the water content is too high, it adversely affects the catalytic performance of the titanium-containing silicon oxide, especially the catalytic activity. The weight of the treatment agent containing water is usually 1 to 1000, preferably 1 to 500, and more preferably 1 to 200, where 1 is the weight of the solid obtained in step B. It is more preferably ~ 100.

The treatment agent contains, for example, a nitrogen-containing base compound, an alcohol, a carboxylic acid and at least one selected from these compounds. The treatment agent is an aprotic polar compound (for example, a nitrogen-containing basic compound), a protonic polar compound (for example, alcohol, a carboxylic acid and a compound thereof), or a mixture of a protonic polar compound and an aprotonic polar compound. could be.

Step C refers to a step of bringing the water contained in the treatment agent into contact with the solid by bringing the treatment agent containing 0.01 to 20% by mass of water into contact with the solid. In the present specification, the "treatment agent" used in step C is distinguished from the "treatment liquid" used in other steps.

In step C, the treatment agent may be brought into contact with the solid obtained through step B one or more times. When the treatment agent is brought into contact with the solid more than once, the treatment agents may be the same or different.

In step C, after contacting the solid obtained through step B with a treatment agent containing water at least once,
Substitute with a treatment solution containing less than 0.01% of water containing a protonic polar solvent, an aprotonic polar solvent, a protonic polar solvent containing a non-polar compound, or an aprotic polar solvent containing a non-polar compound. You may. Examples of the protonic polar solvent include alcohol described later, examples of the aprotic polar solvent include ketones, nitriles and esters described below, and examples of the non-polar compound include toluene and the like.

When the treatment agent contains a nitrogen-containing base compound, a compound represented by the following formula (III) or a compound represented by the following formula (IV) is preferable.
NR ⁸ R ⁹ R ¹⁰ (III)

式（ＩＩＩ）において、Ｒ^８〜Ｒ^１０はそれぞれ独立して水素原子、炭素原子数１〜１８の直鎖状の炭化水素基、炭素原子数３〜１８の分岐状の炭化水素基、又は炭素原子数５〜１８の環状の炭化水素基を表す。

In formula (III), R ^{8 to} R ¹⁰ are independently hydrogen atoms, linear hydrocarbon groups having 1 to 18 carbon atoms, branched hydrocarbon groups having 3 to 18 carbon atoms, or carbon. Represents a cyclic hydrocarbon group having 5 to 18 atoms.

Specific examples of the nitrogen-containing base compound represented by the formula (III) include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, and tri-n-. Propylamine, dimethylethylamine, dimethylpropylamine, diethylmethylamine, diethylbutylamine, methylethylpropylamine, methylethylbutylamine, dipropylmethylamine, methylpropylbutylamine, dibutylmethylamine, triethylamine, diethylpropylamine, dipropylethylamine, ethyl Examples thereof include propylbutylamine, dibutylethylamine, tripropylamine, dipropylbutylamine, dibutylpropylamine, tributylamine, pentylamine, hexylamine, heptylamine, and tri-n-octylamine.

In formula (IV), R ^{11 to} R ¹⁵ are independently (a) a linear hydrocarbon group having 1 to 6 carbon atoms, a branched hydrocarbon group having 3 to 6 carbon atoms, and carbon. Selected from the group consisting of a hydrocarbon group consisting of a cyclic hydrocarbon group having 5 to 6 atoms, (b) a hydrogen atom, (c) a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A group selected from the group consisting of a halogen atom, a group represented by (d) -OA ¹ , and a group represented by (e) -NA ^{2 A 3 , which are A 1} , A ² and A in the formula. ³ is an independent hydrogen atom, a linear hydrocarbon group having 1 to 6 carbon atoms, a branched hydrocarbon group having 3 to 6 carbon atoms, or a cyclic hydrocarbon having 5 to 6 carbon atoms. Represents an atom.

Specific examples of the nitrogen-containing base compound represented by the formula (IV) include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, and quinoline.

Preferred nitrogen-containing base compounds are tertiary amines, ammonia, and pyridine, with tri-n-octylamine, ammonia, and pyridine being even more preferred. These nitrogen-containing base compounds may be used alone or in combination of two or more.

