JP2006255586A - Method for production of titanium-containing silicon oxide catalyst, and catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method for a titanium-containing silicon oxide catalyst usable for reaction of forming an oxirane from a hydroperoxide and an olefin-type compound, having high activity, and capable of maintaining the activity for a long duration. <P>SOLUTION: The production method for a titanium-containing silicon oxide catalyst involves silylation of titanium-containing silicon oxide, wherein the silylation is treatment for introducing two or more silyl groups into the titanium-containing silicon oxide compound by using different kinds of silylation agents. The production method preferably includes: a first step for obtaining a solid containing a catalytic component and a template by mixing and/or stirring a titanium source and the template in liquid state; a second step for obtaining a catalyst component-containing solid by removing the template from the solid obtained in the first step; and a third step for subjecting the solid obtained in the second step to silylation described above. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a titanium-containing silicon oxide catalyst and a catalyst. More specifically, the present invention is a titanium-containing silicon oxide catalyst that can be used, for example, in a reaction for obtaining an oxirane compound from a hydroperoxide and an olefin type compound, exhibits high activity, and can maintain the activity for a long time. The present invention relates to a production method and a catalyst obtained by the production method.

  A method for obtaining an oxirane compound from a hydroperoxide and an olefin type compound in the presence of a catalyst is known. As a catalyst used here, for example, Patent Document 1 discloses a specific titanium-containing silicon oxide catalyst. However, it has been difficult to say that conventional catalysts are sufficiently satisfactory from the viewpoint of developing higher activity.

  On the other hand, for example, Patent Document 2 to Patent Document 13 disclose a highly active and highly selective catalyst for obtaining an oxirane compound from a hydroperoxide and an olefin type compound. It was not enough from the point of view.

US Pat. No. 4,367,342 US Pat. No. 5,783,167 JP-A-7-300312 JP 2000-107604 A JP 2000-107605 A JP 2000-109469 A JP 2000-109470 A JP 2000-117101 A JP 2000-119266 A JP 2001-286768 A JP 2002-224563 A Japanese Patent Laid-Open No. 2002-239381 JP 2004-195379 A

  Under such circumstances, the problem to be solved by the present invention is, for example, a titanium-containing material that can be used in a reaction for obtaining an oxirane compound from a hydroperoxide and an olefin type compound, exhibits high activity, and can maintain its activity for a long time. It exists in the point which provides the manufacturing method of a silicon oxide catalyst, and the catalyst obtained by this manufacturing method.

  That is, the present invention is a method for producing a titanium-containing silicon oxide catalyst in which a titanium-containing silicon oxide is subjected to a silylation treatment, and the silylation treatment is performed using two different silylating agents. The present invention relates to a method for producing a titanium-containing silicon oxide catalyst, which is a treatment for introducing a silyl group.

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

  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, exhibits high activity, and can maintain the activity for a long time, and the method A catalyst obtained by the production method can be provided.

  The method for producing a catalyst of the present invention is a method for producing a titanium-containing silicon oxide catalyst in which a titanium-containing silicon oxide is subjected to a silylation treatment, wherein the silylation treatment is performed using a different silylating agent. It is a manufacturing method of the titanium containing silicon oxide catalyst which is a process which introduce | transduces two or more types of silyl groups into a thing.

  The titanium-containing silicon oxide to be subjected to silylation treatment in the present invention is obtained by supporting a titanium source such as titanium alkoxide or titanium halide on a carrier such as silica gel in a gas phase or in a liquid phase, titanium halide and silicon. Although not particularly limited, such as those obtained by reacting halide or the like in a flame, those obtained by sol-gel reaction of titanium alkoxide and silicon alkoxide, the following (1) to (3) It is preferably made of a titanium-containing silicon oxide that satisfies all the conditions.

  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.

  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 titanium-containing silicon oxide subjected to the silylation treatment in 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.

