WO2012074033A1 - Method for producing titanium-containing silicon oxide moldings and method for producing oxirane compounds - Google Patents

Abstract

The invention relates to a method for producing titanium-containing silicon oxide moldings comprising the following first, second and third processes. First Process: A process of obtaining a swelled lamellar titanium-containing zeolite precursor (2) by bringing a lamellar titanium-containing zeolite precursor (1) into contact with a solution containing a swelling agent and a solvent Second Process: A process of obtaining a molding (3) by pressurizing the precursor (2) Third Process: A process of removing the swelling agent contained in the molding (3).

Description

Method for producing titanium-containing silicon oxide molded body and method for producing oxirane compound

The present invention relates to a method for producing a titanium-containing silicon oxide molded body and a method for producing an oxirane compound, which can produce an oxirane compound from olefin and hydroperoxide in high yield.

It is known that a titanium-containing silicon oxide catalyst having a zeolite structure is active in olefin epoxidation using hydrogen peroxide. The basic unit of the zeolite structure is TO ₄ having a tetrahedral structure (T = Si, Al, P, Ti, B, etc.), and one TO ₄ unit has four apex oxygens, respectively, and the next four TO ₄ units. By sharing with each other, TO ₄ units are successively connected three-dimensionally to form a crystalline porous structure. And there are zeolites with various structures due to the difference in the form of linkage of the TO ₄ units, and they are classified by the Structure Commission of the International Zeolite Association (IZA-SC) according to the structure code of the three letters of the alphabet according to the form. Yes.
For example, a titanium-containing MWW type zeolite catalyst is known as the catalyst. The titanium-containing MWW-type zeolite is a titanium-containing silicon oxide catalyst having a structure similar to that of MCM-22 zeolite well known as an alkylation catalyst and having a structure code represented by MWW. However, the titanium-containing MWW-type zeolite catalyst has insufficient activity for olefin epoxidation using hydrogen peroxide. In addition, since the titanium-containing MWW-type zeolite catalyst has a small pore size, the epoxidation activity is very low when a large olefin or organic hydroperoxide is used. As an approach for obtaining an MWW-type zeolite catalyst capable of reacting larger molecules, for example, after swelling between layers of a MWW-type zeolite layered precursor with a surfactant or the like, the swollen MWW-type zeolite layered precursor is converted into a swollen MWW-type zeolite layered precursor. There is known a method for producing a catalyst in which an MWW-type zeolite layered precursor is delaminated by sonication and calcination. This catalyst is widely known as ITQ2, which is an analog of MWW type zeolite. JP-T-2003-509479 discloses a method of producing a compact having a predetermined size or more by pressing a powder of ITQ2 obtained by delaminating to obtain a tablet, and crushing and classifying the tablet. Has been.
However, when an oxirane compound is produced from an olefin and a hydroperoxide using a titanium-containing zeolite or an analogue thereof as a catalyst, further improvement of the catalyst has been demanded from the viewpoint of yield, operability and handling properties. .

Under such circumstances, the problem to be solved by the present invention is to provide a method for producing a titanium-containing silicon oxide molded body and a method for producing an oxirane compound, which can produce an oxirane compound from olefin and hydroperoxide in high yield. This is what the point is.
That is, this invention relates to the manufacturing method of the titanium containing silicon oxide molded object which has the following 1st process, the following 2nd process, and the following 3rd process.
First step: A step of obtaining a swollen titanium-containing zeolite layered precursor (2) by bringing the titanium-containing zeolite layered precursor (1) into contact with a solution containing a swelling agent and a solvent. Second step: precursor ( Step 2) Pressurizing to obtain molded body (3) Third step: Step of removing swelling agent contained in molded body (3) Further, the present invention is a titanium-containing silicon obtained by the above production method The present invention relates to a method for producing an oxirane compound in which an olefin and a hydroperoxide are reacted in the presence of an oxide compact.

The manufacturing method of the titanium containing silicon oxide molded object of this invention has the following 1st process, the following 2nd process, and the following 3rd process.