When the treatment agent contains alcohol, examples of the alcohol include primary alcohol, secondary alcohol, and tertiary alcohol, and alcohol having 1 to 12 carbon atoms is preferable, tertiary alcohol is more preferable, and tert-butyl alcohol is preferable. More preferred.

When the treatment agent contains a carboxylic acid, the carboxylic acid is preferably a carboxylic acid having 1 to 12 carbon atoms, and more preferably formic acid, acetic acid and propionic acid.

When the treatment agent contains a nitrogen-containing base compound, an alcohol or a carboxylic acid, these may be mixed with each other or diluted with another solvent. Preferred solvents for dilution are non-polar organic solvents (non-polar compounds) such as hydrocarbons with 1 to 12 carbon atoms, halogenated hydrocarbons, etc., which are liquid at room temperature, ketones, ethers, esters, N, N-2. It is an aprotonic polar organic solvent (aprotonic polar compound) such as a substituted amide, nitrile, or sulfoxide. Examples of the hydrocarbon having 1 to 12 carbon atoms that are liquid at room temperature include hexane, cyclohexane, benzene, toluene, and xylene. Examples of the halogenated hydrocarbon include chloroform. Examples of the ketone include acetone, diethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ether include diethyl ether, diisobutyl ether, tetrahydrofuran, and dioxane. Examples of the ester include methyl acetate and ethyl acetate. Examples of the N, N-disubstituted amide include dimethylformamide. Examples of nitrile include acetonitrile. Examples of sulfoxide include dimethyl sulfoxide. As the organic compound, alcohol having 1 to 12 carbon atoms, hydrocarbon having 1 to 12 carbon atoms liquid at room temperature, a ketone and nitrile are preferable, and tert-butyl alcohol, 2-methyl-2-butanol, acetonitrile and hexane are preferable. , Cyclohexane, benzene, toluene, xylene, and acetone are preferred.

The contact temperature between the treatment agent and the solid after removing the mold material is usually 0 to 200 ° C, more preferably 0 to 150 ° C. Such contact can be carried out by, for example, a batch method and a distribution method. If the boiling point of the treatment agent is low, step C may be carried out under pressure.

After the end of step C and before the start of step E below, it is preferable to reduce the amount of the silylation-active component contained in the solid obtained through step C.

Methods of reducing the amount of components active against silylation include liquid substitution and / or drying described below.

Step E is a step of substituting the treatment agent and / or the treatment liquid contained in the solid obtained through the step C with a liquid substantially inactive with respect to the silylating agent, and is referred to as a liquid replacement step. There is also. Examples of the substantially inert liquid include hydrocarbons, haloalkanes and ethers. Examples of the hydrocarbon include aliphatic or aromatic hydrocarbons having 6 to 14 carbon atoms. Examples of the haloalkane include dichloromethane and tetrachlorethylene. Examples of the ether include diethyl ether and tetrahydrofuran. The substantially inert liquid used in step E is preferably a hydrocarbon, more preferably toluene. The temperature of the replacement liquid in the liquid replacement is usually 0 to 200 ° C. The liquid replacement can be carried out by a batch method or a distribution method.

When the solid obtained through the step C is dried (step F), the pressure is preferably normal pressure or reduced pressure. The suitable temperature varies depending on the treatment liquid, but from the viewpoint of catalyst performance, it is generally 0 ° C. or higher and 700 ° C. or lower, and 0 ° C. or higher and 200 ° C. or lower. Drying can be carried out by batch method or gas flow method.

Drying of the solid is not limited to drying after step C, but when performing steps A to C, after the completion of any of these steps and before the next step, the solid is dried under the same conditions as in step F. Drying may be performed. Further, either one or both of the step E and the step F may be performed after the step C and before the step D.

<Process D>
Step D is a step of contacting the solid obtained through step C with a silylating agent to obtain a solid. By carrying out step D, the solid obtained through step C is silylated.

Cyrilization may be carried out by a vapor phase method in which a gaseous silylating agent is brought into contact with the solid obtained through step C to react, or the silylating agent and the solid are brought into contact with each other in a solvent to react. The liquid phase method may be used, and in one aspect of the present invention, the liquid phase method is more preferable. Usually, when the silylation is carried out by the liquid phase method, a hydrocarbon is preferably used as a solvent in the step D. When silylation is performed by the liquid phase method, drying may be performed after that.

