JP4834982B2 - Method for producing titanium-containing silicon oxide catalyst and catalyst - Google Patents

Description

  The present invention relates to a method for producing a titanium-containing silicon oxide catalyst and a catalyst. More specifically, the present invention can be used, for example, in a reaction for obtaining an oxirane compound from hydroperoxide and an olefin type compound, and a method for producing a titanium-containing silicon oxide catalyst capable of exhibiting high activity and selectivity, and the method for producing the same. It is related with the catalyst obtained by this.

  A method for obtaining an oxirane compound from a hydroperoxide and an olefin type compound in the presence of a catalyst is known. Examples of the catalyst used here include a titanium-containing silicide catalyst, and attempts have been made to improve hydrophobicity in order to obtain a high-performance catalyst.

  For example, Patent Documents 1 and 2 and Non-Patent Documents 1 to 4 disclose specific titanium-containing silicon oxide catalysts having improved hydrophobicity by using, as a catalyst raw material, a silicon compound in which a hydrocarbon group is directly bonded to a silicon atom. Has been. However, these catalysts are hardly satisfactory from the viewpoint of developing higher activity and selectivity.

JP-A-10-72212 Japanese Patent Laid-Open No. 2002-320860 Chem. Commun., (1998) 1899 Chem. Lett., (2001) 648 Stud.Surf.Sci.Catal., 141 (2002) 189 J. Mater. Chem., 12 (2002) 3078

  The problems to be solved by the present invention under such circumstances are, for example, a method for producing a titanium-containing silicon oxide catalyst that can be used in a reaction for obtaining olefin oxide from hydroperoxide and olefin, and that can exhibit high activity and selectivity. It is in the point which provides the catalyst obtained by this manufacturing method.

That is, the first invention of the present invention is a method for producing a titanium-containing silicon oxide catalyst that satisfies all the following conditions (1) to (4), and includes the following first to second steps. It is related to the manufacturing method including.
(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): Part or all of the silica source used as a raw material is a silicon compound in which a hydrocarbon group is directly bonded to a silicon atom. First step: Silica source, titanium source and mold (template) Is a step of obtaining a solid containing a catalyst component and a mold agent by mixing and stirring in a solvent, wherein the proportion of water in the solvent is 50% by weight or less. Second step: obtained in the first step Removing mold from solid

  Moreover, 2nd invention among this invention concerns on the titanium containing silicon oxide catalyst obtained by said manufacturing method.

  Furthermore, the third invention of the present invention is a method for producing an oxirane compound characterized by reacting an olefin type compound and hydroperoxide in the presence of a titanium-containing silicon oxide catalyst obtained by the above production method. It is concerned.

  INDUSTRIAL APPLICABILITY According to the present invention, for example, a method for producing a titanium-containing silicon oxide catalyst that can be used in a reaction for obtaining an oxirane compound from a hydroperoxide and an olefin type compound and can exhibit high activity and selectivity, and a catalyst obtained by the production method Can be provided.

  The catalyst of the present invention is a catalyst comprising a titanium-containing silicon oxide that satisfies all the following conditions (1) to (4).

  The condition (1) is that the average pore diameter is 10 mm or more.

  Condition (2) is that 90% or more of the total pore volume has a pore diameter of 5 to 200 mm.

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 catalyst.

  Condition (4) is that a part or all of the silica source used as a raw material is a silicon compound in which a hydrocarbon group is directly bonded to a silicon atom.

  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.

  The catalyst of the present invention may or may not have a peak indicating an interplanar distance d 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.

From the viewpoint of high activity, 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.

The catalyst of the present invention is 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 mold agent (template) in a solvent, and the proportion of water in the solvent is 50 Step that is not more than% by weight Second step: Step of removing the mold from the solid obtained in the first step

  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 mold agent (template) in a solvent, and the proportion of water in the solvent is This is a step of 50% by weight or less. When the reagent to be used is a solid, it may be used as a solution dissolved or dispersed in a solvent.

