Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide

Abstract

A method for producing an epoxide in which a titanium-containing silicon oxide catalyst having a salt at a prescribed concentration is used.

Description

Technical Field

[0001] The present invention relates to a method for producing titanium-containing silicon oxide, a method for producing epoxide from olefin in the presence of the titanium-containing silicon oxide, and the titanium-containing silicon oxide. Background Art

[0002] The method of producing epoxide from hydroperoxide and olefin in the presence of a catalyst is well known. As a catalyst used in this method, for example, Patent Document 1 describes titanium-containing silicon oxide.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent document 1: CN102807537B Summary of the invention

[0006] Problems to be solved by the invention

[0007] A method for producing epoxides in high yield in the reaction of olefins and hydroperoxides to form epoxides is desired.

[0008] Means used to solve problems

[0009] The present invention relates to the following, but is not limited thereto.

[0010] [1] A titanium-containing silicon oxide, wherein the titanium-containing silicon oxide satisfies all of conditions 1 to 5: Condition 1: The average pore size is 10 Condition 2: more than 80% of the total pore volume has 5 ~200 Condition 3: Total pore volume is 0.2 cm 3 / g or more; Condition 4: The titanium-containing silicon oxide is obtained by using a quaternary ammonium ion represented by formula I as a template, and then removing the template by a solvent extraction operation, [NR 1 R 2 R 3 R 4 ] + I (In the formula, R 1 Represents C 2～36 The hydrocarbon group, R 2 ~R 4 Each independently represents C 1～6 Condition 5: the mass ratio of the salt S to the mass ratio of the titanium atom in the titanium-containing silicon oxide is 0.004 to 10, and the salt S is at least one selected from the group consisting of ammonium salts, alkali metal salts and alkaline earth metal salts.

[0011] [2] The titanium-containing silicon oxide according to [1], wherein the ammonium salt is ammonium chloride.

[0012] [3] Use of the titanium-containing silicon oxide according to [1] or [2], wherein the titanium-containing silicon oxide is used to produce epoxide from olefin.

[0013] [4] A method for producing titanium-containing silicon oxide, wherein the method for producing titanium-containing silicon oxide comprises the following steps: a step of mixing a silicon source, a template and a solvent to obtain a solid containing silicon oxide and the template (raw material mixing step); a step of removing the template from the solid obtained in the raw material mixing step to obtain a solid containing silicon oxide (template removal step); a step of contacting the solid obtained in the template removal step with a silylating agent to obtain an individual containing silylated silicon oxide (silylation step); a step of introducing titanium into a system (titanium introduction step); a step of introducing or removing a salt S or a precursor thereof into or from the system to adjust the molar concentration of the salt S or its precursor relative to the amount of substance of titanium atoms in the system, wherein the salt S is at least one selected from the group consisting of ammonium salts, alkali metal salts and alkaline earth metal salts (salt concentration adjustment step).

[0014] [5] A method for producing an epoxide, comprising the step of reacting an olefin with a hydroperoxide in the presence of the titanium-containing silicon oxide according to [1] or [2].

[0015] [6] The method according to [5], wherein the olefin is propylene.

[0016] [7] The method according to [5] or [6], wherein the hydroperoxide is cumene hydroperoxide.

[0017] Effects of the Invention

[0018] According to one embodiment of the present invention, there is provided a method for producing an epoxide in a high yield in a reaction of generating an epoxide from an olefin and a hydroperoxide. DETAILED DESCRIPTION

[0019] definition

[0020] In this specification, the term "solution" includes not only a homogeneous liquid but also a colloid, a suspended mixture, and a gas-liquid mixture.

[0021] In the present specification, the term "α-olefin" refers to a hydrocarbon having a carbon-carbon unsaturated double bond at the α position.

[0022] In this specification, the term "C X～Y The term "hydrocarbon group" refers to a hydrocarbon group having X to Y carbon atoms.

[0023] In this specification, all numbers disclosed are approximate if used in conjunction with the word "about" or "approximately". They may vary by 1%, 2%, 5%, or sometimes within a range of 10% to 20%. L and upper limit R U In the case of a numerical range, any number included in the range is always specifically disclosed. In particular, the following numbers within the range are specifically disclosed. L +k * (R U -R L ) (wherein k is a variable in the range of 1% to 100% in increments of 1%, that is, k is 1%, 2%, 3%, 4%, 5%, ..., 50%, 51%, 52%, ..., 95%, 96%, 97%, 98%, 99% or 100%). In addition, any numerical range defined by the two R numbers described above is also specifically disclosed.