The silylating agent is a silicon compound having a reactivity with a solid, and a hydrolyzable group is bonded to the silicon, and the silicon has an allyl group such as an alkyl group and a vinyl group, a phenyl group and the like. It is a compound to which at least one group selected from the group consisting of an aryl group, an alkyl halide group, a syroxy group and the like is bonded. Examples of the hydrolyzable group bonded to silicon include hydrogen, halogen, alkoxy group, acetoxy group and amino group. The silylating agent preferably has one hydrolyzable group bonded to silicon.

Examples of the silylating agent include organic silane, organic silylamine, organic silylamide and its derivative, and organic silazane.

Examples of the organic silane include chlorotrimethylsilane, dichlorodimethylsilane, chlorobromodimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, iododimethylbutylsilane, chlorodimethylphenylsilane, chlorodimethylsilane, dimethyln-propylchlorosilane, and dimethylisopropyl. Chlorosilane, tert-butyldimethylchlorosilane, tripropylchlorosilane, dimethyloctylchlorosilane, tributylchlorosilane, trihexylchlorosilane, dimethylethylchlorosilane, dimethyloctadecylchlorosilane, n-butyldimethylchlorosilane, bromomethyldimethylchlorosilane, chloromethyldimethylchlorosilane, 3-chloro Propyldimethylchlorosilane, dimethoxymethylchlorosilane, methylphenylchlorosilane, methylphenylvinylchlorosilane, benzyldimethylchlorosilane, diphenylchlorosilane, diphenylmethylchlorosilane, diphenylvinylchlorosilane, tribenzylchlorosilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, ethoxy Trimethylsilane, diethoxydimethylsilane, triethoxymethylsilane, trimethoxyethylsilane, dimethoxydiethylsilane, methoxytriethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, methoxytriphenylsilane, dimethoxydiphenylsilane, tri Methoxyphenylsilane, ethoxytriphenylsilane, diethoxydiphenylsilane, triethoxyphenylsilane, dichlorotetramethyldisiloxane, 3-cyanopropyldimethylchlorosilane, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane , And 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane.

Examples of the organic silylamine include N- (trimethylsilyl) imidazole, N- (tert-butyldimethylsilyl) imidazole, N- (dimethylethylsilyl) imidazole, N- (dimethyln-propylsilyl) imidazole, and N- (dimethylisopropyl). Cyril) imidazole, N- (trimethylsilyl) -N, N-dimethylamine, N- (trimethylsilyl) -N, N-diethylamine, N- (trimethylsilyl) pyrrole, N- (trimethylsilyl) pyrrolidine, N- (trimethylsilyl) piperidine, Examples thereof include 1-cyanoethyl (diethylamino) dimethylsilane and pentafluorophenyldimethylsilylamine.

Examples of the organic silylamide and the derivative include N, O-bis (trimethylsilyl) acetamide, N, O-bis (trimethylsilyl) trifluoroacetamide, N- (trimethylsilyl) acetamide, N-methyl-N- (trimethylsilyl) acetamide, N. -Methyl-N- (trimethylsilyl) trifluoroacetamide, N-methyl-N- (trimethylsilyl) heptafluorobutylamide, N- (tert-butyldimethylsilyl) -N-trifluoroacetamide, and N, O-bis (diethyl). Hydrosilyl) trifluoroacetamide can be mentioned.

Examples of the organic silazane include 1,1,1,3,3,3-hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyldisilazane and 1,3-bis (chloromethyl). ) -1,1,3,3-Tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and 1,3-diphenyl-1,1,3,3-tetra Methyldisilazane can be mentioned.

Further examples of the silylating agent include N-methoxy-N, O-bis (trimethylsilyl) trifluoroacetamide, N-methoxy-N, O-bis (trimethylsilyl) carbamate, N, O-bis (trimethylsilyl) sulfamate, Examples thereof include trimethylsilyl trifluoromethanesulfonate and N, N'-bis (trimethylsilyl) urea.
The preferred silylating agent is organic sislazane, more preferably 1,1,1,3,3,3-hexamethyldisilazane.

Titanium may be introduced into the solid during any of steps A to F. Between process A and process B, between process B and process C, between process C and process E, between process C and process F, between process E and process D, or between process F and process D. In between, titanium may be introduced into the solid.