First step: A step of obtaining a swollen titanium-containing zeolite layered precursor (2) by bringing the titanium-containing zeolite layered precursor (1) into contact with a solution containing a swelling agent and a solvent. Second step: precursor ( Step 2) Pressurizing to obtain molded body (3) Third step: Step of removing swelling agent contained in molded body (3) What is a titanium-containing zeolite layered precursor used as a raw material in the first step? A zeolite layered precursor in which titanium atoms are introduced. Zeolite layered precursor is a structure that has a structure in which multiple layers of sheet-like silicon oxide are laminated. By firing it, a three-dimensional crystalline porous structure is formed to form zeolite. This is a possible structure. Examples of the structure of the zeolite obtained by calcining the zeolite layered precursor include MWW type, FER type, RRO type, and CDO type defined by the Structure Commission of the International Zeolization Association (IZA-SC). Of these, an MWW-type zeolite layered precursor is preferable. Examples of the method for producing the titanium-containing MWW-type zeolite layered precursor include the method described in JP-A No. 2002-102709.
For the introduction of titanium atoms into the zeolite layered precursor, when the structure of the zeolite layered precursor is formed by hydrothermal synthesis or the like, a direct introduction method in which titanium atoms are introduced in the presence of a titanium source, zeolite not containing titanium atoms After synthesizing the layered precursor, any of post-introduction methods in which titanium atoms are introduced by a method such as ion exchange, isomorphous substitution, or atom planting may be used, but the introduction of titanium atoms may be performed by a direct introduction method. preferable.
The structure of the zeolite layered precursor can be observed by X-ray diffraction (XRD). Introduction of titanium atoms into the zeolite layered precursor can be confirmed by ultraviolet-visible spectroscopy (UV-Vis) or the like.
Hereinafter, a case where an MWW-type zeolite layered precursor directly introduced with titanium atoms, which is an example of a preferred embodiment of the present invention, will be described in detail, but the present invention is not limited to this description. Absent.
The titanium-containing MWW-type zeolite layered precursor can be obtained by mixing a silicon compound, a titanium compound, a boron compound, water and a structure directing agent, and then subjecting the obtained mixture to a hydrothermal synthesis reaction.
Examples of the silicon compound include alkoxysilane and amorphous silica. Examples of the alkoxysilane include tetramethylorthosilicate, tetraethylorthosilicate, and tetrapropylorthosilicate. Examples of the amorphous silica include Examples thereof include fumed silica.
Examples of the titanium compound include alkoxy titanium, peroxy titanate, titanium halide, titanium acetate, titanium nitrate, titanium sulfate, and titanium phosphate. Examples of the alkoxy titanium include tetra-n-propyl ortho. Examples thereof include titanate, tetra-isopropyl orthotitanate, tetra-n-butyl orthotitanate, etc., and examples of peroxytitanate include tetra-n-butylammonium peroxytitanate, and examples of titanium halide include, for example, , Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and the like.
Examples of the boron compound include boric acid and anhydrous boric acid.
The structure directing agent is an organic compound that is used as an aid for forming a structure of zeolite or a precursor thereof. Examples of the structure directing agent suitable for obtaining the MWW-type zeolite layered precursor include piperidine, hexamethyleneimine, and trimethyladamanta ammonium hydroxide. These structure directing agents may be used alone, or two or more structure directing agents having a desired ratio may be mixed and used. Of these, piperidine is preferably used alone.
The use ratio of each of the raw materials (silicon compound, titanium compound, boron compound, water and structure directing agent) is based on the number of silicon atoms in the silicon compound, and the titanium compound is 0.01 to 0.2 as titanium atoms. It is preferable that the boron compound is 0.1 to 3 mol times as a boron atom, water is 3 to 50 mol times, and the structure directing agent is 0.1 to 3 mol times.
The raw materials are preferably mixed at a temperature of 0 to 60 ° C., more preferably 10 to 50 ° C.
As the mixing method of the respective raw materials, for example, all the raw materials may be mixed at once, or the respective raw materials may be mixed sequentially. In particular, mixing the raw material that is liquid first and then mixing the raw material that is solid can uniformly stir the raw material, and thus avoid the uneven distribution of titanium atoms in the obtained titanium-containing MWW-type zeolite layered precursor. It is preferable because it is possible.