  In the present invention, a silicon compound in which a hydrocarbon group is directly bonded to a silicon atom is used for a part or all of a silica source used as a raw material, and a monoalkyltrialkoxysilane, a dialkyldialkoxysilane, a trialkylmonoalkoxysilane, bis ( Trialkoxysilyl) alkane, monoaryltrialkoxysilane, diallyldialkoxysilane, bis (trialkoxysilyl) aryl and the like. They can be used alone or in a mixture of several kinds. Of these, monoalkyltrialkoxysilane and / or monoaryltrialkoxysilane are preferably used. For example, as alkyl group or aryl group, methyl, ethyl, propyl, butyl, vinyl, propenyl, cyclopentenyl, cyclohexenyl, phenyl, tolyl C 1-16 hydrocarbon groups such as xylyl, naphthyl and the like. The above alkyl group and aryl group may have a substituent containing N, O, P, halogen or the like. Examples of the alkoxy group include C1-C6 hydrocarbon groups such as methoxy, ethoxy, propoxy and butoxy.

  In order to strengthen the silica skeleton in the catalyst, it is preferable to use amorphous silica or alkoxysilane, such as tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, etc. as the silica source together with the above silica source. Mix with source.

  Titanium alkoxides such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra-2-ethylhexyl titanate, tetra titanate Octadecyl, titanium (IV) oxyacetylacetonate, titanium (IV) di-propoxy bisacetylacetonate, etc., or titanium halides such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, etc. can give.

As the type agent, cationic surfactants such as alkylammonium, dialkylammonium, trialkylammonium and benzylammonium, anionic surfactants such as alkylsulfate ions and alkylphosphate ions, polyalkylene oxides and their block copolymers, alkylamines, etc. Any of the above nonionic surfactants can be applied. Among these, quaternary ammonium ions represented by the following general formula (I) are preferably 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, and hexadecylpyridinium.

  Moreover, the quaternary ammonium ion represented by these general formula (I) can also be used independently, and several types may be mixed and used for it.

  Examples of solvents for dissolving the mold include water and alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, sec-butanol, t-butanol, vinyl alcohol, allyl alcohol, cyclohexanol, benzyl Examples thereof include alcohols, diols, and mixtures thereof.

  In the present invention, it is important that the ratio of water in the solvent in which the mold is dissolved is 50% by weight or less, preferably 5 to 40% by weight, and preferably 10 to 30% by weight. Further preferred. Thereby, the object of the present invention of obtaining a catalyst capable of realizing high activity and high selectivity can be achieved.

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.

  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 a quaternary ammonium hydroxide, and examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, etc., and the quaternary represented by the general formula (I) It is more preferable to use ammonium ion hydroxide. 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.

  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.

  The second step of the present invention is a step of removing the mold from the solid.

  The removal of the mold can be achieved by subjecting the solid containing the catalyst component and the mold obtained in the first step to a solvent extraction operation or a calcination operation, and extraction removal is particularly preferable.

  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 Examples thereof include hydrocarbon esters such as butyl and butyl propionate, and alcohols are preferable from the viewpoint of the solubility of the mold, and methanol is more preferable. The weight ratio of these extraction solvents to the solid containing the catalyst component and the mold is usually 1 to 1000, preferably 5 to 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 5 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 component may be eluted and the catalytic activity may be lowered.

  After thoroughly mixing the solvent, the solid containing the catalyst component and the mold, 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 the mold by a method of filling a solid containing the catalyst component and the mold into a reaction tube and circulating an extraction solvent. The completion of the solvent extraction 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. When the boiling point of the extraction solvent is low, the extraction may be performed by applying pressure.

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

  The extraction solvent contained in the solid after the extraction operation can be removed by a drying operation, and when subsequent silylation is performed, it is replaced with a solvent that is substantially inert to the silylating agent used in the silylation step. be able to.

  In the case of drying and removing, examples of the drying device include a conical dryer and a shelf dryer equipped with hot air or a decompression device.

  In the case of displacement removal, the extraction solvent contained in the solid is replaced with a solvent that is substantially inert to the silylating agent used in the subsequent silylation step. The substitution solvent used in the substitution step is not particularly limited as long as it is substantially inert to the silylating agent and satisfies the condition that the extraction solvent used in the second step can be dissolved.

