JP3788107B2 - Titanium-containing silicon oxide catalyst, method for producing the catalyst, and method for producing propylene oxide - Google Patents

Description

＊１：細孔分布の最小値は窒素吸着法による測定限界値
【００４０】
表１のクメンハイドロパーオキサイドを用いたエポキシ化反応において、本発明による触媒は活性、選択性ともに明らかに高い性能を示していることがわかる。
【００４１】
【発明の効果】
以上説明したとおり、本発明により、高収率及び高選択率下に、プロピレンとエチルベンゼンハイドロパーオキサイド以外のハイドロパーオキサイドからプロピレンオキサイドを製造することができるチタン含有珪素酸化物触媒、該触媒の製造方法及びプロピレンオキサイドの製造方法を提供することができた。
【図面の簡単な説明】
【図１】実施例１の触媒のＸ線回折チャートである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a titanium-containing silicon oxide catalyst, a method for producing the catalyst, and a method for producing propylene oxide. More specifically, the present invention relates to a titanium-containing silicon oxide catalyst capable of producing propylene oxide from hydroperoxide other than propylene and ethylbenzene hydroperoxide under high yield and high selectivity, and a method for producing the catalyst And a method for producing propylene oxide.
[0002]
[Prior art]
Titanium-containing silicon oxides synthesized using quaternary ammonium ions as templates are known. As those having pores having an average pore diameter of 10 mm or more, Ti-MCM41 disclosed in US Pat. No. 5,783,167, Ti-MCM48 disclosed in JP-A-7-301212, and the like are known. Since all of these titanium-containing silicon oxides have large pores of 20 mm or more, epoxidation using a large-sized molecule such as an aromatic compound which is less active in zeolites having a small pore size as a reactant. Also shows high activity in the reaction. Further, since it has a high surface area, it is known that it exhibits higher activity in the reaction than a titanium-supported silica catalyst as disclosed in US Pat. No. 4,367,342. As described above, any known titanium-containing silicon oxides synthesized using quaternary ammonium ions as a template and having pores having an average pore diameter of 10 mm or more have the template removed by firing.
[0003]
On the other hand, extracting and removing the template with a solvent can avoid an increase in the temperature of the catalyst during calcination, and the state of titanium and hydroxyl groups on the catalyst seems to be different from that of the calcination catalyst. A titanium-containing silicon oxide synthesized using such a quaternary ammonium ion as a template and having an average pore diameter of 10 mm or more and obtained by removing the template by a solvent extraction operation is a very effective catalyst in the epoxidation reaction. It has not been reported so far.
[0004]
[Problems to be solved by the invention]
Under such circumstances, the problem to be solved by the present invention is a titanium-containing silicon oxide catalyst capable of producing propylene oxide from hydroperoxides other than propylene and ethylbenzene hydroperoxide under high yield and high selectivity, The present invention resides in providing a method for producing the catalyst and a method for producing propylene oxide.
[0005]
[Means for Solving the Problems]
That is, the first invention of the present invention is a titanium-containing silicon oxide catalyst that satisfies all the following conditions (1) to (5), and reacts hydroperoxide other than propylene and ethylbenzene hydroperoxide. This relates to a catalyst for use in producing propylene oxide .
(1): The average pore diameter is 10 mm or more (2): 90% or more of the total pore volume has a pore diameter of 5 to 200 mm (3): The specific pore volume is 0.2 cm ³ / g (4): It is obtained by using a quaternary ammonium ion represented by the following general formula (I) as a mold (template) and then removing the mold by a solvent extraction operation. [NR ¹ R ² R ³ R ⁴ ] ⁺ (I)
(In the formula, R ¹ represents a linear or branched hydrocarbon group having ² to 36 carbon atoms, and R ^{2 to} R ⁴ represent an alkyl group having 1 to 6 carbon atoms.)
(5): In X-ray diffraction, it has at least one peak having an interplanar spacing d larger than 18 mm. The second invention of the present invention is the production of the catalyst of the first invention including the following steps: It concerns the method.