[0024] The description of "lower limit to upper limit" indicating a numerical range means "above the lower limit and below the upper limit", and the description of "upper limit to lower limit" means "below the upper limit and above the lower limit". That is, these descriptions indicate a numerical range including the lower limit and the upper limit, but in one embodiment, one or both of the upper limit and the lower limit may be excluded, that is, "lower limit to upper limit" may mean "greater than the lower limit and less than or equal to the upper limit", "greater than or equal to the lower limit and less than the upper limit", or "greater than the lower limit and less than the upper limit". Similarly, "above xx" may also mean "greater than xx", and "below xx" may also mean "less than xx".

[0025] Titanium-containing silicon oxide

[0026] In this specification, titanium-containing silicon oxide refers to a compound obtained by replacing part of Si in porous silicate (SiO2) with Ti. This compound has a bond represented by -Si-O-Ti.

[0027] The titanium-containing silicon oxide of the present invention satisfies all of the first to fifth conditions.

[0028] Condition 1 is that the average pore size is 10 above.

[0029] Condition 2 is that more than 80% of the total pore volume has 5 ~200 of aperture.

[0030] Condition 3 is that the total pore volume is 0.2 cm 3 Here, the total pore volume refers to the pore volume per 1 g of titanium-containing silicon oxide.

[0031] The measurement under conditions 1 to 3 can be performed by a common method using a physical adsorption method using a gas such as nitrogen or argon. For example, the measurement can be performed according to the method described in the Examples.

[0032] From the viewpoint of diffusibility, the average pore size is preferably 20 From the perspective of effective area, it is preferred that 90% or more of the total pore volume have 5 ~200 In addition, the total pore volume is preferably 0.5 cm 3 / g or above.

[0033] Condition 4 is that the titanium-containing silicon oxide is obtained by using a quaternary ammonium ion represented by Formula I as a template (template) and then removing the template by a solvent extraction operation.

[0034] [NR 1 R 2 R 3 R 4 ] + I

[0035] (In the formula, R 1 Represents C 2～36 The hydrocarbon group, R 2 ~R 4 Each independently represents C 1～6 of hydrocarbon groups).

[0036] Condition 4 will be described in detail together with the description of the method for producing the titanium-containing silicon oxide (particularly, the raw material mixing step and the template removing step).

[0037] Condition 5 is that the ratio of the mass of the salt S to the mass of the titanium atom in the titanium-containing silicon oxide is 0.004 to 10, and the salt S is at least one selected from the group consisting of ammonium salts, alkali metal salts and alkaline earth metal salts. + ) and anions, and also includes substituted ammonium ions ([NR 1 R 2 R 3 R 4 ] + ) and an anion. Preferably, the salt S is a substituted or unsubstituted ammonium salt, more preferably a substituted or unsubstituted ammonium chloride, and further preferably unsubstituted ammonium chloride. Regarding the above ratio, its lower limit is preferably 0.01 or more, more preferably 0.1 or more. In addition, regarding the above ratio, its upper limit is 4 or less, more preferably 1 or less.

[0038] Condition 5 will be described in detail together with the description of the method for producing the titanium-containing silicon oxide (particularly the salt concentration adjustment step) and the like.

[0039] Manufacturing method

[0040] A method for producing a titanium-containing silicon oxide according to one embodiment of the present invention includes a raw material mixing step, a template removing step, a silylation step, a titanium introducing step, and a salt concentration adjusting step.

[0041] Raw material mixing process

[0042] The raw material mixing step is a step of mixing a silicon source, a template, and a solvent to obtain a solid containing silicon oxide and the template, and is sometimes referred to as step A.

[0043] The “silicon source” refers to silicon oxide and a silicon oxide precursor. The silicon oxide precursor refers to a compound that converts a part or all of the silicon oxide precursor into silicon oxide by reacting the silicon oxide precursor with water.

[0044] As an example of the above silicon oxide, amorphous silicon dioxide can be cited. As an example of the above silicon oxide precursor, alkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane and 1,2-bis(trialkoxysilyl)alkane can be cited. As an example of alkoxysilane, tetramethyl orthosilicate, tetraethyl orthosilicate and tetrapropyl orthosilicate can be cited. As an example of alkyltrialkoxysilane, trimethoxy(methyl)silane can be cited. As a dialkyldialkoxysilane, dimethoxydimethylsilane can be cited. As a silicon source, a single silicon source can be used, or a combination of multiple silicon sources can be used.

[0045] When a silicon oxide precursor is used as the silicon source, water is preferably used as part or all of the solvent in step A. When the silicon oxide precursor is mixed with water, part or all of the silicon oxide precursor is converted into silicon oxide.

[0046] The template agent refers to a substance capable of forming a pore structure in the titanium-containing silicon oxide. As the template agent, a quaternary ammonium compound having a quaternary ammonium ion represented by Formula I can be preferably used.

[0047] [NR 1 R 2 R 3 R 4 ] + I

[0048] (In Formula I, R 1 Represents C 2～36 The hydrocarbon group, R 2 ~R 4 Each independently represents C 1～6 of hydrocarbon groups.)