  Solvents preferably used for the substitution operation are generally hydrocarbons, halogenated hydrocarbons, ketones, ethers, esters, N, N-disubstituted amides, nitriles having a carbon number of 1 to about 12 at room temperature. Such as hexane, cyclohexane, chloroform, benzene, toluene, xylene, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisobutyl ether, tetrahydrofuran, dioxane, methyl acetate, ethyl acetate, Examples include dimethylformamide, acetonitrile, pyridine, triethylamine, dimethyl sulfoxide and the like. In view of the subsequent silylation step, preferred substitution solvents are hydrocarbons, and among these, toluene is more preferred. These solvents can be used alone, or a mixed solution of several kinds can be used.

  In the substitution operation, the substitution solvent and the solid containing the extraction solvent obtained in the second step are sufficiently mixed, and then the liquid phase part is separated by a method such as filtration or decantation. This operation is repeated as many times as necessary. Moreover, it is also possible to replace by a method in which a solid containing an extraction solvent is filled in a reaction tube or the like and a replacement solvent is circulated. From the viewpoint of catalyst productivity, it is preferable to carry out the second step to the silylation step of the present invention in the same reactor. The completion of this replacement operation can be known by, for example, analyzing the liquid phase part. The substitution temperature is preferably 0 to 200 ° C, more preferably 20 to 100 ° C. When the boiling point of the solvent used in this operation is low, substitution may be performed by applying pressure.

  The substitution solvent used in the substitution step can be reused after removing the extraction solvent by a usual method such as distillation or extraction.

  The solid obtained through the first step and the second step of the present invention has high hydrophobicity and acts as a highly active and highly selective catalyst. However, in order to further improve the performance, the solid is subjected to silylation treatment. By attaching, a silylated catalyst can be obtained.

  Silylation may be performed by a gas phase method in which a gaseous silylating agent is reacted with the solid obtained in the second step, or by a liquid phase method in which a silylating agent and a solid are reacted in a solvent. In the present invention, the liquid phase method is more preferable. Usually, when silylation is performed by a liquid phase method, hydrocarbons are preferably used. When the extraction solvent is removed by a substitution operation, the silylation solvent is not necessarily the same as the substitution solvent, but is preferably the same from the viewpoint of reuse of the solvent.

  Examples of silylating agents include organic silanes, organic silylamines, organic silylamides and derivatives thereof, and organic silazanes and other silylating agents.

  Examples of organic silanes include chlorotrimethylsilane, dichlorodimethylsilane, chlorobromodimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, iododimethylbutylsilane, chlorodimethylphenylsilane, chlorodimethylsilane, dimethyl n-propylchlorosilane, dimethylisopropyl Chlorosilane, t-butyldimethylchlorosilane, tripropylchlorosilane, dimethyloctylchlorosilane, tributylchlorosilane, trihexylchlorosilane, dimethylethylchlorosilane, dimethyloctadecylchlorosilane, n-butyldimethylchlorosilane, bromomethyldimethylchlorosilane, chloromethyldimethylchlorosilane, 3-chloro Propyldimethylchlorosilane, dimethoxymethylchlorosilane, methylphenol Examples include nylchlorosilane, triethoxychlorosilane, dimethylphenylchlorosilane, methylphenylvinylchlorosilane, benzyldimethylchlorosilane, diphenylchlorosilane, diphenylmethylchlorosilane, diphenylvinylchlorosilane, tribenzylchlorosilane, and 3-cyanopropyldimethylchlorosilane.

  Examples of organic silylamines include N-trimethylsilylimidazole, Nt-butyldimethylsilylimidazole, N-dimethylethylsilylimidazole, N-dimethyln-propylsilylimidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilylamine, N -Trimethylsilyldimethylamine, N-trimethylsilyldiethylamine, N-trimethylsilylpyrrole, N-trimethylsilylpyrrolidine, N-trimethylsilylpiperidine, 1-cyanoethyl (diethylamino) dimethylsilane, pentafluorophenyldimethylsilylamine.

  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.

  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.

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.

  The catalyst of the present invention is usually used as a catalyst molded body by a step of molding a solid containing a catalyst component. The molding process may be carried out at any stage before or after the above-mentioned mold removing process, after the solvent replacement process, or after the silylation process, but the viewpoint of suppressing deterioration of catalyst physical properties such as specific surface area and pore volume. Therefore, it is preferably performed before the mold removing step. As the molding method, any method such as compression molding or extrusion molding may be used. In extrusion molding, commonly used organic and inorganic binders can be used, but the addition of the binder may cause a decrease in catalytic activity. In producing the catalyst molded body, the compression molding method is most preferable from the viewpoint of catalyst strength and catalyst physical properties.

