Manufacturing methods for titanium-containing silicon oxide molded objects, and titanium-containing silicon oxide molded objects.

Abstract

DEPCT64 What is provided is (i) a method for manufacturing silicon oxide molded parts consisting of Titanium with high acceleration activity and high strength and (ii) silicon oxide forming pieces Composed of titanium with high acceleration activity and high strength, a method for manufacturing parts. The process of forming titanium-containing silicon oxide includes: raw material mixing and material blending steps. Creating the template, silicon source, and solvent; the molding process of obtaining the molded part; and... The process of removing molding material from a molded part; the steps involved. Forming is performed under conditions of 40°C to 100°C, where titanium is inducted into a solid. The parts are molded in and / or after any step in the raw material mixing, molding, and other processes. The process of removing template-forming materials. -----------------------------------------------------------

Description

Method for producing titanium-containing silicon oxide molded body, and titanium-containing silicon oxide molded body

[0001] The present invention relates to a method for producing a titanium-containing silicon oxide molded body, and to a titanium-containing silicon oxide molded body.

[0002] Titanium-containing silicon oxides are known as catalysts for the reaction of olefins with hydroperoxides to obtain epoxides. An example of the production of such catalysts is described in, for example, Patent Document 1.

[0003] Japanese Patent Publication No. 2006-159057

[0004] In recent years, there has been a demand for titanium-containing silicon oxides with higher strength.

[0005] The problem to be solved by the present invention is to provide a method for producing a titanium-containing silicon oxide molded body having high catalytic activity and high strength, and to provide a titanium-containing silicon oxide molded body.

[0006] The present invention provides the following [A] and [B].

[0007] [A] A method for producing a titanium-containing silicon oxide molded body, comprising the following steps: a raw material mixing step: a step of mixing a mold agent, a silicon source, and a solvent to obtain a solid containing the mold agent and silicon oxide; a molding step: a step of molding the solid obtained through the raw material mixing step to obtain a molded body; and a mold removing step: a step of removing the mold agent from the molded body obtained through the molding step to obtain a mold-removed molded body, wherein the molding step comprises molding the solid obtained through the raw material mixing step under conditions where the temperature of the solid is 40 to 100°C, and wherein titanium is introduced into the solid or the molded body during any of the steps and / or after completion of any of the steps.

[0008] [B] A method for producing a titanium-containing silicon oxide molded body, comprising the following steps: a raw material mixing step: a step of mixing a mold agent, a silicon source, and a solvent to obtain a solid containing the mold agent and silicon oxide; a molding step: a step of molding the solid obtained through the raw material mixing step to obtain a molded body; and a mold removing step: a step of removing the mold agent from the molded body obtained through the molding step to obtain a mold-removed molded body, wherein the molding step comprises molding the solid obtained through the raw material mixing step under conditions where the temperature of the solid is 40 to 100°C, and titanium is introduced into the solid or molded body during any of the steps and / or after completion of any of the steps.

[0009] According to one aspect of the present invention, there are provided a method for producing a titanium-containing silicon oxide molded body having high catalytic activity and high strength, and a titanium-containing silicon oxide molded body.

[0010] A method for producing a titanium-containing silicon oxide molded body according to one embodiment of the present invention includes a raw material mixing step, a molding step, and a mold removing step, and may further include a silylation step after the mold removing step.

[0011] In one embodiment of the present invention, the method for producing a titanium-containing silicon oxide molded body simply involves introducing titanium into the solid or molded body during any one of the raw material mixing step, molding step, mold agent removal step, or silylation step. Alternatively, titanium may be introduced into the solid or molded body between the raw material mixing step and the molding step, between the molding step and the mold agent removal step, between the mold agent removal step and the silylation step, or after the silylation step. In other words, titanium may be introduced into the solid or molded body during, between, or after any one of the raw material mixing step, molding step, mold agent removal step, or silylation step.

[0012] As used herein, "introducing titanium into a solid or a molded body" means mixing a solid containing silicon oxide or a molded body molded from the solid with a titanium source, thereby introducing a group represented by --Si--O--Ti into the silicon oxide contained in the solid or a molded body molded from the solid. The solid is a solid containing a mold agent and silicon oxide, and the molded body may be a molded body molded from the solid, a molded body from which the mold agent has been removed, or a titanium-containing silicon oxide molded body.

[0013] The introduction of titanium is preferably carried out before the start of the template removal step, and more preferably during the raw material mixing step. When titanium is introduced during the raw material mixing step, the raw material mixing step is a step of mixing a silicon source, a titanium source, and a template.

[0014] Another embodiment of titanium introduction is a method in which, after the mold removal step is completed, the molded body obtained through the mold removal step is mixed with a titanium source to introduce titanium into the molded body.

[0015] The introduction of titanium may be carried out by mixing a solid or molded body into which titanium is to be introduced with a titanium source in a liquid phase, or by contacting a solid or molded body into which titanium is to be introduced with a titanium source in a gas phase.