The introduction of titanium into the solid may be carried out both during and between the steps described above.

As used herein, "titanium is introduced into a solid" is represented by -Si-O-Ti in the silicon oxide contained in the solid by mixing the solid containing the silicon oxide and the titanium source. Means that a bond is introduced.

Titanium is preferably introduced into the solid prior to the start of step D, at least one selected from the group consisting of within step A, between step B and step C, and between step C and step D. In the above, it is more preferable that titanium is introduced into the solid, and it is further preferable that titanium is introduced into the solid in the step A.

When titanium is introduced into a solid in step A, the silicon source, titanium source and mold are mixed in step A.

Titanium may be introduced into the solid by bringing the solid obtained through the step A into contact with the titanium source after the end of the step A and before the start of the step B.

Titanium may be introduced into the solid by contacting the solid obtained through step B with the titanium source after the end of step B and before the start of step C.

Titanium may be introduced into the solid by contacting the solid obtained through step C with the titanium source after the end of step C and before the start of step D.

Titanium may be introduced into the solid by contacting the solid into which titanium is introduced with the titanium source in the liquid phase, or by contacting the solid into which titanium is introduced with a gas containing the titanium source to bring titanium into place. It may be introduced into a solid.

Examples of the titanium source include titanium alcoholides, chelated titanium complexes, titanium halides, and sulfates containing titanium. Examples of titanium alcoholide include tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra (2-ethylhexyl) titanate, and tetraoctadecyl titanate. Can be mentioned. Examples of the chelated titanium complex include titanium (IV) oxyacetylacetonate and titanium (IV) diisopropoxybisacetylacetonate. Examples of titanium halides include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide. Examples of the sulfate containing titanium include titanyl sulfate.

The produced titanium-containing silicon oxide can be used as a catalyst for an oxidation reaction of an organic compound, for example, an epoxidation reaction of an olefin, and is particularly preferable for the production of an epoxide that reacts an olefin with a hydroperoxide.

The olefin to be subjected to the epoxidation reaction may be an acyclic olefin, a monocyclic olefin, a bicyclic olefin or a polycyclic olefin having three or more rings, and may be a monoolefin, a diolefin or a polyolefin. When there are two or more double bonds in the molecule of the olefin, these double bonds may be conjugated bonds or non-conjugated bonds. Alkenes with 2 to 60 carbon atoms are preferred. The olefin may have a substituent. Examples of such olefins include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 2-hexene, 3-hexene, 1-octene, 1-decene, styrene, and cyclohexene. The olefin may have a substituent containing an oxygen atom, a sulfur atom, or a nitrogen atom together with a hydrogen atom, a carbon atom, or both, and examples of such an olefin include allyl alcohol and crotyl alcohol. Examples include alcohol and allyl chloride. Examples of diolefins include butadiene and isoprene. Particularly preferred olefins include propylene.

Examples of hydroperoxides include organic hydroperoxides. The organic hydroperoxide is given by the formula (V).
ROO-O-H (V)
(In formula (V), R is a hydrocarbon group.)
It is a compound having. Organic hydroperoxides react with olefins to produce epoxides and hydroxyl compounds. R in the formula (V) is preferably a hydrocarbon group having 3 to 20 carbon atoms, and more preferably a hydrocarbon group having 3 to 10 carbon atoms. Specific examples of the organic hydroperoxide include tert-butyl hydroperoxide, 1-phenylethyl hydroperoxide, and cumene hydroperoxide. Cumene hydroperoxide may be abbreviated as CMHP below.

When CMHP is used as the organic hydroperoxide, the resulting hydroxyl compound is 2-phenyl-2-propanol. This 2-phenyl-2-propanol produces cumene by undergoing a dehydration reaction and a hydrogenation reaction. Cumene may be abbreviated as CUM below. Furthermore, by oxidizing this CUM, CHMP is obtained again. From this point of view, it is preferable to use CMHP as the organic hydroperoxide used in the epoxidation reaction.

The epoxidation reaction can be carried out in a liquid phase using a solvent, a diluent, or a mixture thereof. The solvent and diluent must be liquid under the temperature and pressure at the time of reaction and be substantially inert to the reactants and products. When CMHP is subjected to an epoxidation reaction in the presence of CUM as a raw material thereof, CUM can be used as a solvent without adding a solvent.