[0049] In Formula I, R 1 C2～36 The hydrocarbon group may be straight-chain or branched, aliphatic or aromatic. 10～22 The hydrocarbon group R 2 ~R 4 Each independently is C 1～6 The hydrocarbon group is preferably aliphatic and may be straight chain or branched. 2 ~R 4 All are methyl.

[0050] Examples of the quaternary ammonium ion represented by formula I include cations such as tetraethylammonium, tetrapropylammonium, tetrabutylammonium, decyltrimethylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, eicosyltrimethylammonium, docosyltrimethylammonium, and benzyltrimethylammonium.

[0051] As examples of the compound containing the quaternary ammonium ion represented by Formula I, there can be mentioned tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, 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.

[0052] The silicon source and the template are mixed in the presence of a solvent. Examples of the solvent include water and alcohol. Examples of alcohol include methanol, ethanol, 1-propanol, and 2-propanol. Two or more solvents may be mixed and used.

[0053] By going through step A, a solid containing silicon oxide and a template can be obtained. Usually, a solvent removal step is included in step A. The obtained solid containing silicon oxide and a template can be taken out by filtration, decantation, drying, centrifugation, a combination thereof, etc. The mixing of step A is preferably carried out at 0°C to 300°C for 30 minutes to 1000 hours. In one embodiment, the mixing can be carried out at 20°C to 100°C, at the boiling point of the solvent, at 20°C to 60°C, or at 20°C to 40°C. In one embodiment, the mixing can be carried out for 30 minutes to 24 hours, or for 2 hours to 24 hours. In addition, stirring can be implemented during the mixing.

[0054] Template removal process

[0055] The template removal step is a step of removing the template from the solid obtained in step A to obtain a solid containing silicon oxide, and is sometimes referred to as step B. By carrying out step B, a solid containing no template or substantially no template can be obtained.

[0056] The content of the template in the solid obtained in step B is preferably 10% by mass or less, more preferably 1% by mass or less.

[0057] The template can be removed by calcining the solid containing the template at 300° C. to 800° C. in air, or by solvent extraction. The template is preferably removed by extraction.

[0058] Whitehurst et al. reported a technique for extracting a template using a solvent (see U.S. Patent No. 5143879). The solvent can be any solvent that can dissolve the compound used as the template, and C which is liquid at room temperature can be used. 1～12 Compounds, or mixtures of two or more of these compounds. Examples of suitable solvents include alcohols, ketones, non-cyclic ethers 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.

[0059] As an example of a solvent, from the viewpoint of the solubility (dissolving energy) of the template, when the template is a compound containing a quaternary ammonium ion, alcohol is preferred, among which methanol is more preferred. The mass ratio of the solvent to the solid containing the template is generally 1 to 1000, preferably 5 to 300. In order to improve the extraction effect, acids or their salts may be added to these solvents. Examples of the acids used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid; or 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.

[0060] As an example of a method for removing the template, there can be cited a method in which a solvent and a solid containing the template are fully mixed, and then the liquid phase is separated by filtering, decantation, drying, centrifugation, or a combination thereof. This operation can be repeated multiple times. In addition, the template can also be extracted by filling a solid containing the template into a container such as a column and circulating an extraction solvent. The extraction temperature is preferably 0°C to 200°C, more preferably 20°C to 100°C. When the boiling point of the extraction solvent is low, the extraction can be performed under pressure.

[0061] The template in the solution obtained by the extraction treatment can be recovered by subjecting it to ion exchange or other treatment as necessary and reused as the template in step A. Similarly, the extraction solvent can be purified by ordinary distillation operation or the like and reused.

[0062] Silylation process

[0063] The silylation step is a step of obtaining a solid containing silylated silicon oxide by contacting the solid obtained in step B with a silylating agent, and is sometimes referred to as step C. By carrying out step C, the silicon oxide contained in the solid obtained in step B is silylated.

[0064] Silylation can be carried out by a gas phase method in which a gaseous silylating agent is brought into contact with the solid obtained in step B and reacted, or by a liquid phase method in which a silylating agent is brought into contact with the solid in a solvent and reacted. In one embodiment of the present invention, a liquid phase method is preferred. Generally, when silylation is carried out by a liquid phase method, a hydrocarbon is preferably used as a solvent in step C. When silylation is carried out by a liquid phase method, drying may be performed thereafter.

[0065] The silylating agent is a silicon compound reactive with solids, and a hydrolyzable group is bonded to silicon. Examples of hydrolyzable groups bonded to silicon include hydrogen, halogen, alkoxy, acetoxy, and amino. In the silylating agent, the hydrolyzable group bonded to silicon is preferably one. In addition, at least one group selected from the group consisting of alkenyl groups such as alkyl and vinyl; aryl groups such as phenyl; halogenated alkyl and siloxy groups is bonded to silicon.