[0016] Titanium sources include titanium alkoxides, chelate-type titanium complexes, titanium halides, and titanium-containing sulfates. Examples of titanium alkoxides include tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra(2-ethylhexyl) titanate, and tetraoctadecyl titanate. Examples of chelate-type titanium complexes include titanium(IV) oxyacetylacetonate and titanium(IV) diisopropoxybisacetylacetonate. Examples of titanium halides include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide. Examples of titanium-containing sulfates include titanyl sulfate.

[0017] The raw material mixing step according to one embodiment of the present invention is a step of mixing a template, a silicon source, and a solvent to obtain a solid containing the template and silicon oxide.

[0018] The "silicon source" used in the raw material mixing step refers to silicon oxide and silicon oxide precursor. Examples of silicon oxides serving as silicon sources include amorphous silica. Examples of silicon oxide precursors serving as silicon sources include alkoxysilanes, alkyltrialkoxysilanes, dialkyldialkoxysilanes, and 1,2-bis(trialkoxysilyl)alkanes. Examples of alkoxysilanes include tetramethyl orthosilicate, tetraethyl orthosilicate, and tetrapropyl orthosilicate. Examples of alkyltrialkoxysilanes include trimethoxy(methyl)silane. Examples of dialkyldialkoxysilanes include dimethoxydimethylsilane. A single silicon source may be used, or several silicon sources may be used in combination.

[0019] When a silicon oxide precursor is used as the silicon source in the raw material mixing step, water is used as part or all of the solvent in the step, and when the silicon oxide precursor is mixed with water, the silicon oxide precursor is converted partly or entirely into silicon oxide.

[0020] The "mold" used in the raw material mixing step refers to a substance that forms a pore structure in the titanium-containing silicon oxide molded body.

[0021] The template used in the raw material mixing step is preferably a surfactant or piperidine in which at least one hydrogen atom may be substituted with a hydrocarbon group having 1 to 10 carbon atoms.

[0022] Surfactants include cationic surfactants, anionic surfactants, and nonionic surfactants. Cationic surfactants include quaternary ammonium compounds containing quaternary ammonium ions and alkylamine salts. Quaternary ammonium compounds containing quaternary ammonium ions include tetraalkylammonium hydrochloride, tetraalkylammonium acetate, and tetraalkylammonium hydroxide. Alkylamine salts include monoalkylamine hydrochloride, monoalkylamine acetate, dialkylamine hydrochloride, dialkylamine acetate, trialkylamine hydrochloride, and trialkylamine acetate. Anionic surfactants include alkylbenzene sulfonates and their salts, sodium α-olefin sulfonates, alkyl sulfates, alkyl ether sulfates, methyl taurates, alaninates and their salts, ether carboxylic acids and their salts, sulfosuccinates, sulfated oils, polyoxyalkylene ether sulfates, and soaps. Nonionic surfactants include polyalkylene oxides or polyalkylene oxide block copolymers, and alkylamines.

[0023] Among surfactants, cationic surfactants and nonionic surfactants are preferred. The cationic surfactant is preferably a quaternary ammonium compound containing a quaternary ammonium ion represented by the following formula (I). The nonionic surfactant is preferably an amine represented by the following formula (II).

[0024] [NR １ R ２ R ３ R ４ ] ＋ (I) (wherein R １ represents a hydrocarbon group having 2 to 36 carbon atoms, and R ２ ~R ４ each independently represents a hydrocarbon group having 1 to 6 carbon atoms. ５ R ６ R ７ (II) (In formula (II), R ５ represents a hydrocarbon group having 2 to 36 carbon atoms, and R ６ and R７ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. １ is a hydrocarbon group having 2 to 36 carbon atoms, preferably a hydrocarbon group having 6 to 36 carbon atoms, and more preferably a hydrocarbon group having 10 to 22 carbon atoms. ２ ~R ４ are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R ２ ~R ４ It is preferred that all of the groups are methyl groups.

[0025] Specific examples of the quaternary ammonium ion represented by formula (I) include cations such as decyltrimethylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, eicosyltrimethylammonium, behenyltrimethylammonium, benzyltrimethylammonium, and dimethyldidodecylammonium.

[0026] Specific examples of quaternary ammonium compounds containing the quaternary ammonium ion represented by formula (I) include decyltrimethylammonium hydroxide, decyltrimethylammonium chloride, decyltrimethylammonium bromide, dodecyltrimethylammonium hydroxide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium hydroxide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium hydroxide, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, eicosyltrimethylammonium hydroxide, eicosyltrimethylammonium chloride, eicosyltrimethylammonium bromide, behenyltrimethylammonium hydroxide, behenyltrimethylammonium chloride, and behenyltrimethylammonium bromide, as well as dimethyldialkylammonium salts and methyltrialkylammonium salts in which at least one methyl group in a salt containing these quaternary ammonium ions is substituted with an alkyl group having 2 to 22 carbon atoms.

[0027] In formula (II), R ５ is a hydrocarbon group having 2 to 36 carbon atoms, preferably a hydrocarbon group having 6 to 36 carbon atoms, and more preferably a hydrocarbon group having 10 to 22 carbon atoms. ６ and R ７ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R ６ and R ７ is preferably a hydrogen atom.