The epoxidation reaction temperature is generally 0 to 200 ° C, preferably 25 to 200 ° C. The epoxidation reaction pressure may be a pressure sufficient to keep the reaction phase in a liquid state, and is generally preferably 100 to 10000 kPa.

After completion of the epoxidation reaction, the liquid mixture containing the desired product can be separated from the catalyst composition. The liquid mixture can then be purified by a suitable method. Examples of the purification method include distillation, extraction and washing. The solvent and unreacted olefins can be recirculated and used again.

The reaction using the titanium-containing silicon oxide produced according to one aspect of the present invention as a catalyst can be carried out in the form of a slurry or a fixed bed, and in the case of a large-scale industrial operation, it is preferable to use a fixed bed. .. When the titanium-containing silicon oxide produced according to one aspect of the present invention is used as a catalyst, it may be a powder or a molded product. When reacting on a fixed bed, the titanium-containing silicon oxide is preferably a molded product. This reaction can be carried out by a batch method, a semi-continuous method or a continuous method.

Hereinafter, one aspect of the present invention will be described in more detail by way of examples.

[Example 1]
(A) Step A and introduction of titanium Water: Hexadecyltrimethylammonium hydroxide (16% by mass concentration solution) diluted to a concentration of 16% by mass with a mixed solvent having a mixing ratio (mass ratio) of 72:28. 125 parts by mass) was stirred, and a mixed solution of 1.9 parts by mass of tetraisopropyl titanate and 10 parts by mass of 2-propanol was added dropwise at room temperature under stirring. After stirring for 30 minutes after the completion of the dropping, 38 parts by mass of tetramethyl orthosilicate was dropped under stirring. Then, stirring was continued at room temperature for 3 hours, and the resulting solid was filtered off. The obtained solid was dried under reduced pressure at 70 ° C. to obtain a white solid. Hexadecyltrimethylammonium hydroxide, tetramethyl orthosilicate, and tetraisopropyl titanate are molds, silicon sources, and titanium sources, respectively.

Water was added to 10 parts by mass of the obtained white solid so that the water content was 1.3 parts by mass, and the mixture was well mixed. After that, the obtained mixture was compression molded by a roll press machine. The obtained molded product was crushed, and the obtained crushed product was sieved to obtain a molded product containing a mold having a particle size of 1.0 to 2.0 mm. The molded body having a particle size of 1.0 mm or less was compression-molded again in the same manner as described above and crushed.

(B) Step B
20 g of the molded body obtained above was filled in a vertically installed cylindrical glass column having an inner diameter of 30 mm (sheath tube outer diameter of 8 mm) and a height of 27 cm. At that time, the filling length of the molded body was 6.3 cm. Then, the following three kinds of solutions were sequentially passed upward from the bottom of the column. First, 141 g of methanol was passed at a column temperature of 25 ° C. at a liquid passing rate of 3.5 g / min. Next, at a column temperature of 60 ° C., a mixed solution of 326 g of methanol and 8 g of concentrated hydrochloric acid (hydrogen chloride content: 36% by mass) was passed at a liquid passing rate of 3.0 g / min. Next, at a column temperature of 60 ° C., 190 g of methanol was passed at a liquid passing rate of 3.5 g / min, and then 126 g of methanol was passed through while cooling the column to 25 ° C. = 3.5 g / min. The liquid was passed in minutes. After that, the methanol in the column was extracted from the lower part of the column.

(C) Process C
Continuing from step B, first, 53 g of pyridine containing 0.3% by mass of water as a treatment agent was passed upward from the lower part of the column at a column temperature of 60 ° C. at a liquid passing speed of 3.2 g / min. Then, while raising the column temperature to 95 ° C., 170 g of the treatment agent was passed at a liquid passing rate of 3.2 g / min. Then, the treatment agent in the column was extracted from the lower part of the column. Here, the column temperature is equal to the contact temperature between the treatment agent and the solid after removing the mold material.