[0066] Examples of the silylating agent include organosilanes, organosilylamines, organosilylamides and derivatives thereof, and organosilazanes.

[0067] Examples of the organosilane 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, diphenylchlorosilane, diphenylmethylchlorosilane, dimethoxy ... Phenylvinylsilyl chloride, tribenzylsilyl chloride, 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.

[0068] Examples of organosilylamines include N-(trimethylsilyl)imidazole, N-(tert-butyldimethylsilyl)imidazole, N-(dimethylethylsilyl)imidazole, N-(dimethyl-n-propylsilyl)imidazole, N-(dimethylisopropylsilyl)imidazole, N-(trimethylsilyl)-N,N-dimethylamine, N-(trimethylsilyl)-N,N-diethylamine, N-(trimethylsilyl)pyrrole, N-(trimethylsilyl)pyrrolidine, N-(trimethylsilyl)piperidine, 1-cyanoethyl(diethylamino)dimethylsilane, and pentafluorophenyldimethylsilylamine.

[0069] Examples of organosilylamides and their 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(diethylhydrogensilyl)trifluoroacetamide.

[0070] Examples of the organosilazane 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.

[0071] Other examples of the silylating agent include N-methoxy-N,O-bis(trimethylsilyl)trifluoroacetamide, N-methoxy-N,O-bis(trimethylsilyl)carbamate, N,O-bis(trimethylsilyl)aminosulfonate, trimethylsilyl trifluoromethanesulfonate and N,N'-bis(trimethylsilyl)urea.

[0072] The preferred silanizing agent is an organosilazane, more preferably 1,1,1,3,3,3-hexamethyldisilazane.

[0073] The silicon oxide-containing solid obtained in step B is silylated by contacting the solid with a silylating agent. It is presumed that at least a portion of the silicon oxide-containing solid is hydrophobized by introducing silyl groups to surface OH groups, but the present invention is not limited to this theory.

[0074] Titanium introduction process

[0075] The titanium introduction step is a step of introducing titanium into the system, and is sometimes referred to as step D. In the system refers to the reaction system in the method for producing titanium-containing silicon oxide, for example, before step A, in step A, between step A and step B, in step B, between step B and step C, in step C, and after step C.

[0076] By introducing titanium into the system, silicon oxide is mixed with a titanium source, thereby introducing a bond represented by -Si-O-Ti into silicon oxide.

[0077] Titanium can be introduced into silicon oxide by mixing and contacting silicon oxide and a titanium source in a liquid phase, or by mixing and contacting a gas containing a titanium source with silicon oxide.

[0078] When mixing is performed in a liquid phase, examples of the solvent include water and alcohol, and for example, the above-mentioned solvents used in step A can be used. Examples of the mixing temperature include 0° C. to 60° C. Examples of the mixing time include 1 minute to 24 hours.

[0079] When mixing is performed in the gas phase, the titanium source can be gasified and mixed. Examples of mixing temperatures include 100° C. to 500° C. Examples of mixing times include 1 minute to 24 hours. Mixing can be performed at normal pressure or, for example, at 10 kPa to 1000 kPa (absolute pressure).

[0080] Titanium may be introduced at any time before step A, in step A, between step A and step B, in step B, between step B and step C, in step C, and after step C. Titanium may be introduced at two or more of the above-mentioned times.

[0081] It is preferred to introduce titanium before starting step C, more preferably at at least one timing selected from the group consisting of before step A, during step A, and between step B and step C, and even more preferably before step A or during step A.

[0082] In the case where titanium is introduced before step A, the titanium source is mixed with the silicon source, the template or the solvent before the mixing in step A.

[0083] When titanium is introduced in step A, a silicon source, a titanium source, and a template are mixed in step A.

[0084] Titanium can be introduced after step A is completed and before step B is started by contacting the solid obtained in step A with a titanium source.

[0085] Titanium can be introduced after step B is completed and before step C is started by contacting the solid obtained in step B with a titanium source.

[0086] Examples of 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 tetra(octadecyl) titanate. Examples of titanium chelate complexes include titanium acetylacetonate (IV) and diisopropoxy diacetylacetonate titanium (IV). Examples of titanium halides include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide. Examples of titanium-containing sulfates include titanium oxysulfate.

[0087] Salt concentration adjustment process

[0088] The salt concentration adjustment step is a step of introducing salt S or its precursor into the system or removing it from the system to adjust the molar concentration of salt S or its precursor relative to the amount of substance of titanium atoms in the system, and is sometimes referred to as step E. The system refers to the reaction system in the method for producing titanium-containing silicon oxide, for example, before step A, in step A, between step A and step B, in step B, between step B and step C, in step C, and after step C. Salt S is at least one selected from the group consisting of ammonium salts, alkali metal salts, and alkaline earth metal salts. Here, ammonium salts include not only ammonium ions in a narrow sense (NH4 + ) and anions, and also includes substituted ammonium ions ([NR 1 R 2 R 3 R 4 ] + ) with an anion.