[0028] Specific examples of the amine represented by formula (II) include octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, and behenylamine, as well as methylalkylamines and dimethylalkylamines in which at least one hydrogen atom in these amines has been substituted with a methyl group.

[0029] Examples of piperidines in which at least one hydrogen atom may be substituted with a hydrocarbon group having 1 to 10 carbon atoms include piperidine, 1-methylpiperidine, 2-methylpiperidine, 2,6-dimethylpiperidine, and 2,2,6,6-tetramethylpiperidine.

[0030] The above-mentioned template may be used alone or in combination of several kinds.

[0031] The mixture of the template and the silicon source is carried out in the presence of a solvent. Examples of the solvent include water and alcohol. Examples of the alcohol include methanol, ethanol, 1-propanol, and 2-propanol.

[0032] A solid containing a template and silicon oxide is obtained through this raw material mixing step. The solid containing a template and silicon oxide obtained through this raw material mixing step is separated from the solvent used in the raw material mixing step by filtration or the like. This raw material mixing step is preferably carried out at a temperature range of 20 to 200°C for 2 to 1000 hours. Stirring can also be carried out during mixing.

[0033] Furthermore, commonly used binders and the like may be added within the range that does not impair the desired performance.

[0034] The molding step according to one aspect of the present invention is a step of molding a solid containing a mold agent and a silicon oxide to obtain a molded body. The molding step is a process from introducing a solid containing a mold agent and a silicon oxide into an apparatus for pressurizing and molding the solid to obtain a pressurized molded body. In the molding step, as long as the solid is heated when the solid is pressurized and molded, there is no limitation on whether the molding apparatus for molding the solid is equipped with a heating means for adjusting the temperature of the solid. As an example, the molding step may be performed by heating the solid to a temperature within a range of 40 to 100°C using a preheater, and then introducing the solid into a molding apparatus without a heating means while maintaining the temperature within that range.

[0035] The molding method may be any of compression methods such as roll press molding (briquetting, compacting), hydraulic press molding, and tablet molding, or extrusion molding. Commonly used organic and inorganic binders can be used in extrusion molding. From the viewpoint of catalyst strength and catalyst properties, the molding method in the molding step is preferably a compression method.

[0036] When compression molding, it is preferable that the solid containing the mold agent contains an appropriate amount of moisture. By performing compression molding on a solid containing the mold agent in a state where it contains an appropriate amount of moisture, a molded body with sufficient strength can be produced. The moisture content of the solid to be subjected to compression molding is preferably 1 to 70% by weight, more preferably 3 to 40% by weight. The moisture content may be adjusted by the drying conditions when drying a wet solid, or by adding water to a solid that has been thoroughly dried.

[0037] When roll press molding is used as an embodiment, the pressure applied during compression molding is usually 0.1 to 10 ton / cm, preferably 0.5 to 8 ton / cm, and more preferably 1 to 6 ton / cm. When hydraulic press molding or tablet molding is used as an embodiment, the pressure applied during compression molding is usually 0.1 to 10 ton / cm. ２ and preferably 0.2 to 5 ton / cm ２ and more preferably 0.5 to 2 ton / cm ２ is.

[0038] The shape of the molded product obtained by press molding or tableting may be any shape such as a tablet, a sphere, a ring, etc. It may be used for reactions in its original shape, or may be crushed into pieces of an appropriate size before use.

[0039] In the molding step, the solid containing the mold agent and silicon oxide is preferably molded under conditions where the temperature of the solid during molding is 40 to 100°C, and more preferably 40 to 70°C. The temperature of the solid during molding refers to the temperature of the solid immediately before, immediately after, or during molding. The solid temperature is confirmed by directly measuring the temperature of the solid immediately before, immediately after, or during molding using a contact thermometer, radiation thermometer, or the like. Within the range of 40 to 100°C, the heating temperature in the molding step tends to be lower, the more likely it is that a titanium-containing silicon compound molded product with higher catalytic activity will be obtained, and higher temperatures tend to be higher, the more likely it is that a titanium-containing silicon compound molded product with a lower powdering rate will be obtained.

[0040] By keeping the temperature of the solid during molding within the above range, a molded body containing a template with a powdering rate of 3% or less can be produced, and by removing the template in a subsequent step, a titanium-containing silicon oxide molded body with high catalytic activity and high strength can be produced, as will be described later. The method for evaluating the powdering rate of a molded body containing a template is explained in detail in the Examples section of this specification.

[0041] The temperature of the solid during molding can be controlled, for example, by preheating the solid to be molded before molding, by molding the solid in a heated molding section, or by both methods. Specifically, when roll press molding is employed, examples include a method of heating the solid in a raw material supply hopper and a method of heating the roll itself to a predetermined temperature. When hydraulic press or tablet molding is employed, examples include a method of heating a mold to a predetermined temperature and a method of preheating the solid to be introduced into the mold.

[0042] The mold-agent removing step according to one embodiment of the present invention is a step of removing the mold agent from the molded body obtained through the molding step to obtain a mold-agent-free molded body. By performing the mold-agent removing step, a molded body that does not contain a mold agent or that is substantially free of a mold agent can be obtained.