Next, a treatment agent obtained by mixing 272 g of tert-butyl alcohol, 48 g of acetone, and 0.96 g of water was passed through the column at a column temperature of 45 ° C. and upward from the bottom of the column at a liquid passing speed of 2.6 g / min. .. The amount of water contained in the treatment agent was 0.3% by mass. The amount of the treatment agent supplied to the column was 270 g. Then, the mixed solution of tert-butyl alcohol, acetone and water in the column was withdrawn from the lower part of the column.

(D) Step E
Following step C, 47 g of toluene is passed through the column at a column temperature of 50 ° C. and a flow rate of 2.8 g / min, and then 157 g of toluene is passed while raising the column temperature to 100 ° C. Liquid. As a result, the mixed solution remaining in the column at the end of step C was replaced with toluene. Then, the toluene in the column was extracted from the lower part of the column.

(E) Step D
Following step E, a mixed solution of 8 g of 1,1,1,3,3,3-hexamethyldisilazane (hereinafter, also referred to as HMDS) and 93 g of toluene was prepared at a column temperature of 100 ° C. and a liquid passing rate of 3.9 g. Liquid was passed from the bottom of the column at / min. At this time, the liquid passed through the column was collected by the receiver and continuously circulated by the pump for 3 hours. As a result, the molded product in the column was silylated. Then, the toluene and HMDS mixed solution in the column was withdrawn from the lower part of the column. Then, at a column temperature of 120 ° C., nitrogen gas was flowed upward from the lower part of the column into the column at a flow rate of 50 NmL / min, and after confirming that the distilling of the liquid from the upper part of the column had stopped, the flow rate was changed to 150 NmL / min. The mixture was changed and nitrogen gas was circulated for a total of 4 hours to dry the molded product. As a result, a molded body of a titanium-containing silicon oxide catalyst was obtained.

The life performance evaluation was performed by a series of methods described in the following (F) to (H).

(F) Evaluation of initial performance of catalyst [activity and selectivity]
The initial performance of the catalyst molded product obtained through the steps (A) to (E) was evaluated by a batch type reaction apparatus (autoclave). A catalyst molded product (1.5 ml), 60 g of a solution of CMHP dissolved in CUM at a concentration of 25% by mass (hereinafter referred to as 25% by mass CMHP / CUM), and 33 g of propylene were supplied to an autoclave, and the reaction temperature was controlled under natural pressure. The reaction was carried out at 100 ° C. and a reaction time of 1.5 hours (including a temperature rising time). The reaction results are shown in Table 1. The "conversion rate" in the table is the "CMHP conversion rate (%)" described later.

(G) Synthesis of Propylene Oxide by Fixed Bed Epoxidation Reaction 10 ml of catalyst molded body (space between molded bodies) obtained through the steps (A) to (E) in a reactor having an inner diameter of 16 mm (sheath tube outer diameter of 5 mm). The catalyst layer was formed by filling (apparent volume including volume), and propylene, CMHP, and CUM were supplied to the filled catalyst layer, and propylene oxide was synthesized by an epoxidation reaction for 42 hours. Hereinafter, propylene oxide is also referred to as PO. The reaction pressure is 6 MPa-G, and the reactor is heated by an electric furnace provided on the outside of the reactor so that the position 2 cm from the catalyst layer inlet is 135 ° C. After 2 hours, the set temperature of the electric furnace is constant. And said. The temperature of the catalyst layer was 99 ° C to 139 ° C.

(H) Evaluation of recovery catalyst performance after use for PO synthesis [activity and selectivity]
After the above-mentioned PO synthesis reaction (G) was carried out for 42 hours, the catalyst molded body was extracted from the reactor and recovered. The performance of the recovery catalyst was evaluated with a batch reactor. 1.5 mL of the catalyst compact, 60 g of 25 mass% CMHP / CUM, and 33 g of propylene were supplied to the autoclave, and the reaction was carried out under natural pressure at a reaction temperature of 100 ° C. and a reaction time of 1.5 hours (including temperature rise time). The reaction results are shown in Table 1.