[0089] The concentration of the salt S or its precursor in the system can be appropriately adjusted according to the composition of the desired target product, and can be preferably adjusted so that the molar concentration of the salt S is 0.004 to 10 relative to the amount of titanium atoms in the titanium-containing silicon oxide.

[0090] As a method for introducing or removing the salt S or its precursor into or from the system, the following method is preferred, but the method is not limited thereto.

[0091] Method for introducing salt S or its precursor into the raw materials of step A, step B and / or step C

[0092] As an example of the method of introduction, a method of adding salt S to the raw materials of each step and mixing them can be cited. It is also possible to introduce the generated salts by adding precursors of multiple salts S to the raw materials of each step and reacting them on the spot. In addition, the introduction can also be carried out in multiple steps.

[0093] Method for removing the above-mentioned salt or its precursor from the reaction solution in the system

[0094] Examples of the removal method include filtration, distillation, splitting, recrystallization, sublimation, chromatography, ion exchange, adsorption separation, extraction separation, and any combination thereof. In addition, the removal may be performed in a plurality of steps.

[0095] Method for introducing the above-mentioned salt into the solid obtained in step A, step B and / or step C

[0096] As an example of the method of introduction, it can be listed: an impregnation method of introducing a solution obtained by dissolving salt S or its precursor in an alcohol solvent such as methanol, ethanol and / or water into the solid by a pore filling method, an impregnation method of introducing the solid into the solution, a spraying method of introducing the solution into the solid, a method of contacting the steam (vapor) obtained by gasifying the salt S or its precursor or the gas of the salt S or its precursor with the solid, etc. It is also possible to introduce the generated salt by adding a plurality of salt S precursors and reacting on the spot at this time. In addition, the introduction can also be implemented in multiple steps.

[0097] Method for removing salt S or its precursor from the solid obtained in step A, step B, and step C

[0098] As the example of the method of removing, the method of removing by sublimation or thermal decomposition in high temperature, decompression or its both sides environment, the screening, centrifugation, gas flow classification etc. utilizing difference in particle size can be enumerated. In addition, the method of removing the salt S or its precursor in the solid by making the solvent with high solubility to the salt S or its precursor contact with the solid can also be used. At this moment, as pre-treatment, the pre-treatment of the salt S or its precursor being converted to the salt that is easily dissolved in a specific solvent can be implemented. In addition, this removal can also be implemented in a plurality of steps.

[0099] Types of salt

[0100] A salt is a compound in which an anion from an acid (anion) is ionically bonded to a cation from a base (cation). A salt S suitable for the purpose of the present invention is any combination of the following cations and anions: the cation is selected from ammonium ions ([NR 5 R 6 R 7 R 8 ] + ; R 5 ~R 8 Each independently represents C 1～6 hydrocarbon groups or H), alkali metal ions (especially Li + 、Na + , K + , Rb + , Cs + ) and alkaline earth metal ions (especially Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ ) or more. The anion is selected from halide ions (especially Cl - Br - ,I - ), nitrate ion (NO3 - ), sulfate ion (SO4 2-), phosphate ion (PO4 3- ), hydroxide ion (OH - ), carbonate ions (CO3 2- ), bicarbonate ion (HCO3 - ), organic acid radical ions (RCOO - ; R is C 1～6 Hydrocarbon or H), alkoxide ions (RO - ; R is C 1～6 As examples of the salt S of the present invention, any combination of the following cations and anions can be cited: the cation is selected from ammonium ions (NH4 + ), sodium ion (Na + ), the anion is selected from chloride ions (Cl - ), formate ion (HCOO - ), acetate ion (CH3COO - ) or more. In addition, more specific examples of the salt S include ammonium chloride (NH4Cl), ammonium formate (HCOONH4) and sodium acetate (CH3COONa).

[0101] Types of salt precursors

[0102] The precursor of the salt refers to the anion and cation that form the salt and the compound in the stage before the anion or cation is generated. Examples of precursor compounds for generating cations suitable for the purpose of the present invention include: 1 R 2 R 3 ; R 1 ~R 3 Each independently is an alkyl group or H, and the alkyl group is preferably C 1～6 of hydrocarbon), alkylsilazane (NR 1 R 2 R 3 ; R 1 ~R 3 Each independently represents an alkylsilyl group, an alkyl group, or H, at least one of which is a silyl group), ammonia complexes of metals, cyanamides, alkali metals (especially Li, Na, K, Rb, Cs) and alkaline earth metals (especially Mg, Ca, Sr, Ba). Examples of precursor compounds for generating anions suitable for the purpose of the present invention include: hydrogen halides (especially HCl, HBr, HI), nitric acid (HNO3), sulfate ions (H2SO4), phosphoric acid (H3PO4), carbonic acid (H2CO3), organic acids (RCOOH; R is an alkyl group or H, and the alkyl group is preferably C 1～6alkyl), metal alkoxide ((RO)nM; R is an alkyl group or H, the alkyl group is preferably C 1～6 M is an alkali metal or an alkaline earth metal, preferably one or more selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and n is 1 or 2).