The mixture of each raw material is subjected to a hydrothermal synthesis reaction to obtain a titanium-containing MWW-type zeolite layered precursor. Here, the titanium-containing MWW-type zeolite layered precursor is a structure that changes to the structure of the MWW-type zeolite upon firing, and has a structure in and between each layer of titanium-containing silicon oxide. It means the structure in which the directing agent is included.
In general, hydrothermal synthesis refers to a synthesis method and crystal growth method of a substance carried out in the presence of high-temperature and high-pressure water (“Iwanami Physical and Chemical Dictionary”, 4th edition, Iwanami Shoten, 1987, p. In the present invention, specifically, the raw materials are mixed, and the mixture of raw materials is heated at a temperature of about 100 to 200 ° C. under autoclaving in an autoclave for several hours to several days. It is carried out by stirring or standing the mixture.
Solids generated by hydrothermal synthesis may contain compounds other than titanium-containing MWW-type zeolite layered precursors, and solids containing titanium-containing MWW-type zeolite layered precursors usually require filtration of the reaction mixture and residue. Depending on the case, it can be obtained by washing with an organic solvent such as water or methanol and then drying.
The drying method is preferably, for example, a method in which the residue is heated at 10 to 200 ° C. in a reduced pressure atmosphere or in the presence of a non-reducing gas such as nitrogen, argon, carbon dioxide or oxygen-containing gas, and 50 to 100 ° C. is preferable. Further preferred.
The titanium-containing MWW-type zeolite layered precursor produced by hydrothermal synthesis is preferably treated with an acid before being subjected to the first step described later to remove unnecessary Ti that does not function as a reactive site. Examples of acids used for removing unnecessary Ti include inorganic acids and organic acids. Examples of inorganic acids include hydrochloric acid, sulfuric acid, and nitric acid. Examples of organic acids include formic acid and acetic acid. An inorganic acid is preferable. Usually, the acid is used as a solution obtained by diluting the acid with a solvent. The concentration of the acid in the solution is preferably 0.5 to 10 N, and an organic solvent such as alcohol or ketone and water can be used as the solvent.
A swollen titanium-containing zeolite layered precursor (2) can be obtained by bringing the titanium-containing MWW-type zeolite layered precursor (1) obtained by the above operation into contact with a solution containing a swelling agent and a solvent. Examples of the method of bringing the precursor (1) into contact with the solution include a method of immersing the precursor (1) in the solution.
The swelling of the titanium-containing MWW-type zeolite layered precursor is that the peak of the precursor (2) derived from the 002 plane of the MWW structure in the X-ray diffraction method (XRD) is lower than the peak of the precursor (1). It can be confirmed from the difference in the amount of organic substances contained in the precursor (1) and the precursor (2) by elemental analysis or ignition loss analysis.
The swelling agent used in the first step is a compound having a characteristic of entering the interlayer of the titanium-containing MWW-type zeolite layered precursor to increase the interlayer distance. As the swelling agent, a surfactant can be suitably used, and among them, a compound containing a quaternary ammonium ion represented by the following general formula (I) is preferable.
[NR ¹ R ² R ³ R ⁴ ] ⁺ (I)
(In Formula (I), R ¹ represents a linear or branched hydrocarbon group having 2 to 36 carbon atoms, and R ² to R ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms. .)
In the general formula (I), R ¹ is a linear or branched hydrocarbon group having 2 to 36 carbon atoms, preferably a linear or branched hydrocarbon group having 10 to 18 carbon atoms. . R ² to R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms, and preferably all of R ² to R ⁴ are methyl groups.
Examples of the quaternary ammonium ion represented by the general formula (I) include hexadecyltrimethylammonium, dodecyltrimethylammonium, benzyltrimethylammonium, dimethyldidodecylammonium, hexadecylpyridinium, and the like. More preferred.
The swelling agent may contain only one type of quaternary ammonium ion represented by the general formula (I), or may contain two or more types.
Examples of the solvent contained in the solution can dissolve the swelling agent. Examples of the solvent include water, alcohol, and ketone. Examples of the alcohol include methanol, ethanol, 1-propanol, and 2-propanol. Examples of ketones include acetone. Two or more solvents may be mixed and used.
