[go: up one dir, main page]

WO2018186491A1 - Procédé de production d'oxyde de silicium contenant du titane, procédé de production d'époxyde, et oxyde de silicium contenant du titane - Google Patents

Procédé de production d'oxyde de silicium contenant du titane, procédé de production d'époxyde, et oxyde de silicium contenant du titane Download PDF

Info

Publication number
WO2018186491A1
WO2018186491A1 PCT/JP2018/014753 JP2018014753W WO2018186491A1 WO 2018186491 A1 WO2018186491 A1 WO 2018186491A1 JP 2018014753 W JP2018014753 W JP 2018014753W WO 2018186491 A1 WO2018186491 A1 WO 2018186491A1
Authority
WO
WIPO (PCT)
Prior art keywords
titanium
silicon oxide
solid
carbon atoms
hydrocarbon group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/014753
Other languages
English (en)
Japanese (ja)
Inventor
史一 山下
翔子 池田
卓也 小澤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Priority to CN201880022900.2A priority Critical patent/CN110475748B/zh
Priority to JP2019511321A priority patent/JP6970739B2/ja
Priority to KR1020197032490A priority patent/KR102493560B1/ko
Publication of WO2018186491A1 publication Critical patent/WO2018186491A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/36—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for producing a titanium-containing silicon oxide, a method for producing an epoxide from an olefin using a titanium-containing silicon oxide produced by the method as a catalyst, and a titanium-containing silicon oxide.
  • a method for producing an epoxide from hydroperoxide and olefin in the presence of a catalyst is known.
  • a catalyst used in this method for example, in Patent Document 1, a silica source, a titanium source, and a mold agent are mixed in a liquid state to obtain a solid containing a catalyst component and a mold agent.
  • the second step of removing the mold from the obtained solid by solvent extraction operation, and the extraction solvent contained in the solid after removing the mold obtained in the second step are substantially the same as the silylating agent used in the following fourth step.
  • Containing titanium obtained by a production method comprising a third step of substituting with a chemically inert solvent and a fourth step of obtaining a silylated catalyst by subjecting the solid obtained in the third step to silylation treatment
  • a silicon oxide catalyst is described.
  • the problem to be solved by the present invention is to provide a method for producing a titanium-containing silicon oxide capable of maintaining a high catalytic activity over a long period of time when used as a catalyst in a reaction for producing an epoxide from an olefin and a hydroperoxide. There is in point to do.
  • One embodiment of the present invention includes the following steps: Step A: Mixing a mold, a silicon source, and a solvent to obtain a solid containing the mold and silicon oxide Step B: Removing the mold from the solid obtained through the process A to obtain a solid Process Step C: A treatment agent containing 0.01 to 20% by mass of water is brought into contact with the solid obtained through Step B to obtain a solid. Step D: The solid obtained through Step C is combined with a silylating agent. Contacting to obtain a solid, At least selected from the group consisting of Step A, Step B, Step C, Step D, Step A and Step B, Step B and Step C, and Step C and Step D In one or more, the present invention relates to a titanium-containing silicon oxide that introduces titanium into a solid.
  • a titanium-containing silicon oxide that can maintain a high catalytic activity over a long period of time when used as a catalyst in a reaction for producing an epoxide from an olefin and a hydroperoxide.
  • the method for producing a titanium-containing silicon oxide according to one embodiment of the present invention includes steps AD.
  • Titanium-containing silicon oxide refers to a compound having a bond represented by -Si-O-Ti.
  • Step A is a step of mixing a mold agent, a silicon source, and a solvent to obtain a solid containing the mold agent and silicon oxide, and may be referred to as a raw material mixing step.
  • Silicon source refers to silicon oxide and silicon oxide precursor.