[0103] Uses of titanium-containing silicon oxides

[0104] The titanium-containing silicon oxide of the present invention can be used as a catalyst for an oxidation reaction of an organic compound, for example, an epoxidation reaction of an olefin, and is particularly preferably used for reacting an olefin with a hydroperoxide to produce an epoxide.

[0105] The olefin used in 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 has two or more double bonds in the molecule, these double bonds may be conjugated bonds or non-conjugated bonds. 2～60 Olefins. Olefins may have substituents. Examples of such olefins include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 2-hexene, 3-hexene, 1-octene, 1-decene, styrene and cyclohexene. Olefins may contain substituents containing oxygen atoms, sulfur atoms or nitrogen atoms together with hydrogen atoms or carbon atoms, or both. Examples of such olefins include allyl alcohol, crotyl alcohol and allyl chloride. Examples of dienes include butadiene and isoprene. Examples of preferred olefins include α-olefins. Examples of particularly preferred olefins include propylene.

[0106] Examples of methods for producing propylene for the epoxidation reaction are not particularly limited, and examples thereof include cracking of naphtha and ethane; fluid catalytic cracking of vacuum gas oil; dehydrogenation of propane; disproportionation of ethylene and 2-butene; MTO (methanol to olefins) reaction for converting methanol or dimethyl ether; Fischer-Tropsch (FT) synthesis for reacting carbon monoxide with hydrogen; dehydration of isopropanol, etc. Propylene produced by methods that reduce the load on the environment, such as a method for obtaining propylene by producing bioethanol and / or isopropanol from plants as raw materials; a FT synthesis method using carbon dioxide or biomass; a method for catalytic cracking of waste plastics, etc., can also be used as a substrate for the above-mentioned epoxidation reaction.

[0107] Examples of hydroperoxides include organic hydroperoxides. Organic hydroperoxides are compounds having the formula III.

[0108] ROOH III

[0109] (In Formula III, R is a hydrocarbon group.)

[0110] Organic hydroperoxides react with olefins to form epoxides and hydroxy compounds. R in formula III is preferably C 3～20 The hydrocarbon group is more preferably C 3～10 The organic hydroperoxide may be a straight chain or a branched chain, and may be aliphatic or aromatic. Examples of organic hydroperoxides include tert-butyl hydroperoxide, 1-phenylethyl hydroperoxide, and cumene hydroperoxide. Hereinafter, cumene hydroperoxide may be referred to as CMHP.

[0111] When CMHP is used as an organic hydroperoxide, the obtained hydroxy compound is 2-phenyl-2-propanol. The 2-phenyl-2-propanol undergoes a dehydration reaction and a hydrogenation reaction to generate cumene. Hereinafter, cumene is sometimes referred to as CUM. In addition, by oxidizing the CUM, CMHP can be obtained again. From such a viewpoint, it is preferred to use CMHP as an organic hydroperoxide for epoxidation reaction.

[0112] The epoxidation reaction can be carried out in a liquid phase using a solvent, a diluent or a mixture thereof. The solvent and the diluent must be liquid at the temperature and pressure during the reaction and be substantially inert to the reactants and products. When CMHP is subjected to the epoxidation reaction in the presence of CUM as its raw material, CUM may be used as a solvent without adding a solvent in particular.

[0113] The epoxidation reaction temperature is usually 0° C. to 200° C., preferably 25° C. to 200° C. The epoxidation reaction pressure may be a pressure sufficient to keep the reaction phase in a liquid state, and is usually preferably 100 kPa to 10000 kPa.

[0114] After the epoxidation reaction is completed, a liquid mixture containing the desired product can be separated from the titanium-containing silicon oxide. The liquid mixture can then be purified by an appropriate method. Examples of purification methods include distillation, extraction, and washing. The solvent and unreacted olefin can be recycled and reused.

[0115] The reaction using the titanium-containing silicon oxide manufactured by one embodiment of the present invention as a catalyst can be carried out in the form of a slurry or a fixed bed, and preferably a fixed bed is used in the case of large-scale industrial operation. In the case of using the titanium-containing silicon oxide manufactured by one embodiment of the present invention as a catalyst, it can be a powder or a molded body. In the case of using a fixed bed reaction, the titanium-containing silicon oxide is preferably a molded body. This reaction can be implemented by a batch type, a semi-continuous method or a continuous method.

[0116] Example

[0117] Hereinafter, one embodiment of the present invention will be described in more detail with reference to examples.