In order to promote swelling of the precursor (1), the solution is preferably alkaline. As the alkali source, quaternary ammonium hydroxide is preferable, and examples thereof include ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and the like, and the fourth represented by the general formula (I). More preferred is a hydroxide of a quaternary ammonium ion.
The temperature at which the precursor (1) is brought into contact with the solution is usually 40 to 120 ° C, more preferably 60 to 100 ° C. The time for bringing the precursor (1) into contact with the solution is usually 5 to 50 hours. Moreover, you may irradiate the solution containing a precursor (1) with an ultrasonic wave as needed, or may adjust pH of the solution containing a precursor (1).
Usually, a contact product obtained by bringing the precursor (1) into contact with the solution is filtered or centrifuged to obtain a solid. If necessary, the solid is washed with an organic solvent such as water or methanol, and then dried. A swollen titanium-containing zeolite layered precursor (2) can be obtained.
The drying method is preferably, for example, a method in which the residue is heated at 10 to 200 ° C. in a reduced pressure atmosphere or in the presence of a non-reducing gas such as nitrogen, argon, carbon dioxide or oxygen-containing gas, and 50 to 100 ° C. is preferable. Further preferred.
The second step of the present invention is a step of pressing the swollen titanium-containing zeolite layered precursor (2) obtained in the first step to obtain a molded body (3). It is the most important matter of the present invention to pressurize the swollen titanium-containing zeolite layered precursor (2), thereby removing the swelling agent from the molded body (3) in the subsequent third step, thereby providing catalyst physical properties. Can be obtained.
As a molding method for pressurizing the precursor (2), any method such as roll press molding (briqueting, compacting), hydraulic press molding, compression molding represented by tableting molding, extrusion molding or the like is used. However, compression molding is more preferable. In the case of extruding the precursor (2), generally used organic or inorganic binders can be used. In the present invention, a method using no binder is preferred.
The pressure when pressurizing the precursor (2) is usually 0.1 to 10 ton / cm ² , preferably 0.2 to 5 ton / cm ² , and more preferably 0.5 ton / cm ^2. ~ 2 tons / cm ² .
The water content of the solid subjected to compression molding is preferably 15% or less, more preferably 10% or less.
The shape of the molded body (3) may be any shape such as a tablet, a sphere, and a ring. In the subsequent third step, the molded body (3) may be used as it is, or may be used after being crushed to an appropriate size. When using the crushed compact (3), it is preferable to classify the crushed material of the compact (3) and use a crushed material of a predetermined size or more. The size of the molded body is preferably from 0.2 mm to 10 mm, and more preferably from 0.5 mm to 5 mm.
The 3rd process of this invention is a process of removing the swelling agent contained in the molded object (3) obtained at the 2nd process, and obtaining a titanium containing silicon oxide molded object.
Examples of the method for removing the swelling agent include a method of firing the molded product (3) obtained in the second step at a high temperature of 400 to 700 ° C. in air, and a method of extracting the swelling agent with a solvent. A method of removing the swelling agent is preferred.
The solvent used for the extraction is not particularly limited as long as it can dissolve the swelling agent. Generally, oxa and / or oxo substituted hydrocarbons having 1 to 12 carbon atoms and liquid at normal temperature can be used. Suitable solvents of this type include, for example, alcohols, ketones, ethers (acyclic compounds and cyclic compounds), esters, etc., and alcohols include, for example, methanol, ethanol, ethylene glycol , Propylene glycol, isopropanol, n-butanol, octanol and the like. Examples of ketones include acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone and the like. Examples of ethers include diisobutyl ether, tetrahydrofuran and the like. Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, butyl propionate, and the like. Moreover, a mixed solution with water or the above-mentioned solvent can also be used.
The weight ratio of these solvents to the molded body (3) is usually 1 to 1000, preferably 5 to 300.
In order to improve the extraction effect, it is preferable to add an acid or an acid salt to these solvents. Examples of the acid used include inorganic acids and organic acids. Examples of the inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and odorous acid. Examples of the organic acids include formic acid, acetic acid, and propionic acid. Etc. Examples of acid salts include alkali metal salts, alkaline earth metal salts, ammonium salts and the like. The concentration of the acid or acid salt in the solvent is preferably 10 mol / l or less, and more preferably 5 mol / l or less.