[0043] The mold agent can be removed by firing the molded body containing the mold agent in air at 300 to 800° C. or by extraction with a solvent, but it is preferable to remove the mold agent by extraction with a solvent.

[0044] A technique for extracting a template using a solvent has been reported by Whitehurst et al. (see U.S. Patent No. 5,143,879). The solvent used for extraction may be any solvent capable of dissolving the compound used as the template. Generally, a compound having 1 to 12 carbon atoms that is liquid at room temperature, or a mixture of two or more such compounds, can be used. Suitable solvents include alcohols, ketones, and acyclic and cyclic ethers and esters. Examples of alcohols include methanol, ethanol, ethylene glycol, propylene glycol, 1-propanol, 2-propanol, 1-butanol, and octanol. Examples of ketones include acetone, diethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of ethers include diisobutyl ether and tetrahydrofuran. Examples of esters include methyl acetate, ethyl acetate, butyl acetate, and butyl propionate.

[0045] The solvent used to remove the template is preferably one that can dissolve the template used, from the viewpoint of its dissolving ability. For example, when the template is a salt containing a quaternary ammonium ion, alcohol is preferred, with methanol being more preferred. The mass ratio of these extraction solvents to the molded body is typically 1 to 1,000, preferably 5 to 300. To improve the extraction effect, an acid or a salt thereof may be added to these solvents. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrobromic acid, and organic acids such as formic acid, acetic acid, and propionic acid. Examples of their salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. The concentration of the added acid or its salt in the solvent is preferably 30% by mass or less, more preferably 15% by mass or less.

[0046] The template can be removed by thoroughly mixing the solvent and the molded body and then separating the liquid phase by filtration, decantation, or other methods. This procedure may be repeated multiple times. Alternatively, the template can be extracted by filling the molded body into a container such as a column and passing an extraction solvent through it. The extraction temperature is preferably 0 to 200°C, more preferably 20 to 100°C. If the boiling point of the extraction solvent is low, the extraction may be performed under pressure.

[0047] The template in the solution obtained by the extraction treatment can be recovered and reused as a template in the raw material mixing step. Similarly, the extraction solvent can be purified by ordinary distillation or the like and reused.

[0048] The silylation step according to one embodiment of the present invention is a step of contacting the molded body obtained through the mold-removing step with a silylating agent to obtain a titanium-containing silicon oxide molded body. By carrying out the silylation step, the molded body obtained through the mold-removing step is silylated.

[0049] The silylation may be carried out by a gas phase method in which a gaseous silylating agent is brought into contact with the molded body obtained through the mold removal step to cause a reaction, or by a liquid phase method in which a silylating agent is brought into contact with the molded body in a solvent to cause a reaction. In one embodiment of the present invention, the liquid phase method is more preferred. Usually, when silylation is carried out by a liquid phase method, a hydrocarbon is preferably used as a solvent in the silylation step. When silylation is carried out by a liquid phase method, drying may be carried out thereafter.

[0050] In this specification, a silylating agent is a silicon compound that is reactive with molded bodies, and has a hydrolyzable group bonded to silicon, and at least one group selected from the group consisting of alkyl groups, allyl groups such as vinyl groups, aryl groups such as phenyl groups, halogenated alkyl groups, and siloxy groups is bonded to the silicon. Examples of the hydrolyzable group bonded to silicon include hydrogen, halogen, an alkoxy group, an acetoxy group, and an amino group. It is preferable that the silylating agent have one hydrolyzable group bonded to silicon.

[0051] Examples of silylating agents include organosilanes, organosilylamines, organosilylamides and their derivatives, and organosilazanes.

[0052] Examples of organic silanes include chlorotrimethylsilane, dichlorodimethylsilane, chlorobromodimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, iododimethylbutylsilane, chlorodimethylphenylsilane, chlorodimethylsilane, dimethyl n-propylchlorosilane, dimethylisopropylchlorosilane, tert-butyldimethylchlorosilane, tripropylchlorosilane, dimethyloctylchlorosilane, tributylchlorosilane, trihexylchlorosilane, dimethylethylchlorosilane, dimethyloctadecylchlorosilane, n-butyldimethylchlorosilane, bromomethyldimethylchlorosilane, chloromethyldimethylchlorosilane, 3-chloropropyldimethylchlorosilane, dimethoxymethylchlorosilane, methylphenylchlorosilane, methylphenylvinylchlorosilane, benzyldimethylchlorosilane, and diphenylchlorosilane. silane, diphenylmethylchlorosilane, diphenylvinylchlorosilane, tribenzylchlorosilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, ethoxytrimethylsilane, diethoxydimethylsilane, triethoxymethylsilane, trimethoxyethylsilane, dimethoxydiethylsilane, methoxytriethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, methoxytriphenylsilane, dimethoxydiphenylsilane, trimethoxyphenylsilane, ethoxytriphenylsilane, diethoxydiphenylsilane, triethoxyphenylsilane, dichlorotetramethyldisiloxane, 3-cyanopropyldimethylchlorosilane, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane, and 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane.