The titanium-containing silicon oxide subjected to the silylation treatment in the present invention preferably has an absorption peak in the region of 960 ± 5 cm ⁻¹ in the infrared absorption spectrum from the viewpoint of high activity. This peak is considered to correspond to titanium introduced into the silica skeleton.

The catalyst of the present invention is preferably produced by a production method having the following steps.
1st process: The process which obtains the solid which contains a catalyst component and a mold agent by mixing and stirring a silica source, a titanium source, and a mold agent (template) in liquid state 2nd process: The mold agent from the solid obtained at the 1st process Step of obtaining a solid containing a catalyst component by removing the catalyst Third step: Step of introducing two or more silyl groups into the solid obtained in the second step using a different silylating agent

  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 liquid state. When the reagent to be used is a solid, it may be used as a solution dissolved or dispersed in a solvent.

  Examples of the silica source include amorphous silica and alkoxysilanes such as tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate and the like. Silica sources containing organic groups such as alkyltrialkoxysilanes, dialkyldialkoxysilanes, 1,2-bis (trialkoxysilyl) alkanes can also be used. They can be used alone or in a mixture of several kinds.

  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.

  Non-ionic surfactant polyalkylene oxides such as alkylammonium, dialkylammonium, trialkylammonium and benzylammonium derived from cationic surfactants, alkyl sulfate ions and alkylphosphate ions derived from anionic surfactants, etc. Any of block copolymers, alkylamines and the like 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, hexadecylpyridinium and the like.

  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 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. 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 include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, etc., but the mold and alkali source are contained in the same compound. It is more preferable to use a quaternary ammonium ion hydroxide represented by the general formula (I). 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 is a step of obtaining a solid containing a catalyst component by removing the mold from the solid obtained in the first step.
The mold agent may be removed by either high-temperature calcination or solvent extraction, but from the viewpoint of obtaining a highly active catalyst, solvent extraction is preferable.

  The extraction and 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.

  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 room 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 sufficiently mixing the solid containing the solvent, 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 quaternary ammonium ion represented by the general formula (I) in the solution obtained after the extraction treatment can be recovered and reused as a mold raw material in the first step. Similarly, the extraction solvent can be purified and reused by a normal distillation operation or the like.

  Also, from the viewpoint of efficiently producing the catalyst, it is preferable to replace the extraction solvent contained in the solid obtained in the second step with a solvent that is substantially inert to the silylating agent used in the subsequent silylation step. .

  Alcohols that are preferably used for removing the mold will react with the silylating agent in the silylation of the next step and inhibit the desired reaction. Therefore, the extraction solvent contained in the solid after extraction of the mold is usually removed by a drying operation. Is done. Examples of the drying device include a conical dryer and a shelf dryer equipped with warm air or a decompression device. However, it takes a very long time to perform such drying economically and efficiently, and it may not be sufficient from the viewpoint of catalyst productivity. Depending on the drying conditions, pore shrinkage, changes in catalyst surface properties, etc. may occur and catalyst performance may deteriorate.

  In order to produce the catalyst efficiently, it is preferable to replace the extraction solvent contained in the solid obtained in the second step with a solvent that is substantially inert to the silylating agent used in the subsequent silylation step. The substitution solvent used in this 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 suitably used for this substitution operation are generally hydrocarbons, halogenated hydrocarbons, ketones, ethers, esters, N, N-disubstituted amides having 1 to about 12 carbon atoms at room temperature, Nitriles and tertiary amines 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 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 this substitution operation, the solid containing the substitution solvent and the extraction solvent obtained in the second step is 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 passed. From the viewpoint of catalyst productivity, it is preferable to perform the second step, the solvent replacement step, and the subsequent silylation step 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.

  Further, the substitution solvent used in this step can be reused after removing the extraction solvent by an ordinary method such as distillation or extraction.

  Silylation, which is the greatest feature of the present invention, is a step of introducing two or more types of silyl groups into titanium-containing silicon oxide using different silylating agents. In particular, it is preferable to subject the solid obtained in the second step in the above production method to the present silylation treatment.