Examples of the compression molding method include roll press molding (briquetting and compacting), hydraulic press molding, tableting molding and the like. The compression pressure is usually 0.1 to 10 ton / cm ² , preferably 0.2 to 5 ton / cm ² , more preferably 0.5 to 2 ton / cm ² . If the pressure is too low, the strength of the molded body may be insufficient. On the other hand, if the pressure is too high, the pores may be destroyed and the physical properties of the catalyst may be insufficient. In performing compression molding, it is preferable that the solid containing the catalyst component contains an appropriate amount of moisture, so that a molded body having sufficient strength can be produced even at a low compression pressure. The water content of the material subjected to compression molding is preferably 1 to 70% by weight, more preferably 5 to 40% by weight. The amount of moisture may be adjusted by the degree of drying when the damp solid is dried, or may be adjusted by adding water to the sufficiently dried solid. In addition, a generally used binder or the like may be added as long as desired performance is not hindered.

  The shape of the molded body may be any shape such as a tablet, a sphere, or a ring. It may be used in the reaction as it is, or may be crushed to an appropriate size.

  Since the catalyst of the present invention has a high surface area, highly dispersed titanium active sites and high hydrophobicity, it can be used for various oxidation reactions of organic compounds in addition to selective oxidation reactions such as olefin epoxidation reactions. It is. 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.

  In particular, the catalyst of the present invention can be optimally used in a method for producing an oxirane compound in which an olefin type compound and a hydroperoxide are reacted.

  The olefinic compound may be an acyclic, monocyclic, bicyclic or polycyclic compound, and may be of monoolefin type, diolefin type or polyolefin type. If there are two or more olefinic bonds, this may be a conjugated bond or a non-conjugated bond. Olefin type compounds having 2 to 60 carbon atoms are generally preferred. Although it may have a substituent, the substituent is preferably a relatively stable group. Examples of such hydrocarbons include ethylene, propylene, butene-1, isobutylene, hexene-1, hexene-2, hexene-3, octene-1, decene-1, styrene, cyclohexene and the like. Examples of suitable diolefin type compounds are butadiene and isoprene. Substituents may be present, examples include halogen atoms, and various substituents containing oxygen, sulfur, and nitrogen atoms together with hydrogen and / or carbon atoms may also be present. Particularly preferred olefin type compounds are olefin type unsaturated alcohols and olefin type unsaturated hydrocarbons substituted with halogen. Examples thereof include allyl alcohol, crotyl alcohol and allyl chloride. Particularly preferred are alkenes having 3 to 40 carbon atoms, which may be substituted with hydroxyl groups or halogen atoms.

An organic hydroperoxide can be mention | raise | lifted as an example of a hydroperoxide. Organic hydroperoxides have the general formula R—O—O—H
(Where R is a monovalent hydrocarbyl 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 this is a hydrocarbyl 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.

  The epoxidation reaction can be carried out in the liquid phase using a solvent and / or 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 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. The liquid mixture can then be purified by a suitable method. Purification includes fractional distillation, selective extraction, filtration, washing and the like. The solvent, catalyst, unreacted olefin type compound and unreacted hydroperoxide can be recycled and reused.

  The reaction using the catalyst of the present invention can be carried out in the form of a slurry or a fixed bed. In the case of a large-scale industrial operation, it is preferable to use a fixed bed. This reaction can be carried out by a batch method, a semi-continuous method or a continuous method. When the liquid containing the reactants is passed through a fixed bed, the liquid mixture exiting the reaction zone contains no or substantially no catalyst.

The following examples illustrate the invention.
Example 1
Preparation of catalyst powder 125.0 g of a template solution composed of 16% by weight hexadecyltrimethylammonium hydroxide, 64% by weight methanol and 20% by weight water was stirred, and 1.85 g of tetraisopropyl titanate at 50 ° C. A mixed solution of 10.0 g of 2-propanol was added dropwise. After stirring for 30 minutes, a mixed solution of 30.5 g of tetramethylorthosilicate and 6.8 g of methyltrimethoxysilane was added dropwise. Thereafter, stirring was continued at 50 ° C. for 3 hours. The resulting precipitate was filtered off.
The obtained precipitate was dried at 70 ° C. under reduced pressure for 8 hours.