1st process: The process of obtaining the solid which contains a catalyst component and a mold agent by mixing and stirring the quaternary ammonium ion as a silica source, a titanium source, and a mold agent in a solvent 2nd process: Obtained at the 1st process The step of obtaining the catalyst by removing the mold agent by subjecting the obtained solid to solvent extraction operation The third invention of the present invention is propylene and ethylbenzene hydroperoxide in the presence of the catalyst of the first invention. This relates to a method for producing propylene oxide in which a hydroperoxide other than the above is reacted.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The catalyst of the present invention is a catalyst comprising a titanium-containing silicon oxide that satisfies all the following conditions (1) to (5). By using such a catalyst, the problem of producing propylene oxide from hydroperoxides other than propylene and ethylbenzene hydroperoxide can be achieved at a high level for the first time with high yield and high selectivity.
[0007]
The condition (1) is that the average pore diameter is 10 mm or more.
[0008]
Condition (2) is that 90% or more of the total pore volume has a pore diameter of 5 to 200 mm.
[0009]
The condition (3) is that the specific pore volume is 0.2 cm ³ / g or more. Here, the specific pore volume means the pore volume per 1 g of the catalyst.
[0010]
The measurement about said conditions (1)-(3) can be measured by a normal method using the physical adsorption method of gas, such as nitrogen and argon.
[0011]
Condition (4) is obtained by using a quaternary ammonium ion represented by the following general formula (I) as a mold, and then removing the mold by a solvent extraction operation.
[NR ¹ R ² R ³ R ⁴ ] ⁺ (I)
(In the formula, R ¹ represents a linear or branched hydrocarbon group having ² to 36 carbon atoms, and R ^{2 to} R ⁴ represent an alkyl group having 1 to 6 carbon atoms.)
Condition (4) will be described in detail in the catalyst production method.
[0012]
The condition (5) is to have at least one peak having an interplanar spacing d larger than 18 mm in X-ray diffraction (XRD). The peak indicating the interplanar spacing d here is a peak derived from the crystallinity or regularity of the solid, and there may be a broad peak derived from an amorphous part. Note that, in X-ray diffraction, it is preferable that a peak having an interplanar spacing d larger than 18Å is a part of a peak group representing a hexagonal structure.
[0013]
The catalyst of the present invention preferably has an absorption peak in the region of 960 ± 5 cm ⁻¹ in the infrared absorption spectrum. This peak is considered to correspond to titanium introduced into the silica skeleton.
[0014]
The catalyst of the present invention can be optimally produced by a production method having the following steps.
First step: A step of obtaining a solid containing a catalyst component and a mold agent by mixing and stirring a silica source, a titanium source and a quaternary ammonium ion as a mold agent in a liquid state. Second step: obtained in the first step A step of obtaining a catalyst by removing a mold agent by subjecting a solid to an extraction operation.
The first step is a step of obtaining a solid containing a catalyst component and a mold agent by mixing and stirring a silica source, a titanium source and a quaternary ammonium ion as a mold agent in a liquid state. When the reagent to be used is a solid, it may be used as a solution dissolved or dispersed in a solvent.
[0016]
Examples of the silica source include amorphous silica and alkoxysilanes such as tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate and the like.
[0017]
Titanium alkoxides such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra-2-ethylhexyl titanate, tetra titanate Examples include octadecyl, titanium (IV) oxyacetylacetonate, titanium (IV) diipropoxybisacetylacetonate, and titanium halides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide.
[0018]
As the mold agent, a quaternary ammonium ion represented by the following general formula (I) is used.
[NR ¹ R ² R ³ R ⁴ ] ⁺ (I)
(In the formula, R ¹ represents a linear or branched hydrocarbon group having ² to 36 carbon atoms, and R ^{2 to} R ⁴ represent an alkyl group having 1 to 6 carbon atoms.)
R ¹ is a linear or branched hydrocarbon group having 2 to 36 carbon atoms, preferably 10 to 18 carbon atoms. R ^{2 to} R ⁴ are each an alkyl group having 1 to 6 carbon atoms, and all of R ^{2 to} R ⁴ are preferably methyl groups.
Specific examples of the quaternary ammonium ion represented by the general formula (I) include cations such as hexadecyltrimethylammonium, dodecyltrimethylammonium, benzyltrimethylammonium, dimethyldidodecylammonium, hexadecylpyridinium and the like.
[0019]
Examples of solvents include water and alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, sec-butanol, t-butanol, vinyl alcohol, allyl alcohol, cyclohexanol, benzyl alcohol, and the like, diols, Moreover, those mixtures can be mentioned. However, when diluted with excess alcohol, the obtained catalyst may hardly have a peak indicating an interplanar spacing d larger than 18 mm in XRD.