[0053] Examples of organic silylamines include N-trimethylsilylimidazole, N-tert-butyldimethylsilylimidazole, N-dimethylethylsilylimidazole, N-dimethyl-n-propylsilylimidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilyldimethylamine, N-trimethylsilyldiethylamine, N-trimethylsilylpyrrole, N-trimethylsilylpyrrolidine, N-trimethylsilylpiperidine, 1-cyanoethyl(diethylamino)dimethylsilane, and pentafluorophenyldimethylsilylamine.

[0054] Examples of organic silylamides and derivatives include N,O-bis(trimethylsilyl)acetamide, N,O-bis(trimethylsilyl)trifluoroacetamide, N-(trimethylsilyl)acetamide, N-methyl-N-(trimethylsilyl)acetamide, N-methyl-N-(trimethylsilyl)trifluoroacetamide, N-methyl-N-(trimethylsilyl)heptafluorobutyramide, N-(tert-butyldimethylsilyl)-N-trifluoroacetamide, and N,O-bis(diethylhydrosilyl)trifluoroacetamide.

[0055] Examples of organosilazanes include 1,1,1,3,3,3-hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and 1,3-diphenyl-1,1,3,3-tetramethyldisilazane.

[0056] Further examples of silylating agents include N-methoxy-N,O-bis(trimethylsilyl)trifluoroacetamide, N-methoxy-N,O-bis(trimethylsilyl)carbamate, N,O-bis(trimethylsilyl)sulfamate, trimethylsilyl trifluoromethanesulfonate, and N,N'-bis(trimethylsilyl)urea. Preferred silylating agents are organosilazanes, more preferably 1,1,1,3,3,3-hexamethyldisilazane.

[0057] The titanium-containing silicon oxide molded body produced according to one embodiment of the present invention can be used as a catalyst for the oxidation reaction of organic compounds, for example, the epoxidation reaction of olefins, and is particularly preferably used for the production of epoxides by reacting olefins with hydroperoxides. That is, the method for producing epoxides according to one embodiment of the present invention preferably involves reacting olefins with hydroperoxides in the presence of a catalyst containing the titanium-containing silicon oxide molded body produced by the above-mentioned method.

[0058] The olefin to be subjected to the epoxidation reaction may be an acyclic olefin, a monocyclic olefin, a bicyclic olefin, or a tricyclic or higher polycyclic olefin, and may be a monoolefin, a diolefin, or a polyolefin. When the olefin molecule contains two or more double bonds, these double bonds may be conjugated or non-conjugated. Olefins having 2 to 60 carbon atoms are generally preferred. The olefin may have a substituent. Examples of such olefins include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 2-hexene, 3-hexene, 1-octene, 1-decene, styrene, and cyclohexene. The olefin may also have a substituent containing an oxygen atom, a sulfur atom, or a nitrogen atom together with a hydrogen atom, a carbon atom, or both. Examples of such olefins include allyl alcohol, crotyl alcohol, and allyl chloride. Examples of diolefins include butadiene and isoprene. A particularly preferred olefin is propylene.

[0059] Examples of hydroperoxides include organic hydroperoxides. Organic hydroperoxides are compounds having the formula (III): R-O-O-H (III) (in formula (III), R is a hydrocarbon group). Organic hydroperoxides react with olefins to produce epoxides and hydroxyl compounds. R in formula (III) is preferably a hydrocarbon group having 3 to 20 carbon atoms, and more preferably a hydrocarbon group having 3 to 10 carbon atoms. Specific examples of organic hydroperoxides include tert-butyl hydroperoxide, 1-phenylethyl hydroperoxide, and cumene hydroperoxide. Cumene hydroperoxide will hereinafter be abbreviated as CMHP.

[0060] When CMHP is used as the organic hydroperoxide, the resulting hydroxyl compound is 2-phenyl-2-propanol. This 2-phenyl-2-propanol undergoes dehydration and hydrogenation reactions to produce cumene. Hereinafter, cumene may be abbreviated as CUM. Furthermore, CHMP can be obtained again by oxidizing this CUM. From this perspective, it is preferable to use CMHP as the organic hydroperoxide used in the epoxidation reaction.

[0061] The epoxidation reaction can be carried out in a liquid phase using a solvent, a diluent, or a mixture thereof. The solvent and diluent must be liquid under the temperature and pressure of the reaction and be substantially inert to the reactants and products. When CMHP is subjected to the epoxidation reaction in the presence of its raw material, CUM, the CUM can be used as the solvent without adding a solvent.

[0062] The epoxidation reaction temperature is generally 0 to 200° C., preferably 25 to 200° C. The epoxidation reaction pressure may be sufficient to keep the reaction phase in a liquid state, and is generally advantageously 100 to 10,000 kPa.

[0063] After the epoxidation reaction is complete, the liquid mixture containing the desired product can be separated from the catalyst composition. The liquid mixture can then be purified by an appropriate method, such as distillation, extraction, or washing. The solvent and unreacted olefin can be recycled and reused.