  Silylation may be performed by a gas phase method in which a gaseous silylating agent is reacted with titanium-containing silicon oxide, or by a liquid phase method in which a silylating agent and titanium-containing silicon oxide are reacted in a solvent. However, the liquid phase method is more preferable in the present invention. Usually, when silylation is performed by a liquid phase method, hydrocarbons are used as a suitable 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 thereof include nylchlorosilane, triethoxychlorosilane, dimethylphenylchlorosilane, methylphenylvinylchlorosilane, benzyldimethylchlorosilane, diphenylchlorosilane, diphenylmethylchlorosilane, diphenylvinylchlorosilane, tribenzylchlorosilane, and 3-cyanopropyldimethylchlorosilane.

  Examples of organic silylamines include N-trimethylsilyldimethylamine, N-trimethylsilyldiethylamine, N-triethylsilylamine, N-triethylsilyldimethylamine, N-triethylsilyldiethylamine, N-tri-n-propylsilylamine, N-t -Butyldimethylsilylamine, N-trimethylsilylimidazole, N-triethylsilylimidazole, N-tri-n-propylsilylimidazole, Nt-butyldimethylsilylimidazole, N-dimethylethylsilylimidazole, N-dimethyln-propylsilyl Imidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilyldimethylamine, N-trimethylsilyldiethylamine, N-trimethylsilylpyrrole, N-trimethylsilylpyrrolidine, N-trimethylsilylpyrrole Lysine, 1-cyanoethyl (diethylamino) dimethylsilane, pentafluorophenyl butyldimethylsilyl amine.

  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, hexaethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-bis (chloromethyl) tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, and hexamethylcyclotrisilazane.

  Other silylating agents include N-methoxy-N, O-bistrimethylsilyl trifluoroacetamide, N-methoxy-N, O-bistrimethylsilyl carbamate, N, O-bistrimethylsilylsulfamate, trimethylsilyl trifluoromethanesulfonate, Examples thereof include triethylsilyl trifluoromethanesulfonate and N, N′-bistrimethylsilylurea.

  The most important feature of the catalyst production method of the present invention is that two or more silyl groups are introduced into the titanium-containing silicon oxide using different silylating agents. The reason will be described below.

  Titanium-containing silicon oxides are known to become highly active and highly selective catalysts by silylation, while the silyl group is used from the catalyst along with its use by reaction with moisture contained in the reaction system. Desorbed and the catalyst performance decreases.

  From the viewpoint of obtaining a catalyst exhibiting high activity over a long period of time, a prescription for making the silyl group more bulky in order to suppress the elimination of the silyl group due to moisture or the like can be considered, but by using a bulky silyl group As a result, a highly active and highly selective catalyst may not be obtained by reducing the amount of silyl groups introduced into the catalyst or increasing the steric hindrance around titanium, which is the catalytic active point.

In order to solve the above problem, in the present invention, different silylating agents are used to introduce into the titanium-containing silicon oxide a silyl group that has a positive effect on activity and a bulky silyl group that is difficult to be removed by water.
In the production method of the present invention, it is preferable to introduce each silyl group separately in order to control the amount of silyl group to be introduced to a desired ratio. Among these, from the viewpoint of obtaining a highly active catalyst, the silyl group initially introduced into the catalyst is preferably a trimethylsilyl group. For the introduction of the trimethylsilyl group, hexamethyldisilazane, N-trimethylsilyldimethylamine, or N-trimethylsilyldiethylamine is preferably used.

  The silylation may be carried out by either a batch method or a flow method, but it is preferable to select reaction conditions and the like so that introduction of different silyl groups is uniform throughout the catalyst.