[0020]
The amount of titanium source used relative to the silica source is ^10-5 to 1, preferably 0.00008 to 0.4, in molar ratio. Moreover, it is preferable that the usage-amount of the quaternary ammonium ion with respect to the total amount of these silica sources and titanium sources shall be 10 ^<-2 > ^-2 by molar ratio.
[0021]
Moreover, in order to accelerate | stimulate reaction of a silica source and a titanium source, it is preferable to provide alkalinity or acidity to a mixed solution. The alkali source is preferably quaternary ammonium hydroxide, and examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and the like. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and propionic acid.
[0022]
The mixing / stirring temperature is usually -30 to 100 ° C. A solid is produced by mixing and stirring, and this may be aged in order to further grow the solid. The aging time is usually 180 hours or less, and the aging temperature is usually 0 to 200 ° C. When heating is required at the time of aging, it is preferably carried out by transferring to a pressure vessel and sealing in order to avoid vaporization of the solvent.
[0023]
Next, the second step is a step of obtaining a catalyst by removing the mold by subjecting the solid obtained in the first step to a solvent extraction operation with a solvent. A technique for extracting a template with a solvent has been reported by Whitehurst et al. (See US Pat. No. 5,143,879). The solvent used for the extraction is not particularly limited as long as it can dissolve the compound used in the mold, and oxa- and / or oxo-substituted hydrocarbons that are liquid at normal temperature having 1 to about 12 carbon atoms can be used. Suitable solvents of this type can include alcohols, ketones, ethers (acyclic and cyclic) and esters such as methanol, ethanol, ethylene glycol, propylene glycol, isopropanol, hydroxy-substituted hydrocarbons such as n-butanol and octanol; oxo-substituted hydrocarbons such as acetone, diethyl ketone, methyl ethyl ketone and methyl isobutyl ketone; hydrocarbon ethers such as diisobutyl ether and tetrahydrofuran; and methyl acetate, ethyl acetate, acetic acid And hydrocarbon esters such as butyl and butyl propionate. The weight ratio of these solvents to the catalyst is usually 1-1000, preferably 10-300. Moreover, in order to improve the extraction effect, an acid or a salt thereof may be added to these solvents. 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 such salts include alkali metal salts, alkaline earth metal salts, ammonium salts and the like. The concentration of the acid to be added or a salt thereof in the solvent is preferably 10 mol / l or less, more preferably 1 mol / l or less. If the concentration of the acid to be added or the salt thereof in the solvent is excessive, titanium present in the catalyst may be eluted and the catalytic activity may be lowered. In addition, when a large amount of water is mixed in the solvent, the structure of the catalyst is broken during the extraction operation, and a regular structure is not observed in X-ray diffraction.
[0024]
After thoroughly mixing the solvent and the catalyst, the liquid phase part 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 by a method in which a washing solvent is passed through the catalyst layer. The end of the cleaning can be known, for example, by analyzing the liquid phase part. The extraction temperature is preferably 0 to 200 ° C, more preferably 20 to 100 ° C.
[0025]
It is also possible to perform extraction using a supercritical fluid instead of using the organic extraction solvent. Carbon dioxide is preferred as the supercritical fluid. The critical temperature of carbon dioxide is about 31 ° C. or higher, and the extraction temperature is preferably 31 to 100 ° C., more preferably 35 to 60 ° C. The critical pressure is approximately 7.4 MPa, preferably 10-30 MPa. Preferably, 50 to 500 g of supercritical carbon dioxide per minute is used for extraction per liter of catalyst, and the extraction time is 4 to 20 hours.
[0026]
The solid obtained after the extraction treatment may be subjected to a drying treatment. That is, heating is preferably performed at 10 to 800 ° C. in an atmosphere of a non-reducing gas such as nitrogen, argon, carbon dioxide, or an oxygen-containing gas such as air. 50-300 degreeC is still more preferable.
[0027]
In producing the catalyst, it is preferable to use the following third step following the first step and the second step.
Third step: A step of obtaining a silylated catalyst by subjecting the catalyst obtained in the second step to a silylation treatment. In the silylation treatment, the catalyst obtained in the second step is brought into contact with a silylating agent. This is carried out by converting a hydroxyl group present on the surface of the substrate into a silyl group. Examples of silylating agents include organic silanes, organic silylamines, organic silylamides and derivatives thereof, and organic silazanes and other silylating agents.