The conversion rate of CMHP and the selectivity of PO were determined as follows.
-CMHP conversion rate (%) = M ₁ / (M _0- M ₁ ) x 100
M ₀ : Raw material CMHP molar amount M ₁ : CMHP molar amount in the liquid after the reaction / PO selectivity (%) = M _PO / (M _0- M ₁ )
M _PO: here generated PO molar _{amount, M PO = M 2 - (} M ph + M ac + M pg + 2 × M dpg + 3 × M tpg)
M _2: reacted CMHP molar amount _{M ph:} produced phenol molar amount _{M ac:} resulting acetophenone molar amount _{M pg:} formed propylene glycol molar amount _{M dpg:} generated dipropylene glycol molar amount _{M tpg:} generated tripropylene Glycol molar amount In Table 1, TBA is an abbreviation for tert-butyl alcohol and ACT is an abbreviation for acetone. In the table, for example, "TBA (230 g) / ACT (40 g)" refers to a mixture of 230 g of tert-butyl alcohol and 40 g of acetone. Further, in Table 3, ATN is an abbreviation for acetonitrile, and AMA is an abbreviation for tert-amyl alcohol (2-methyl-2-butanol).

[Examples 2 to 9]
Regarding Examples 2 to 8, the methods described in (A), (B) and (E) were carried out in the same manner as in Example 1. The methods described in (C) and (D) were carried out in the same manner as in Example 1 except that the treatment liquid and the treatment conditions were changed as described in Tables 1 to 4.

Regarding Example 9, the methods described in (A) and (B) are carried out in the same manner as in Example 1, and in the method described in (E), the total time of nitrogen gas distribution is 3 hours. It was carried out by the same method as in Example 1 except that. Further, the methods described in (C) and (D) were carried out in the same manner as in Example 1 except that the treatment liquid and the treatment conditions were changed as described in Table 4. Further, the life performance evaluation of Examples 2 to 9 was carried out by the method described in (F) to (H) of Example 1. The evaluation results are shown in Tables 1 to 3.

[Example 10]
(B) and (C) are carried out in the same manner as in Example 1 without adding tetraisopropyl titanate in (A). Following (C), nitrogen gas is flowed upward from the bottom of the column into the column at a column temperature of about 120 ° C. to dry the molded product. Then, nitrogen gas containing 50% by volume of titanium tetrachloride is flowed upward from the lower part of the column into the column at a flow rate of about 10 NmL / min at a column temperature of about 200 ° C., and is brought into contact with the molded body for about 2 hours. Then, nitrogen gas is flowed upward from the bottom of the column into the column at a flow rate of about 100 NmL / min at a column temperature of about 500 ° C. Then, by carrying out (E) in the same manner as in Example 1, a titanium-containing silicon oxide catalyst can be obtained.

〔比較例〕
比較例では、（Ａ）、（Ｂ）及び（Ｅ）に記載の方法については、実施例１と同様の方法で実施し、（Ｃ）〜（Ｄ）に記載の方法ついては、処理液、及び処理条件を、表５の通りに変えた以外は、実施例１と同様の方法で実施した。さらに、寿命性能評価は実施例１の（Ｆ）〜（Ｈ）に記載の方法で実施した。評価結果を表５に示す。

[Comparative example]
In the comparative example, the methods described in (A), (B) and (E) are carried out in the same manner as in Example 1, and the methods described in (C) to (D) are the treatment liquid and the treatment liquid. The treatment was carried out in the same manner as in Example 1 except that the treatment conditions were changed as shown in Table 5. Further, the life performance evaluation was carried out by the method described in Examples 1 (F) to (H). The evaluation results are shown in Table 5.

The method for producing a titanium-containing silicon oxide according to one aspect of the present invention can be applied to the production of a catalyst used in a reaction for producing an epoxide from an olefin and a hydroperoxide, and the titanium obtained by the method can be applied. The contained silicon oxide can be used, for example, as a catalyst in the production of propylene oxide.

The specification of Japanese Patent Application No. 2017-076970 (filed on April 7, 2017), which is the basic application for the priority claim of this application, is referred to herein in its entirety. It shall be incorporated into the book.