  The titanium-containing silicon oxide suitably used in the present invention is usually used as a molded body by a process 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 obtained by the above production method 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 epoxidation reactions of olefinic compounds. Is possible. 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, 1-butene, isobutylene, 1-hexene, 2-hexene, 3-hexene, 1-octene, 1-decene, 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
(Here, R is a monovalent hydrocarbon group.)
Which reacts with an olefinic compound to produce an oxirane compound and a compound R—OH. Preferably, 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, and 2-phenyl-2. -Propyl group, and various tetranyl groups generated by removing a hydrogen atom 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. The resulting α-methylstyrene can be converted to cumene by reaction with hydrogen in the presence of a catalyst, and the resulting cumene can be converted to cumene hydroperoxide by reaction with oxygen. Can be used.

  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 (first step)
125.1 parts by weight of a 16% by weight hexadecyltrimethylammonium hydroxide aqueous solution (containing 25% by weight of methanol) was stirred, and at 40 ° C., 1.85 parts by weight of tetraisopropyl titanate and 10.0 parts by weight of 2-propanol were stirred. The mixed solution was added dropwise. After stirring for 30 minutes, 38.1 parts by weight of tetramethylorthosilicate was added dropwise. Thereafter, stirring was continued at 40 ° C. for 1 hour. The resulting precipitate was filtered off. The resulting precipitate was dried at 70 ° C. under reduced pressure.

Production of molded body A mixture of 10.0 parts by weight of a white solid obtained by drying and well mixed with water so as to have a water content of 1.5 parts by weight was compression molded with a roll press. 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.

Extraction and removal of mold (second step)
Next, 10.0 parts by weight of the molded body obtained as described above was packed in a glass lining column, and (1) 91.1 parts by weight of methanol at room temperature and (2) heating at 45 ° C. at LHSV = 6 h ^−1. Below, 168.1 parts by weight of a 0.2 mol / l hydrochloric acid / methanol solution and (3) 132.3 parts by weight of methanol were sequentially passed through the column under heating at 45 ° C. After passing through, methanol in the column was extracted from the bottom of the column.

Replacement of extraction solvent 100 parts by weight of the molded product after removal of the mold wetted with methanol and 1500 parts by weight of toluene were placed in a flask, and the solvent was replaced by heating at 80C for 1 hour. After cooling, the solvent was removed by decantation and dried at 110 ° C. under reduced pressure to obtain 46 parts by weight of titanium-containing silicon oxide.

Silylation (third step)
23.0 parts by weight of the titanium-containing silicon oxide obtained by the above treatment, 3.8 parts by weight of hexamethyldisilazane and 230 parts by weight of toluene were placed in a flask, and silylation was performed for 1 hour while heating at 110 ° C. After removing the solvent by decantation, it was dried at 110 ° C. under reduced pressure to obtain 25.0 parts by weight of a partially trimethylsilylated solid. Subsequently, 24.0 parts by weight of a partially trimethylsilylated solid, 23.3 parts by weight of hexaethyldisilazane, and 200 parts by weight of toluene were added to the flask, and silylation was performed for 5 hours while heating at 110 ° C. By drying at 110 ° C. under reduced pressure, 25.9 parts by weight of a titanium-containing silicon oxide catalyst partially trimethylsilylated and the rest triethylsilylated was obtained.

Synthesis of Propylene Oxide (PO) The catalyst obtained as described above was evaluated in a batch reactor (autoclave) using 25% cumene hydroperoxide cumene solution (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.

Comparative Example 1
A titanium-containing silicon oxide obtained by the same operation as in Example 1 was evaluated in a batch reactor as in Example 1, except that the silylation step in Example 1 was not performed. The reaction results are shown in Table 1.

Comparative Example 2
A catalyst obtained in the same manner as in Example 1 except that the silylation in Example 1 was performed under the following conditions was evaluated in a batch reactor as in Example 1. The reaction results are shown in Table 1.