[0064] The reaction using the titanium-containing silicon oxide molded body produced according to one embodiment of the present invention as a catalyst can be carried out in the form of a slurry or a fixed bed, and in the case of large-scale industrial operation, it is preferable to use a fixed bed. The reaction can be carried out by a batch method, a semi-continuous method, or a continuous method.

[0065] The titanium-containing silicon oxide molded body obtained by the above-mentioned production method and a catalyst containing the titanium-containing silicon oxide molded body are also included in the scope of the present invention.

[0066] The titanium-containing silicon oxide molded body according to one embodiment of the present invention preferably satisfies the following conditions (1) and (2).

[0067] (1) 90% or more of the total pore volume has a pore diameter of 5 to 200 Å. (2) The specific pore volume is 0.2 cm ３ / g or more.

[0068] Here, the specific pore volume means the pore volume per 1 g of catalyst.

[0069] The above conditions (1) and (2) can be measured by a conventional method using the physical adsorption method (gas adsorption method) of a gas such as nitrogen or argon.

[0070] In this specification, the "hydroperoxide conversion rate" in the titanium-containing silicon oxide molded product is a value determined by the following method and calculation formula.

[0071] 0.5 g of the titanium-containing silicon oxide molded body obtained according to one embodiment of the present invention, 60 g of a solution in which CMHP was dissolved in CUM at a concentration of 25% by mass, and 33 g of propylene were fed into an autoclave and reacted under autogenous pressure at a reaction temperature of 100°C for a reaction time of 1.5 hours (including the time for heating). １ / (M０ -M １ ) x 100M ０ : Molar amount of raw material hydroperoxide M １ : Molar amount of hydroperoxide in the liquid after the reaction

[0072] Here, the titanium-containing silicon oxide molded body according to one embodiment of the present invention preferably has a hydroperoxide conversion rate, which is an index of catalytic activity, of 80% or more.

[0073] The titanium-containing silicon oxide molded body according to one embodiment of the present invention has high catalytic activity and, due to the high strength of the titanium-containing silicon oxide (low powdering rate), can prevent pressure loss when used as a catalyst. In industrial practice, this titanium-containing silicon oxide molded body can effectively prevent an increase in the amount of catalyst-derived fine powder over time due to continuous operation, and the resulting increase in pressure loss over time. [Summary] The present invention provides the following [1] to [9].

[0074] [1] A method for producing a titanium-containing silicon oxide molded body, comprising the following steps: a raw material mixing step: a step of mixing a mold agent, a silicon source, and a solvent to obtain a solid containing the mold agent and silicon oxide; a molding step: a step of molding the solid obtained through the raw material mixing step under conditions where the temperature of the solid is 40 to 100°C to obtain a molded body; and a mold agent removing step: a step of removing the mold agent from the molded body obtained through the molding step to obtain a mold-removed molded body, wherein titanium is introduced into the solid or molded body during any of the steps and / or after completion of any of the steps.

[0075] [2] The method for producing a titanium-containing silicon oxide molded body according to [1], wherein the mold is a surfactant.

[0076] [3] The method for producing a titanium-containing silicon oxide molded body according to [1], wherein the template is piperidine in which at least one hydrogen atom may be substituted with a hydrocarbon group having 1 to 10 carbon atoms.

[0077] [4] The method for producing a titanium-containing silicon oxide molded body according to [2], wherein the template is a quaternary ammonium compound containing a quaternary ammonium ion represented by the following formula (I) or an amine represented by the following formula (II): [NR １ R ２ R ３ R ４ ] ＋ (I) (wherein R １ represents a hydrocarbon group having 2 to 36 carbon atoms, and R ２ ~R ４ each independently represents a hydrocarbon group having 1 to 6 carbon atoms. ５ R ６ R ７ (II) (In formula (II), R ５ represents a hydrocarbon group having 2 to 36 carbon atoms, and R ６ and R ７ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0078] [5] The method for producing a titanium-containing silicon oxide molded body according to any one of [1] to [4], wherein the titanium is introduced during the raw material mixing step.

[0079] [6] The method for producing a titanium-containing silicon oxide molded body according to any one of [1] to [5], wherein the molding method in the molding step is a compression method.

[0080] [7] The method for producing a titanium-containing silicon oxide molded body according to any one of [1] to [6], wherein the template removal step is performed by extraction with a solvent.

[0081] [8] A method for producing an epoxide, comprising reacting an olefin with a hydroperoxide in the presence of a catalyst containing the titanium-containing silicon oxide molded product produced by the method according to any one of [1] to [7].

[0082] [9] A method for producing a titanium-containing silicon oxide molded body, comprising the following steps: a raw material mixing step: a step of mixing a mold agent, a silicon source, and a solvent to obtain a solid containing the mold agent and silicon oxide; a molding step: a step of molding the solid obtained through the raw material mixing step under conditions where the temperature of the solid is 40°C to 100°C to obtain a molded body; and a mold agent removing step: a step of removing the mold agent from the molded body obtained through the molding step to obtain a mold-removed molded body, wherein the titanium-containing silicon oxide molded body is produced by a method characterized in that titanium is introduced into the solid or molded body during any of the steps and / or after completion of any of the steps.