[0028]
Examples of organosilanes include chlorotrimethylsilane, dichlorodimethylsilane, chlorobromodimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, iododimethylbutylsilane, chlorodimethylphenylsilane, dichlorodimethylsilane, dimethyl n-propylchlorosilane, dimethylisopropyl Chlorosilane, t-butyldimethylchlorosilane, tripropylchlorosilane, dimethyloctylchlorosilane, tributylchlorosilane, trihexylchlorosilane, dimethylethylchlorosilane, dimethyloctadecylchlorosilane, n-butyldimethylchlorosilane, bromomethyldimethylchlorosilane, chloromethyldimethylchlorosilane, 3-chloro Propyldimethylchlorosilane, dimethoxymethylchlorosilane, dimethyl Examples include phenylchlorosilane, triethoxychlorosilane, dimethylphenylchlorosilane, methylphenylvinylchlorosilane, benzyldimethylchlorosilane, diphenyldichlorosilane, diphenylmethylchlorosilane, diphenylvinylchlorosilane, tribenzylchlorosilane, and 3-cyanopropyldimethylchlorosilane.
[0029]
Examples of organic silylamines include N-trimethylsilylimidazole, Nt-butyldimethylsilylimidazole, N-dimethylethylsilylimidazole, N-dimethyln-propylsilylimidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilyldimethylamine, Examples thereof include N-trimethylsilyldiethylamine, N-trimethylsilylpyrrole, N-trimethylsilylpyrrolidine, N-trimethylsilylpiperidine, 1-cyanoethyl (diethylamino) dimethylsilane, and pentafluorophenyldimethylsilylamine.
[0030]
Examples of organic silylamides and derivatives include N, O-bistrimethylsilylacetamide, N, O-bistrimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoro Examples include acetamide, N-methyl-N-trimethylsilylheptafluorobutyramide, N- (t-butyldimethylsilyl) -N-trifluoroacetamide, N, O-bis (diethylhydrosilyl) trifluoroacetamide.
[0031]
Examples of organic silazanes 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.
[0032]
Other silylating agents include N-methoxy-N, O-bistrimethylsilyl trifluoroacetamide, N-methoxy-N, O-bistrimethylsilyl carbamate, N, O-bistrimethylsilylsulfamate, trimethylsilyl trifluoromethanesulfonate, N, N′-bistrimethylsilylurea is exemplified. A preferred silylating agent is hexamethyldisilazane.
[0033]
Since the catalyst thus prepared has a high surface area and highly dispersed titanium active sites, it can be used for various oxidation reactions of organic compounds in addition to selective oxidation reactions such as olefin epoxidation reactions. is there. If desired, the acid point of the catalyst can be further strengthened by adding a third component such as alumina, and can be used for an alkylation reaction, a catalytic reforming reaction, or the like.
[0034]
In particular, the catalyst of the present invention can be optimally used in a method for producing propylene oxide in which hydroperoxide other than propylene and ethylbenzene hydroperoxide is reacted. Examples of hydroperoxides other than ethylbenzene hydroperoxide include organic hydroperoxide. Organic hydroperoxides have the general formula R—O—O—H
(Here, R is a monovalent hydrocarbon group.)
Which reacts with an olefinic compound to produce an oxirane compound and a compound R—OH. Preferably, the group R is a group having 3 to 20 carbon atoms. Most preferably it is a hydrocarbon group of 3 to 10 carbon atoms, in particular a secondary or tertiary alkyl group or an aralkyl group. Among these groups, particularly preferred groups are a tertiary alkyl group and a second or third aralkyl group, and specific examples thereof include a tertiary butyl group, a tertiary pentyl group, a cyclopentyl group, 2-phenylpropyl- 2 groups, and various tetranyl groups generated by removing hydrogen atoms from the aliphatic side chain of the tetralin molecule. When cumene hydroperoxide is used as the organic hydroperoxide, the resulting hydroxyl compound is 2-phenyl-2-propanol. This can be converted to α-methylstyrene by a dehydration reaction. α-Methylstyrene is an industrially useful substance. The third amylene produced by the dehydration reaction of the third pentyl alcohol obtained when the third pentyl hydroperoxide is used as the organic hydroperoxide is a substance useful as a precursor of isoprene. Tertiary pentyl alcohol is also useful as a precursor of methyl tertiary pentyl ether which is an octane improver. T-Butyl alcohol obtained when t-butyl hydroperoxide is used as the organic hydroperoxide is a useful substance as a precursor of methyl-t-butyl ether which is an octane number improver. Hydrogen peroxide can be given as an example of hydroperoxide other than organic hydroperoxide. Hydrogen peroxide is a compound of the chemical formula HOOH and can usually be obtained in the form of an aqueous solution. This reacts with the olefinic compound to produce an oxirane compound and water. The organic hydroperoxide and hydrogen peroxide used as raw materials may be a diluted or concentrated purified product or non-purified product.