Silylation (third step)
Titanium-containing silicon oxide 3.0 parts by weight obtained by solvent substitution treatment and drying, 2.0 parts by weight of hexamethyldisilazane and 30.0 parts by weight of toluene were placed in a flask and heated at 110 ° C. for 1.5 hours. Made. Then, 3.5 parts by weight of trimethylsilylated titanium-containing silicon oxide catalyst was obtained by drying at 110 ° C. under reduced pressure.

On the other hand, in order to evaluate the stability of silyl groups in water, the catalyst was treated under the following conditions. The ratio of the detached silyl group was quantified from the result of Si-NMR analysis of the catalyst before and after the treatment. The results are shown in Table 1.
Treating the catalyst with water / acetone solvent 0.5 g of silylated catalyst, 5.0 g of water and 15.0 g of acetone were charged into a 150 ml autoclave, and after sealing, the system was pressurized to 2 MPa with nitrogen. The autoclave was heated at 140 ° C. for 3 hours. After cooling, it was depressurized and opened, and the catalyst was recovered by filtration. The recovered catalyst was dried at 110 ° C. under reduced pressure for 1.5 hours.

Comparative Example 3
A catalyst obtained in the same manner as in Example 1 except that the silylation in Example 1 was performed under the following conditions was evaluated in a batch reactor as in Example 1. The reaction results are shown in Table 1.

Silylation (third step)
Titanium-containing silicon oxide (3.0 parts by weight) obtained by solvent replacement treatment and drying, 3.3 parts by weight of triethylsilylamine and 30.0 parts by weight of toluene were placed in a flask and heated at 110 ° C. for 1.5 hours. Went. Then, 3.7 parts by weight of a triethylsilylated titanium-containing silicon oxide catalyst was obtained by drying at 110 ° C. under reduced pressure.

  On the other hand, in order to evaluate the stability of the silyl group to water, the catalyst was treated under the same conditions as in Comparative Example 2. The ratio of the detached silyl group was quantified from the result of Si-NMR analysis of the catalyst before and after the treatment. The results are shown in Table 1.

* 1: TMS represents trimethylsilyl group, TES represents triethylsilyl group * 2: Result of catalyst in water / acetone solvent treatment (model test) * 3: PO / C ₃ 'selectivity = generated PO mole / reaction C ₃ 'Mole * 100
Here, the reaction C ₃ 'mol = reaction CHPO mole-formed phenol mole-formed acetophenone mole

Claims (9)

A method for producing a titanium-containing silicon oxide catalyst comprising subjecting a titanium-containing silicon oxide to a silylation treatment, wherein the silylation treatment uses two or more different silyl groups on the titanium-containing silicon oxide using different silylating agents. A method for producing a titanium-containing silicon oxide catalyst which is a treatment to be introduced. The production method according to claim 1, wherein two or more types of silyl groups are introduced separately. The process according to claim 2, wherein the silyl group initially introduced into the catalyst is a trimethylsilyl group. The manufacturing method according to one of claims 1 to 3, which is manufactured by a manufacturing method including the following first step to third step.
1st process: The process which obtains the solid which contains a catalyst component and a mold agent by mixing and stirring a silica source, a titanium source, and a mold agent (template) in liquid state 2nd process: The mold agent from the solid obtained at the 1st process A step of obtaining a solid containing a catalyst component by removing the catalyst. Third step: A step of subjecting the solid obtained in the second step to the silylation treatment according to claim 1. The production method according to claim 4, wherein the mold is removed in the second step by a solvent extraction operation. A method for producing a titanium-containing silicon oxide catalyst that satisfies all of the following conditions (1) to (3), wherein the mold used in the first step is represented by the following general formula (I): The production method according to claim 4 or 5, which is a quaternary ammonium ion.
(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 [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, further comprising a step of molding a solid containing a catalyst component. A titanium-containing silicon oxide catalyst obtained by the production method according to one of claims 1 to 7. A method for producing an oxirane compound, comprising reacting an olefin type compound and a hydroperoxide in the presence of the catalyst according to claim 8.