[0083] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0084] Hereinafter, one embodiment of the present invention will be described in more detail with reference to an example.

[0085] Example 1 (A) Raw Material Mixing Step and Titanium Introduction Hexadecyltrimethylammonium hydroxide (277 parts by mass of a 16% by mass solution) diluted to a concentration of 16% by mass with a mixed solvent having a mixing ratio (mass ratio) of water:methanol = 72:28 was stirred, and a mixed solution of 4 parts by mass of tetraisopropyl titanate and 10 parts by mass of 2-propanol was added dropwise to the stirred solution at 40°C with stirring. After the dropwise addition was completed, the mixture was stirred at 40°C for 30 minutes, and then 84 parts by mass of tetramethyl orthosilicate was added dropwise at 40°C with stirring. Stirring was then continued for 3 hours at 40°C, and the resulting solid was filtered off. The resulting solid was dried under reduced pressure at 70°C. The hexadecyltrimethylammonium hydroxide, tetramethyl orthosilicate, and tetraisopropyl titanate served as a template, silicon source, and titanium source, respectively.

[0086] (B) Molding step: Water was added to 100 parts by mass of the white solid obtained in the raw material mixing step so that the water content was 13 parts by mass, and after thorough mixing, the mixture was pressed into a heated tablet press at 1.3 ton / cm. ２The temperature of the compressed solid was measured with a contact thermometer and found to be 40°C. The obtained solid was crushed and sieved to obtain a molded body with a particle size of 1.0 to 2.0 mm.

[0087] (C) Mold Removal Step: 3 g of the molded body obtained in the above molding step was placed in a flask, and a mixed solution of 30 ml of methanol and 1.5 g of concentrated hydrochloric acid (content 36 wt%) was added. The flask was immersed in a 70°C oil bath, heated for 1 hour, allowed to cool, and the solution was removed by decantation. The same procedure was repeated once more using a mixed solution of 30 ml of methanol and 0.7 g of concentrated hydrochloric acid. 30 ml of methanol was then added, and the mixture was heated in a 70°C oil bath for 1 hour, after which the solution was removed by decantation. The flask was immersed in a 120°C oil bath under a reduced pressure of 10 mmHg, and the solvent was dried and removed for 1.5 hours to obtain a molded body from which the mold was removed.

[0088] (D) Silylation Step: A mixed solution of 1 g of 1,1,1,3,3,3-hexamethyldisilazane and 15 g of toluene was added to the molded body from which the template had been removed. The flask was immersed in a 120°C oil bath and heated for 1.5 hours. After cooling, the solvent was removed by decantation. The flask was immersed in a 120°C oil bath under a reduced pressure of 10 mmHg and the molded body was dried for 1.5 hours to obtain a titanium-containing silicon oxide molded body. The pore size distribution of the obtained titanium-containing silicon oxide molded body measured by nitrogen adsorption was in the range of 5 to 80 Å, and the specific pore volume was 0.89 ml / g.

[0089] Example 2 A molded body and a titanium-containing silicon oxide molded body were obtained in the same manner as in Example 1, except that in the molding step of Example 1, the solid to be molded and the tablet molding machine were preheated and molding was performed under conditions such that the temperature of the compressed solid was 100° C. The pore size distribution ranged from 5 to 80 Å, and the specific pore volume was 0.94 ml / g.

[0090] Comparative Example 1 A molded body and a titanium-containing silicon oxide molded body were obtained in the same manner as in Example 1, except that in the molding step of Example 1, the solid to be molded and the tablet molding machine were preheated and molding was performed under conditions where the temperature of the compressed solid was 150° C. The pore distribution range was 5 to 80 Å, and the specific pore volume was 0.70 ml / g.

[0091] Example 3 In the molding step of Example 1, a heated roll press was used, and molding was performed at a linear pressure of 4 tons / cm. The temperature of the molded body discharged from the roll press was measured with a contact thermometer and found to be 40°C. A molded body and a titanium-containing silicon oxide molded body were obtained under the same conditions as in Example 1, except that the above roll press was used. The pore distribution range was 5 to 80 Å, and the specific pore volume was 1.05 ml / g.

[0092] Example 4 A molded body and a titanium-containing silicon oxide molded body were obtained in the same manner as in Example 3, except that in the molding step of Example 3, the temperature of the molded body discharged from the roll press was 62° C. The pore size distribution ranged from 5 to 100 Å, and the specific pore volume was 1.07 ml / g.

[0093] Comparative Example 2 A molded body and a titanium-containing silicon oxide molded body were obtained in the same manner as in Example 3, except that in the molding step of Example 3, a roll press at room temperature was used and molding was performed under conditions where the temperature of the molded body discharged from the roll press was 23° C. The pore size distribution ranged from 5 to 80 Å, and the specific pore volume was 1.10 ml / g.