Claims (12)

The following process:
Step A: Mix the mold, the silicon source, and the solvent to obtain a solid containing the mold and the silicon oxide. Step B: Remove the mold from the solid obtained through the step A to obtain the mold. Step C to obtain a solid having a content of 10% by mass or less: Step D: Step to obtain a solid by contacting the solid obtained through step B with a treatment agent containing 0.01 to 20% by mass of water. It has a step of contacting a solid obtained through C with a silylating agent to obtain a solid.
At least selected from the group consisting of in process A, in process B, in process C, in process D, between process A and process B, between process B and process C, and between process C and process D. In one or more, introduce titanium into the solid ,
The treatment agent used in the step C is selected from the group consisting of a compound represented by the following formula (III), a compound represented by the following formula (IV), an alcohol having 1 to 12 carbon atoms, and a carboxylic acid. A method for producing a titanium-containing silicon oxide , which comprises at least one.
NR ⁸ R ⁹ R ¹⁰ (III)
(In formula (III), R ^{8 to} R ¹⁰ are independently hydrogen atoms, linear hydrocarbon groups having 1 to 18 carbon atoms, branched hydrocarbon groups having 3 to 18 carbon atoms, or Represents a cyclic hydrocarbon group having 5 to 18 carbon atoms.)

(In formula (IV), R ^{11 to} R ¹⁵ are independently (a) a linear hydrocarbon group having 1 to 6 carbon atoms, a branched hydrocarbon group having 3 to 6 carbon atoms, and Selected from the group consisting of a hydrocarbon group consisting of a cyclic hydrocarbon group having 5 to 6 carbon atoms, (b) a hydrogen atom, (c) a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A group selected from the group consisting of a halogen atom, a group represented by (d) -OA ¹ , and a group represented by (e) -NA ^{2 A 3 , and are represented by A 1} and A ^{2 in the formula.} and a ³ are each independently a hydrogen atom, a linear 1 to 6 carbon atoms hydrocarbon group, a hydrocarbon group of branched 3-6 carbon atoms, or cyclic carbon atoms 5-6 Represents a hydrocarbon group.) The titanium-containing silicon according to claim 1, wherein titanium is introduced into a solid in at least one selected from the group consisting of steps A, between steps B and C, and between steps C and D. Method for producing oxide. The method for producing a titanium-containing silicon oxide according to claim 1 or 2, wherein titanium is introduced into a solid in step A. The method for producing a titanium-containing silicon oxide according to any one of claims 1 to 3, wherein the mold is a surfactant. The titanium-containing product according to any one of claims 1 to 4, wherein the mold is a salt containing a quaternary ammonium ion represented by the following formula (I) or an amine represented by the following formula (II). Method for producing silicon oxide.
[NR ¹ R ² R ³ R ⁴ ] + (I)
(In the formula (I), R ¹ represents a linear or branched hydrocarbon group having ^{2 to 36 carbon atoms, and R 2 to} R ⁴ are independent hydrocarbon groups having 1 to 6 carbon atoms, respectively. Represents.)
NR ⁵ R ⁶ R ⁷ (II)
(In formula (II), R ⁵ represents a linear or branched hydrocarbon group having 2 to 36 carbon atoms, and R ⁶ and R ⁷ independently have hydrogen atoms or carbon atoms 1 to 6 respectively. Represents a hydrocarbon group.) The titanium-containing silicon oxide according to any one of claims 1 to 5, wherein the treatment agent used in the step C contains a compound represented by the above formula (III) or a compound represented by the above formula (IV). Manufacturing method. The method for producing a titanium-containing silicon oxide according to any one of claims 1 to 6, wherein the treatment agent used in the step C contains an alcohol having 1 to 12 carbon atoms. The method for producing a titanium-containing silicon oxide according to claim 7 , wherein the alcohol having 1 to 12 carbon atoms is a tertiary alcohol. The method for producing a titanium-containing silicon oxide according to any one of claims 1 to 6, wherein the treatment agent used in the step C contains a carboxylic acid. The method for producing a titanium-containing silicon oxide according to any one of claims 1 to 9 , wherein the water content in the treatment agent used in the step C is 2 to 20% by mass. The method for producing a titanium-containing silicon oxide according to any one of claims 1 to 10 , further comprising step E and / or step F after the end of step C and before the start of step D.
Step E: The treatment agent and / or the treatment liquid contained in the solid obtained through the step C is replaced with a liquid substantially inactive with respect to the silylating agent. Step F: Obtained through the step C. The process of drying a solid An epoxide having a step of producing a titanium-containing silicon oxide by the method according to any one of claims 1 to 11 and reacting the olefin with the hydroperoxide in the presence of the produced titanium-containing silicon oxide. Production method.