[0035]
The epoxidation reaction can be performed by bringing a hydroperoxide other than propylene and ethylbenzene hydroperoxide into contact with the catalyst. This reaction can be carried out in a liquid phase using a solvent and / or a diluent. The solvent and diluent must be liquid under the temperature and pressure during the reaction and be substantially inert to the reactants and products. The solvent may consist of substances present in the hydroperoxide solution used. For example, when cumene hydroperoxide is a mixture of cumene hydroperoxide and cumene, which is a raw material thereof, it can be used as a substitute for a solvent without particularly adding a solvent. The epoxidation reaction temperature is generally 0 to 200 ° C, but a temperature of 25 to 200 ° C is preferable. The pressure may be sufficient to keep at least a portion of the reaction mixture in a liquid state. In general, the pressure is advantageously between 100 and 10000 kPa. After completion of the epoxidation reaction, the liquid mixture containing the desired product can be easily separated from the catalyst composition. Next, the desired mixture of propylene oxide can be obtained by purifying the liquid mixture by an appropriate method. Purification includes fractional distillation, selective extraction, filtration, washing and the like. The solvent, catalyst, unreacted propylene and unreacted hydroperoxide can be recycled and used again. The process according to the invention can advantageously be carried out using a catalyst in the form of a slurry or a fixed bed. For large scale industrial operations, it is preferred to use a fixed bed. The process according to the invention can be carried out by batch, semi-continuous or continuous processes. When the liquid containing the reaction raw material is passed through the fixed bed, the liquid mixture discharged from the reaction zone contains no or substantially no catalyst.
[0036]
Propylene oxide can be converted to industrially useful polymer products by polymerization or copolymerization reactions.
[0037]
【Example】
The following examples illustrate the invention.
Example 1
Catalyst preparation (according to the invention)
175 g of water was mixed with 28 g of cetyltrimethylammonium bromide and 48 g of 25% tetramethylammonium hydroxide aqueous solution, and this was mixed with 77 g of tetramethylorthosilicate and 6.3 g of 75% titanium (IV) diisopropoxybisacetylacetonate at room temperature. The solution was added. After stirring for 3 hours, the resulting precipitate was filtered off and washed with water. Washing with water was performed until the washing solution became neutral. The obtained precipitate was put into a flask and mixed with 500 ml of hydrochloric acid / ethanol mixed solution (hydrochloric acid 0.1 mol / l) per 10 g of catalyst. While stirring, the mixture was continuously heated at 60 ° C. for 1 hour, allowed to cool to 40 ° C. or lower, and then the solvent was removed by filtration. The same operation was repeated once more, and the finally filtered white solid was transferred to a tube furnace and dried under a nitrogen stream at 150 ° C. for 5 hours.
This material (5 g), hexamethyldisilazane (3.4 g), and toluene (50 g) were mixed and heated to reflux for 1 hour with stirring. The liquid was distilled off from the mixture by filtration. The catalyst was obtained by washing with toluene (100 g) and vacuum drying (120 ° C., 10 mmHg, 3 hours). The catalyst thus synthesized had a specific surface area of 936 m ² / g, an average pore diameter of 30 kg, a pore volume of 0.7 cc / g, and a pore distribution range of 5 to 80 kg.
Synthesis of propylene oxide (PO) 0.75 g of the catalyst synthesized in this way was charged with 17 g of cumene solution containing 41% cumene hydroperoxide (CHPO) and 13 g of propylene in a 150 cc SUS autoclave, and the reaction temperature was increased. Epoxidation reaction was performed by batch reaction at 80 ° C. and reaction time of 90 minutes. The reaction results are shown in Table 1.