[0118] Example 1

[0119] (1) Raw material mixing process and titanium introduction process

[0120] Hexadecyltrimethylammonium hydroxide (CTAH) (125 parts by mass in terms of the amount of a 16% by mass solution) diluted to a concentration of 16% by mass by a mixed solvent having a mixing ratio (mass ratio) of water: methanol = 72:28 was stirred, and a mixed solution of 1.9 parts by mass of tetraisopropyl titanate and 4.5 parts by mass of 2-propanol was added dropwise thereto at room temperature while stirring. After the addition was completed, it was stirred for 30 minutes, and then 38 parts by mass of tetramethyl orthosilicate was added dropwise while stirring. Then, stirring was continued at room temperature for 3 hours, and the resulting solid was filtered out. The obtained solid was dried at 70°C under reduced pressure to obtain 34.8 parts by weight of a white solid. Hexadecyltrimethylammonium hydroxide, tetramethyl orthosilicate, and tetraisopropyl titanate are templates, silicon sources, and titanium sources, respectively.

[0121] Water was added to 15 parts by weight of the obtained white solid so that the water content reached 1.3 parts by weight, and the mixture was fully mixed. Then, the obtained mixture was compression molded. The obtained molded body was crushed, and the obtained crushed material was sieved to obtain 10 parts by weight of a classified molded body containing a template having a particle size of 1.0 mm to 2.0 mm.

[0122] (2) Template removal process

[0123] The above-obtained molded body 20g was filled into a cylindrical glass column with an inner diameter of 30mm (outer diameter of the sheath tube 8mm) and a height of 27cm set vertically. At this time, the filling length of the molded body was 6.3cm. Then, the following three solutions were passed from the bottom of the column to the top in sequence. First, at a column temperature of 25°C, 141g of methanol was passed at a liquid flow rate of 3.5g / min. Then, at a column temperature of 38°C, a mixed solution of 326g of methanol and 8g of concentrated hydrochloric acid (hydrogen chloride content 36% by mass) was passed at a liquid flow rate of 3.0g / min. Then, at a column temperature of 38°C, 190g of methanol was passed at a liquid flow rate of 3.5g / min, and thereafter, 126g of methanol was passed at a liquid flow rate of 3.5g / min while the column was cooled to 25°C. Then, a solution containing a template and methanol in the column was extracted from the bottom of the column.

[0124] Next, 47 g of toluene was introduced into the column at a column temperature of 75 ° C and a liquid flow rate of 2.8 g / min, and then 157 g of toluene was introduced while the column temperature was raised to 90 ° C. Thus, the above-mentioned mixed solution remaining in the column at the end of the template removal process was replaced with toluene. Then, the toluene in the column was extracted from the lower part of the column. Then, nitrogen was made to flow upward from the lower part of the column at a flow rate of 50 NmL / min at a column temperature of 120 ° C. After confirming that the distillation of the liquid from the upper part of the column stopped, it was changed to a flow rate of 150 NmL / min, and nitrogen was circulated for a total of 2 hours, thereby drying the molded body. Thus, 8 g of solid was obtained.

[0125] (3) Silylation step

[0126] 8 g of the solid obtained in the template removal step, 8 g of trimethylsilyl chloride, and 80 g of toluene were mixed and heated under reflux for 1.5 hours. After natural cooling, the solid was filtered out. The obtained solid was washed twice with 80 g of toluene and dried under reduced pressure at 120° C. and 10 mmHg for 2 hours to obtain 11 g of solid.

[0127] (4) Salt concentration adjustment process

[0128] 100 g of a methanol solution in which 0.03 g of ammonium chloride was dissolved was added to 10 g of the solid obtained in the silylation step, and the mixture was stirred at room temperature for 1 hour. The solvent was removed under reduced pressure using a rotary evaporator at 40° C. and 50 mmHg, and then dried at 60° C. and 10 mmHg for 2 hours to obtain 10 g of titanium-containing silicon oxide.

[0129] Catalyst performance evaluation was performed by the method described below.

[0130] (5) Evaluation of catalyst performance

[0131] The performance of the titanium-containing silicon oxide obtained through the above steps (1) to (4) was evaluated using a batch reactor (autoclave). 0.5 g of the titanium-containing silicon oxide, 60 g of a solution in which CMHP was dissolved in CUM at a concentration of 25% by mass (hereinafter referred to as 25% by mass CMHP / CUM), and 33 g of propylene were supplied to the autoclave, and reacted under autogenous pressure at a reaction temperature of 100° C. for a reaction time of 1.5 hours (including the heating time). The reaction results are shown in Table 1.

[0132] The "CMHP conversion rate", "PO selectivity" and "PGs (polypropylene glycols) selectivity)" in the table were calculated as follows.