After sufficiently mixing the solvent and the molded body (3), the liquid phase is separated by a method such as filtration or decantation. This operation is repeated as many times as necessary. It is also possible to extract the swelling agent by a method in which the molded body (3) is filled and fixed in a tube and a washing solvent is passed through the fixed molded body (3). The end of extraction of the swelling agent can be known, for example, by liquid phase analysis. The extraction temperature is preferably 0 to 200 ° C, more preferably 20 to 100 ° C. When the boiling point of the extraction solvent is low, the extraction may be performed under pressure.
The titanium-containing silicon oxide molded body obtained after the extraction treatment may be dried. The drying method is preferably a method of heating at 10 to 700 ° C., more preferably 50 to 200 ° C. in an atmosphere of a non-reducing gas such as nitrogen, argon or carbon dioxide or an oxygen-containing gas such as air.
The titanium-containing silicon oxide molded body obtained by the above operation may contain titanium-containing MWW-type zeolite and the like, but the content of titanium-containing MWW-type zeolite is preferably 50% or less, 30 % Or less is more preferable.
The titanium-containing silicon oxide molded article is suitable as a catalyst in a method for producing an oxirane compound from an olefin and a hydroperoxide. A silylated titanium-containing silicon oxide molded body obtained by silylating a titanium-containing silicon oxide molded body obtained by the above method is also suitable as a catalyst in a method for producing an oxirane compound from an olefin and a hydroperoxide. Silylated titanium-containing silicon oxide compacts are more hydrophobic than titanium-containing silicon oxide compacts. Therefore, an oxirane compound can be produced in high yield from an olefin and a hydroperoxide by using a silylated titanium-containing silicon oxide molded article as a catalyst.
Examples of the method for silylating the titanium-containing silicon oxide molded body include a method of bringing the molded body into contact with a silylating agent. Examples of the silylating agent include organic silanes, organic silylamines, organic silylamides and derivatives thereof, organic silazanes, and other silylating agents.
Examples of the organic silane include chlorotrimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, chlorodimethylphenylsilane, dimethyl-n-propylchlorosilane, dimethylisopropylchlorosilane, t-butyldimethylchlorosilane, tripropylchlorosilane, dimethyloctylchlorosilane, and tributyl. Chlorosilane, trihexylchlorosilane, dimethylethylchlorosilane, dimethyloctadecylchlorosilane, n-butyldimethylchlorosilane, 3-chloropropyldimethylchlorosilane, dimethoxymethylchlorosilane, triethoxychlorosilane, dimethylphenylchlorosilane, benzyldimethylchlorosilane, diphenylmethylchlorosilane, diphenylvinylchlorosilane , Tribenzylchloro Orchids include 3-cyanopropyl dimethylchlorosilane.
Examples of the organic silylamine include N-trimethylsilylimidazole, Nt-butyldimethylsilylimidazole, N-dimethylethylsilylimidazole, N-dimethyl-n-propylsilylimidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilyldimethylamine. N-trimethylsilyldiethylamine, N-trimethylsilylpyrrole, N-trimethylsilylpyrrolidine, N-trimethylsilylpiperidine, 1-cyanoethyl (diethylamino) dimethylsilane, pentafluorophenyldimethylsilylamine.
Examples of organic silylamides and derivatives thereof include N, O-bistrimethylsilylacetamide, N, O-bistrimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltriamide. Examples include fluoroacetamide, N-methyl-N-trimethylsilylheptafluorobutyramide, N- (t-butyldimethylsilyl) -N-trifluoroacetamide, and N, O-bis (diethylhydrosilyl) trifluoroacetamide.
Examples of the organic silazane include hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-bis (chloromethyl) tetramethyldisilazane, 1,3-divinyl- Examples include 1,1,3,3-tetramethyldisilazane and 1,3-diphenyltetramethyldisilazane.