Production of molded body A mixture of 30.0 g of a white solid obtained by drying and well mixed with 4.5 g of water by spraying was compression molded with a tablet molding machine. The obtained solid was crushed, and a 1.0 to 2.0 mm catalyst molded body was obtained using a sieve. Solids of 1.0 mm or less were recycled and compression molded again.

Extracting and removing the mold agents Next, the molded body 11.5g obtained as described above was packed into a glass column having an inner diameter diameter of 16 mm, LHSV = at 6h ^-1 (1) at room temperature, 100 ml of methanol, (2) 45 Under heating at 0 ° C., a mixed solution of 200 ml of methanol and 4 g of concentrated hydrochloric acid (content 36% by weight), (3) Under heating at 45 ° C., 200 ml of methanol was sequentially passed through the column in an up flow. After completion of the flow, methanol in the column was extracted from the lower part of the column, and the catalyst molded body was dried under reduced pressure at 10 mmHg for 1.5 hours under heating at 80 ° C.

Synthesis of Propylene Oxide (PO) The molded catalyst obtained as described above was evaluated in a batch reactor (autoclave) using 25% cumene hydroperoxide (CHPO) and propylene (C ₃ '). 1.0 g of catalyst, 30.0 g of CHPO, and 16.6 g of C ₃ ′ were charged into an autoclave and reacted at a reaction temperature of 85 ° C. and a reaction time of 1.5 hours (temperature increase) under autogenous pressure. The reaction results are shown in Table 1.

Example 2
3.0 g of the molded catalyst obtained in silylation Example 1 was placed in a glass flask equipped with a cooling tube, 2.0 g of hexamethyldisilazane and 30.0 g of toluene were added, and heated at 110 ° C. for 1.5. Time silylation was performed. After the liquid separation, the molded catalyst was dried under reduced pressure at 10 mmHg for 1.5 hours under heating at 110 ° C.
The obtained silylation catalyst was evaluated by a batch reactor in the same manner as in Example 1. The reaction results are shown in Table 1.

Comparative Example 1
A batch reaction apparatus was prepared by preparing a catalyst molding in the same manner as in Example 1 except that 125.0 g of a mold solution composed of 16% by weight hexadecyltrimethylammonium hydroxide, 11% by weight methanol, and 73% by weight water was used. It was evaluated with. The reaction results are shown in Table 1.

Comparative Example 2
The molded catalyst obtained in Comparative Example 1 was silylated in the same manner as in Example 2 and evaluated with a batch reactor. The reaction results are shown in Table 1.

＊１：ＰＯ/Ｃ_３’選択率＝生成ＰＯモル/反応Ｃ_３’モル＊１００

* 1: PO / C ₃ 'selectivity = product PO mol / reaction C ₃ ' mol * 100

Claims (5)

A method for producing a titanium-containing silicon oxide catalyst that satisfies all of the following conditions (1) to (4), comprising the following first step to second step.
(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): Part or all of the silica source used as a raw material is a silicon compound in which a hydrocarbon group is directly bonded to a silicon atom. First step: Silica source, titanium source and mold (template) Is a step of obtaining a solid containing a catalyst component and a mold agent by mixing and stirring in a solvent, wherein the ratio of water in the solvent is 10 to 30% by weight . Second step: In the first step The step of removing the mold from the obtained solid The production method according to claim 1, wherein the mold used in the first step is a quaternary ammonium ion represented by the following general formula (I).
[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.) The manufacturing method according to claim 1, wherein a part of the silica source used in the first step is monoalkyltrialkoxysilane and / or monoaryltrialkoxysilane. The manufacturing method according to claim 1, wherein the mold removing method used in the second step is a solvent extraction operation. In addition to the process of Claim 1, it has the process of obtaining the silylated catalyst by attaching | subjecting a silylation process to the solid after mold removal, The manufacture of Claim 1 of Claim 1-4 Method.