[0133] CMHP conversion rate (%) = M1 / M2×100

[0134] M0: molar amount of raw material CMHP

[0135] M1: molar amount of CMHP in the liquid after the reaction

[0136] M2: molar amount of CMHP reacted

[0137] Here, M2=M0-M1

[0138] PO selection rate (%) = M PO / M2×100

[0139] M PO : Molar amount of PO generated

[0140] Here, M PO =M2-(M ph +M ac +M pg +2×M dpg +3×M tpg )

[0141] M ph : Molar amount of phenol generated

[0142] M ac : Molar amount of acetophenone generated

[0143] M pg : Molar amount of propylene glycol generated

[0144] M dpg : Molar amount of dipropylene glycol generated

[0145] M tpg : Molar amount of tripropylene glycol generated

[0146] PGs selection rate (%) = M PGs / M2×100

[0147] M PGs : Molar amount of PGs generated

[0148] Here, M PGs =M pg +2×M dpg +3×M tpg

[0149] (6) Evaluation of pore structure

[0150] In order to evaluate the pore structure of the titanium-containing silicon oxide obtained through the above steps (1) to (4), a pretreatment of vacuum heating and degassing was carried out at 120°C for 2 hours using BELSORP MINI X manufactured by Microtrac BEL. Then, nitrogen adsorption of the titanium-containing silicon oxide was measured, and the average pore size, total pore volume and pore distribution were calculated by the BJH method. ~200 The total pore volume of 5 ~200 The pore structure is shown in Table 2.

[0151] Examples 2 to 5 and Comparative Examples 1 and 2

[0152] For Examples 2 to 5 and Comparative Examples 1 and 2, the steps (1), (2) and (3) and the evaluations (5) and (6) were carried out in the same manner as in Example 1. The step (4) was carried out in the same manner as in Example 1 except that the amount of ammonium chloride added was changed as described in Table 1.

[0153]

[0154]

[0155] Examples 6 and 7

[0156] In Examples 6 and 7, the steps (1), (2) and (3) and the evaluations (5) and (6) were carried out in the same manner as in Example 1. The step (4) was carried out in the same manner as in Example 1 except that the type (ammonium chloride) and concentration of the salt described in Table 1 were changed as described in Table 3.

[0157]

[0158]

[0159] Industrial Applicability

[0160] The method for producing titanium-containing silicon oxide according to one embodiment of the present invention can be applied to the production of a catalyst that can be used in a reaction of producing epoxide from olefin and hydroperoxide. The titanium-containing silicon oxide obtained by this method can be used as a catalyst for producing propylene oxide, for example.

Claims

1. A titanium-containing silicon oxide, wherein: The titanium-containing silicon oxide satisfies all of conditions 1 to 5: Condition 1: Average pore size is 10 above; Condition 2: More than 80% of the total pore volume has 5 ~200 The aperture of Condition 3: Total pore volume is 0.2 cm 3 / g or more; Condition 4: The titanium-containing silicon oxide is obtained by using a quaternary ammonium ion represented by formula I as a template and then removing the template by a solvent extraction operation, [NR 1 R 2 R 3 R 4 ] + I (In Formula I, R 1 Represents C 2～36 The hydrocarbon group, R 2 ~R 4 Each independently represents C 1～6 alkyl of Condition 5: The ratio of the amount of the salt S to the amount of the titanium atoms in the titanium-containing silicon oxide is 0.004 to 10, and the salt S is at least one selected from the group consisting of ammonium salts, alkali metal salts, and alkaline earth metal salts.

2. The titanium-containing silicon oxide according to claim 1, wherein The ammonium salt is ammonium chloride.

3. Use of the titanium-containing silicon oxide according to claim 1 or 2, wherein: The titanium-containing silicon oxide is used for producing epoxides from olefins.

4. A method for producing titanium-containing silicon oxide, wherein: The method for producing titanium-containing silicon oxide comprises the following steps: A step of mixing a silicon source, a template, and a solvent to obtain a solid containing silicon oxide and the template (raw material mixing step); a step of removing the template from the solid obtained in the raw material mixing step to obtain a solid containing silicon oxide (template removal step); a step of obtaining a solid body including silylated silicon oxide by contacting the solid obtained in the template removal step with a silylating agent (silylation step); A step of introducing titanium into the system (titanium introduction step); A process of introducing salt S or its precursor into or removing it from the system to adjust the molar concentration of salt S or its precursor relative to the amount of substance of titanium atoms in the system, wherein salt S is at least one selected from the group consisting of ammonium salts, alkali metal salts and alkaline earth metal salts (salt concentration adjustment process).

5. A method for producing an epoxide, wherein: The method for producing epoxide comprises the step of reacting olefin and hydroperoxide in the presence of the titanium-containing silicon oxide according to claim 1 or 2.

6. The method according to claim 5, wherein: The olefin is propylene.

7. The method according to claim 5 or 6, wherein: The hydroperoxide is cumene hydroperoxide.

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