Examples of other silylating agents include N-methoxy-N, O-bistrimethylsilyltrifluoroacetamide, N-methoxy-N, O-bistrimethylsilylcarbamate, N, O-bistrimethylsilylsulfamate, trimethylsilyltrifluoromethane. Examples thereof include sulfonate and N, N′-bistrimethylsilylurea.
A preferred silylating agent is hexamethyldisilazane.
The silylation of the titanium-containing silicon oxide molded body can be performed in either a gas phase or a liquid phase. When silylation is carried out in the liquid phase, silylation is usually carried out in a solvent that does not essentially react with the silylating agent, and a hydrocarbon is preferably used as the solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Examples of the aliphatic hydrocarbons include hexane and heptane. Examples of the aromatic hydrocarbon include benzene, Examples include toluene and xylene. The silylation temperature is preferably 0 to 300 ° C, more preferably 50 to 150 ° C.
The titanium-containing silicon oxide molded body and silylated titanium-containing silicon oxide molded body obtained by the method of the present invention can be suitably used as a catalyst particularly in a method for producing an oxirane compound in which an olefin and a hydroperoxide are reacted.
The olefin may be an acyclic, monocyclic, bicyclic or polycyclic compound, and may be a monoolefin, diolefin or polyolefin. If there are two or more olefinic bonds, this may be a conjugated bond or a non-conjugated bond. Olefins having 2 to 60 carbon atoms are generally preferred. The olefin may have a substituent, and the substituent is preferably a relatively stable group. Examples of the monoolefin include ethylene, propylene, butene-1, isobutylene, hexene-1, hexene-2, hexene-3, octene-1, decene-1, styrene, cyclohexene, and propylene is preferable. Examples of the diolefin include butadiene and isoprene. Examples of the substituent include various substituents containing a halogen atom, an oxygen atom, a sulfur atom, or a nitrogen atom together with hydrogen and / or a carbon atom. Examples of the olefin having a substituent include Saturated alcohols, olefins substituted with a halogen atom, and the like. Examples of unsaturated alcohols include allyl alcohol and crotyl alcohol. Examples of olefins substituted with a halogen atom include allyl chloride. Can be mentioned.
Examples of the hydroperoxide suitably used in the present invention include hydrogen peroxide and organic hydroperoxide, and organic hydroperoxide is more preferable.
Organic hydroperoxides have the general formula R—O—O—H
(Where R is a monovalent hydrocarbyl group.)
Which reacts with an olefin to produce an oxirane compound and a compound R—OH. R is preferably a hydrocarbyl group having 3 to 20 carbon atoms, more preferably a hydrocarbyl group having 3 to 10 carbon atoms, and still more preferably a secondary or tertiary alkyl group having 3 to 10 carbon atoms. Group and a cycloalkyl group, or a secondary or tertiary aralkyl group having 8 to 10 carbon atoms, particularly preferably a tertiary alkyl group having 3 to 10 carbon atoms or a secondary alkyl group having 8 to 10 carbon atoms. Or it is a tertiary aralkyl group. Examples of the tertiary alkyl group having 3 to 10 carbon atoms include a tertiary butyl group and a third pentyl group. Examples of the tertiary aralkyl group having 8 to 10 carbon atoms include 2-phenylpropyl. -2 groups and the like. Furthermore, various tetranylyl groups generated by removing hydrogen atoms from the aliphatic side chain of the tetralin molecule are also exemplified as R.
The organic hydroperoxide is preferably cumene hydroperoxide, and in that case, the method for producing an oxirane compound of the present invention can be suitably used as part of the propylene oxide single production process described in JP-A-2008-266304. .
The oxirane compound can be produced in a liquid phase using a solvent. The solvent is preferably a liquid under the temperature and pressure during the reaction, and is substantially inert to the reactants and products. The solvent may be a substance present in the hydroperoxide solution used. For example, when the cumene hydroperoxide solution is a mixture of cumene hydroperoxide and cumene, which is a raw material thereof, this solution can be used as a substitute for the solvent without particularly adding a solvent.
The reaction temperature is generally 0 to 200 ° C., but a temperature of 25 to 200 ° C. is preferred. The pressure may be any pressure that can keep the reaction mixture in a liquid state. In general, the pressure is preferably 100 to 10,000 kPa.