[0094] (E) Strength evaluation of molded body obtained in molding process (measurement of powdering rate) 1.5 g of the molded body obtained in the molding process of Example 1 was collected on a sieve with 1 mm openings, and the side of the sieve was strongly struck for 30 seconds to remove fine powder. 1 g of the molded body from which the fine powder had been removed was placed in a 2 ml syringe (inner diameter 0.9 cm) and tapped to tightly pack it. A pressure of 6.0 kgf / cm was applied to the plunger of the 2 ml syringe. ２ A load of 0.5 mm was applied for 1 minute. The molded product to which the load was applied was collected on a sieve with 0.5 mm openings, and the side of the sieve was struck strongly for 30 seconds. The weight of the fine powder that passed through the sieve openings was measured, and the powdering rate was calculated using the following formula. The results are shown in Table 1. F = W1 / W2 x 100 F: powdering rate (%) W1: mass (g) of particles with sieve openings smaller than 0.5 mm W2: mass (g) of molded product filled into a 2 ml syringe The powdering rate was also measured in the same manner for Examples 2 to 4 and Comparative Examples 1 and 2. The results are shown in Table 1.

[0095] A low powdering rate of the molded body obtained in the molding step means that the molded body obtained in the molding step has high strength. Furthermore, if the powdering rate of the molded body obtained in the molding step is low, the strength of the molded body from which the mold agent has been removed after the mold agent removal step and the strength of the titanium-containing silicon oxide molded body after the silylation step will also be relatively high.

[0096] (F) Evaluation of catalytic performance (production of propylene oxide) The catalytic performance of the titanium-containing silicon oxide molded body obtained in the silylation step of Example 1 was evaluated using a batch reaction apparatus (autoclave). 0.5 g of titanium-containing silicon oxide molded body, 60 g of a solution in which CMHP was dissolved in CUM at a concentration of 25% by mass, and 33 g of propylene were supplied to an autoclave and reacted under autogenous pressure at a reaction temperature of 100°C for a reaction time of 1.5 hours (including heating time). The reaction results are shown in Table 2. Note that the "conversion rate" in the table refers to the "CMHP conversion rate (%)" described below.

[0097] The conversion rate of CMHP was calculated as follows: Conversion rate of CMHP (%) = M １ / (M ０ -M １ ) x 100M ０ : Molar amount of raw material CMHP M １ Conversion rates were similarly measured for Examples 2 to 4 and Comparative Examples 1 and 2. The results are shown in Table 2.

[0098]

[0099]

[0100] The method for producing a titanium-containing silicon oxide molded body according to one embodiment of the present invention can be applied to the production of a high-strength catalyst used in the reaction of producing an epoxide from an olefin and a hydroperoxide, and the titanium-containing silicon oxide molded body obtained by this method can be used, for example, as a catalyst in the production of propylene oxide.

Claims

DEPCT641. A method for the fabrication of titanium-containing silicon oxide parts, comprising: a mixing step of the forming agent, silicon source, and solvent to obtain a solid containing the forming agent and silicon oxide; a forming step of the solid obtained through the mixing step to obtain the part; and a forming step of removing the forming agent from the part obtained through the forming step to obtain the part from which the forming agent has been removed. In the forming step, the solid obtained through the mixing step is formed under conditions where the solid temperature is between 40°C and 100°C. In and / or after any of the steps in the mixing, forming, and forming steps, titanium is introduced into the solid or part.

2. The method as described in Reputation 1, where the forming agent is a surfactant.3.The method described in claim 1, where the template material is piperidine which at least one hydrogen atom may be replaced by a hydrocarbon group of 1 to 10 carbon atoms; and the method described in claim 2, where the template material is a quaternary ammonium compound consisting of quaternary ammonium ions denoted by the following formula (I) or an amine denoted by the following formula (II): [NR1R2R3R4]+(I) where: R1 represents a hydrocarbon group of 2 to 36 carbon atoms; and R2 to R4 are independent of each other. Each represents a hydrocarbon group with 1 to 6 carbon atoms; and NR5R6R7(II) in which:R5 represents a hydrocarbon group with 2 to 36 carbon atoms; and R6 and R7 independently each represent a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms.

5. The method described in one of Claims 1 through 4, where titanium induction is carried out in the raw material mixing stage.

6. The method described in one of Claims 1 through 5, where the forming method used in the forming stage is compression.7.A method as described in one of Claims 1 through 6, where, in the template removal step, the template is removed by solvent extraction.

8. A method for the production of epoxide, consisting of an olefin reaction with hydroperoxide, with a catalyst consisting of a titanium-containing silicon oxide mold, which is produced by one of the methods described in Claims 1 through 7.9.Titanium-infused silicon oxide molded parts are manufactured using a process that involves: a mixing step of raw materials, a molding agent, a silicon source, and a solvent to obtain a solid composed of the molding agent and silicon oxide; a molding step to form the solid obtained from the mixing step; and a mold removal step to remove the molding agent from the molded part obtained from the molding step. In the molding step, the solid obtained from the mixing step is molded under conditions where the solid temperature is between 40°C and 100°C. In and / or after any of the steps in the mixing, molding, and mold removal steps, titanium is injected into the solid or molded part.