[0038]
Comparative Example 1
Preparation of titanium-supporting silica catalyst Under a nitrogen stream, acetylacetone (3.2 g) was slowly added dropwise to a solution of tetraisopropyl titanate (4.4 g) in isopropanol (20 ml) with stirring, followed by stirring for 30 minutes at room temperature. . The above solution was added dropwise to a mixture of commercially available silica gel (10 to 20 mesh, surface area 326 m ² / g, average pore diameter 100 mm) (50 g) and isopropanol (230 ml), and the mixture was filtered after stirring at room temperature for 1 hour. The solid portion was washed 3 times with isopropanol (total 250 ml). The solid part was dried at 150 ° C. for 2 hours in an air atmosphere. Further, it was calcined at 600 ° C. for 4 hours in an air atmosphere. This material (10 g), hexamethyldisilazane (4 g), and toluene (50 g) were mixed and heated to reflux for 1 hour with stirring. The liquid was distilled off from the mixture by filtration. The catalyst was obtained by washing with toluene (100 g) and vacuum drying (120 ° C., 10 mmHg, 3 hours). The catalyst thus synthesized had a specific surface area of 244 m ² / g, an average pore diameter of 148 kg, a pore volume of 0.9 cm ³ / g, and a pore distribution range of 5 to 200 kg. Reaction evaluation was performed in the same manner as in Example 1. The epoxidation reaction results are shown in Table 1.
[0039]
[Table 1]

* 1: The minimum value of the pore distribution is the measurement limit value by the nitrogen adsorption method.
In the epoxidation reaction using cumene hydroperoxide of Table 1, it can be seen that the catalyst according to the present invention clearly shows high performance in both activity and selectivity.
[0041]
【The invention's effect】
As described above, according to the present invention, a titanium-containing silicon oxide catalyst capable of producing propylene oxide from hydroperoxide other than propylene and ethylbenzene hydroperoxide with high yield and high selectivity, and production of the catalyst And a method for producing propylene oxide could be provided.
[Brief description of the drawings]
1 is an X-ray diffraction chart of a catalyst of Example 1. FIG.

Claims (9)

A titanium-containing silicon oxide catalyst that satisfies all of the following conditions (1) to (5) , which is used for producing propylene oxide by reacting propylene and a hydroperoxide other than ethylbenzene hydroperoxide .
(1): The average pore diameter is 10 mm or more (2): 90% or more of the total pore volume has a pore diameter of 5 to 200 mm (3): The specific pore volume is 0.2 cm ³ / g (4): It is obtained by using a quaternary ammonium ion represented by the following general formula (I) as a mold (template) and then removing the mold by a solvent extraction operation. [NR ¹ R ² R ³ R ⁴ ] ⁺ (I)
(In the formula, R ¹ represents a linear or branched hydrocarbon group having ² to 36 carbon atoms, and R ^{2 to} R ⁴ represent an alkyl group having 1 to 6 carbon atoms.)
(5): In X-ray diffraction, it has at least one peak showing a surface separation d larger than 18 mm.   The catalyst according to claim 1, wherein the peak in the X-ray diffraction is a part of a peak group representing a hexagonal structure. The catalyst according to claim 1, which has an absorption peak in a region of 960 ± 5 cm ^{-1 in} an infrared absorption spectrum. The manufacturing method of the catalyst of Claim 1 which has the following process.
1st process: The process of obtaining the solid which contains a catalyst component and a mold agent by mixing and stirring the quaternary ammonium ion as a silica source, a titanium source, and a mold agent in a solvent 2nd process: Obtained at the 1st process A catalyst is obtained by removing the mold by subjecting the solid to a solvent extraction operation. The manufacturing method of the catalyst of Claim 1 which has the 1st process of Claim 4, a 2nd process, and the following process.
Third step: A step of obtaining a silylation-treated catalyst by subjecting the catalyst obtained in the second step to silylation treatment. A method for producing propylene oxide, comprising reacting propylene with a hydroperoxide other than ethylbenzene hydroperoxide in the presence of the catalyst according to claim 1. The process according to claim 6, wherein the hydroperoxide other than ethylbenzene hydroperoxide is an organic hydroperoxide. The method according to claim 7, wherein the organic hydroperoxide is cumene hydroperoxide or t-butyl hydroperoxide. The process according to claim 6, wherein the hydroperoxide other than ethylbenzene hydroperoxide is hydrogen peroxide.

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