After completion of the reaction, the liquid mixture containing the oxirane compound can be easily separated from the catalyst.
The liquid mixture may then be purified by an appropriate method. Purification includes fractional distillation, selective extraction, filtration, washing and the like. The solvent, catalyst, unreacted olefin and unreacted hydroperoxide can be recycled and reused.
Manufacture of an oxirane compound may be performed with a slurry and may be performed using a fixed bed. In the case of large-scale industrial operation, a method using a fixed bed is preferable. When the titanium-containing silicon oxide molded body or silylated titanium-containing silicon oxide molded body obtained by the present invention is used for a fixed bed, the pressure loss before and after the reaction tube is smaller than when powder is used. In addition, the catalyst is less likely to flow out downstream, and is excellent in handling properties during filling.

The following examples illustrate the invention.
[Example 1]
(1) Preparation of Titanium-containing Zeolite Layered Precursor 171 g of ion exchange water and 60 g of piperidine were placed in a 1 liter separable flask and stirred, and 5 g of tetra-n-butyl orthotitanate was added dropwise thereto at room temperature. After stirring these for 0.5 hour, 42 g of boric acid was added and further stirred for 0.5 hour. Subsequently, 30 g of fumed silica (Cabot-O-Sil M-7D manufactured by Cabot) was added, followed by stirring for 1 hour. Thereafter, 171 g of ion-exchanged water was added and stirred, and the homogenous mixture was divided into 4 parts. Each mixture was charged into 4 200 ml polytetrafluoroethylene inner cylinder autoclaves, and hydrothermal synthesis was performed at 170 ° C. for 7 days with stirring. went. The resulting solid was collected by filtration and washed with a small amount of ion-exchanged water. 211 g of the obtained solid was put into a 2 liter flask and 1125 ml of methanol was added. While stirring, the mixture was heated at the reflux temperature for 1.5 hours, allowed to cool, and then the solution was removed by filtration. For the recovered solid, the same operation was repeated once again using 1125 ml of methanol. Finally, the solid collected by filtration was washed with a small amount of methanol, and then dried at 70 ° C. and 10 mmHg for 7 hours to obtain 27 g of a solid containing a titanium-containing zeolite layered precursor.
(2) Step of obtaining swollen titanium-containing zeolite layered precursor (first step)
4 g of a solid containing a titanium-containing zeolite layered precursor obtained by the method (1) (700 ° C. loss on ignition 19.7%), 54 g of ion-exchanged water, 30 g of 29% hexadecyltrimethylammonium hydroxide water / methanol solution, Then, 11 g of hexadecyltrimethylammonium chloride was charged into a 200 ml polytetrafluoroethylene inner cylinder autoclave and heated at 80 ° C. for 16 hours with stirring. The resulting solid was centrifuged, washed with 1 liter of ion-exchanged water, and then dried at 70 ° C. and 10 mmHg for 7 hours. As a result, 4.4 g of swollen titanium-containing zeolite layered precursor (white solid, 700 ° C. heated) 4.4 g) was obtained.
(3) Production of molded body (second step)
4.4 g of the white solid obtained in the first step was compression-molded at a pressure of 0.5 ton / cm ² using a tablet molding machine having an inner diameter of 3 cm. The obtained tablets were crushed and a 1.0 to 1.7 mm shaped body was obtained using a sieve. Solids less than 1.0 mm were recycled and compression-molded again, and the resulting tablets were crushed and a 1.0 to 1.7 mm shaped body was obtained using a sieve. Moreover, when the obtained molded body was pulverized and subjected to powder X-ray diffraction (XRD) analysis using MiniFlex II manufactured by Rigaku Corporation, a peak derived from the 002 plane of the MWW structure showed a titanium-containing zeolite layered precursor. Compared to the peak observed by measuring the body, it was confirmed that it shifted to the lower angle side.
(4) Removal of swelling agent (third step)
4 g of the molded product obtained in the second step was placed in a flask, and a mixed solution of 200 ml of methanol and 40 g of concentrated hydrochloric acid (content 36% by weight) was added. While stirring, the mixture was heated at the reflux temperature for 1 hour. After standing to cool, the solution was removed by decantation. Next, 200 ml of methanol was added and refluxed for 1 hour. After allowing to cool, a solid was obtained by filtration. The solid was washed with a small amount of methanol and then dried at 70 ° C. and 10 mmHg for 3 hours. As a result, 1.7 g of a titanium-containing silicon oxide compact was obtained.
(5) Silylation (fourth step)
1 g of the titanium-containing silicon oxide molded body obtained in the third step, 1 g of hexamethyldisilazane, and 20 g of toluene were mixed and heated under reflux for 1.5 hours. After allowing to cool, the solid was collected by filtration and dried at 120 ° C. and 10 mmHg for 1.5 hours to obtain 1 g of a silylated titanium-containing silicon oxide molded body.
(6) Propylene oxide (PO) synthesis 0.25 g of a silylated titanium-containing silicon oxide molded body obtained by the above method, 60 g of 25% cumene hydroperoxide (CHPO) / cumene solution and 33 g of propylene were autoclaved. The reaction was carried out at 100 ° C. for 1.5 hours (including the heating time) under autogenous pressure. After the autoclave was cooled and purged with propylene, the autoclave was opened, and the reaction mixture was sampled and analyzed. The reaction results are shown in Table 1.
(7) Catalyst analysis Using MiniFlex II manufactured by Rigaku Corporation, a powder X-ray diffraction (XRD) analysis of the silylated titanium-containing silicon oxide molded body obtained by the above method was performed. The results of catalyst analysis are shown in Table 1.
[Example 2]
The same operation as in Example 1 was performed except that the swelling agent was removed in the third step not by solvent extraction but by firing the molded body for 5 hours at 540 ° C. in an air stream of 100 ml / min. The catalyst analysis results and reaction results are shown in Table 1.
[Comparative Example 1]
The same operation as in Example 1 was performed except that the order of the second step and the third step in Example 1 was changed and molding was performed after removal of the swelling agent (solvent extraction). The catalyst analysis results and reaction results are shown in Table 1.
[Comparative Example 2]
The same operation as in Example 2 was performed except that the order of the second step and the third step in Example 2 was changed and molding was performed after removing (sintering) the swelling agent. The catalyst analysis results and reaction results are shown in Table 1.

According to the present invention, an oxirane compound can be produced from olefin and hydroperoxide in high yield.

Claims (9)

1. The manufacturing method of the titanium containing silicon oxide molded object which has the following 1st processes, 2nd processes, and 3rd processes.
   First step: A step of obtaining a swollen titanium-containing zeolite layered precursor (2) by bringing the titanium-containing zeolite layered precursor (1) into contact with a solution containing a swelling agent and a solvent. Second step: precursor ( Step of pressurizing 2) to obtain a molded body (3) Third step: Step of removing a swelling agent contained in the molded body (3)
2. The production method according to item 1, wherein the precursor (1) is a titanium-containing MWW-type zeolite layered precursor.
3. Item 3. The method according to Item 1 or 2, wherein the swelling agent contains a quaternary ammonium ion represented by the formula (I).
   [NR ¹ R ² R ³ R ⁴ ] ⁺ (I)
   (R ¹ represents a linear or branched hydrocarbon group having 2 to 36 carbon atoms, and R ² , R ³ and R ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms.)
4. 4. The method according to any one of items 1 to 3, wherein the solution containing the swelling agent and the solvent is alkaline.
5. A method for producing a silylated titanium-containing silicon oxide molded article, comprising a step of silylating a titanium-containing silicon oxide molded article obtained by the method according to any one of Items 1 to 4.
6. A method for producing an oxirane compound, comprising a titanium-containing silicon oxide molded body obtained by the method according to any one of Items 1 to 4 or a titanium silicide-containing material obtained by the method according to Item 5. A method of reacting an olefin and a hydroperoxide in the presence of a silicon oxide molded body.
7. 7. The method according to item 6, wherein the olefin is propylene.
8. Item 8. The method according to Item 6 or 7, wherein the hydroperoxide is an organic hydroperoxide.
9. 9. The method according to item 8, wherein the organic hydroperoxide is cumene hydroperoxide.