  • the silicon oxide precursor refers to a compound in which part or all of the silicon oxide precursor is converted into silicon oxide by mixing the silicon oxide precursor and water.
  • Examples of the silicon oxide as the silicon source include amorphous silica.
  • Examples of the silicon oxide precursor as the silicon source include alkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and 1,2-bis (trialkoxysilyl) alkane.
  • Alkoxysilanes include tetramethylorthosilicate, tetraethylorthosilicate, and tetrapropylorthosilicate.
  • Examples of the alkyltrialkoxysilane include trimethoxy (methyl) silane.
  • Examples of the dialkyl dialkoxysilane include dimethoxydimethylsilane.
  • a single silicon source may be used, or several types may be used in combination.
  • silicon oxide precursor When a silicon oxide precursor is used as the silicon source, water is used as a part or all of the solvent in the step. When the silicon oxide precursor is mixed with water, part or all of the silicon oxide precursor is changed to silicon oxide.
  • the mold agent refers to a substance that can form a pore structure in titanium-containing silicon oxide.
  • a surfactant is preferable.
  • the surfactant include a cationic surfactant, an anionic surfactant, and a nonionic surfactant.
  • the cationic surfactant include quaternary ammonium compounds containing quaternary ammonium ions and alkylamine salts.
  • the quaternary ammonium compound containing a quaternary ammonium ion include tetraalkylammonium hydrochloride, tetraalkylammonium acetate, and tetraalkylammonium hydroxide.
  • Alkylamine salts include monoalkylamine hydrochloride, monoalkylamine acetate, dialkylamine hydrochloride, dialkylamine acetate, trialkylamine hydrochloride, and trialkylamine acetate.
  • the anionic surfactant include alkylbenzene sulfonic acid and its salt, ⁇ -olefin sulfonic acid sodium salt, alkyl sulfate ester salt, alkyl ether sulfate ester salt, methyl tauric acid, alaninate and salt thereof, ether carboxylic acid and salt thereof, sulfosuccinate.
  • Nonionic surfactants include polyalkylene oxides or block copolymers of polyalkylene oxides, and alkylamines.
  • the cationic surfactant is preferably a salt containing a quaternary ammonium ion represented by the following formula (I).
  • the nonionic surfactant is preferably an amine represented by the following formula (II).
  • R 1 represents a linear or branched hydrocarbon group having 2 to 36 carbon atoms
  • R 2 to R 4 each independently represents a hydrocarbon group having 1 to 6 carbon atoms.
  • NR 5 R 6 R 7 (II)
  • R 5 represents a linear or branched hydrocarbon group having 2 to 36 carbon atoms
  • R 6 and R 7 are each independently a hydrogen atom or a carbon atom having 1 to 6 carbon atoms.
  • R 1 is a linear or branched hydrocarbon group having 2 to 36 carbon atoms, preferably a hydrocarbon group having 10 to 22 carbon atoms.
  • R 2 to R 4 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and it is preferable that all of R 2 to R 4 are methyl groups.
  • quaternary ammonium ion represented by the formula (I) include tetraethylammonium, tetrapropylammonium, tetrabutylammonium, decyltrimethylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, eicosyltrimethyl. Mention may be made of cations such as ammonium, behenyltrimethylammonium, benzyltrimethylammonium, dimethyldidodecylammonium and hexadecylpyridinium.
  • the salt containing a quaternary ammonium ion represented by the formula (I) include 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 , Octadec Contains trimethylammonium bromide, eicosyltri
  • R 5 is a linear or branched hydrocarbon group having 2 to 36 carbon atoms, preferably 10 to 22 carbon atoms.
  • R 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 are preferably hydrogen atoms.
  • amine represented by the formula (II) include ethylamine, propylamine, butylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecyl.
  • a single material may be used, or several types may be used in combination.
  • Mixing of mold and silicon source is performed in the presence of a solvent.
  • a solvent examples include water and alcohol.
  • examples of the alcohol include methanol, ethanol, 1-propanol, and 2-propanol.
  • the solid containing a mold agent and silicon oxide is obtained.
  • the solid containing the mold and silicon oxide obtained through step A can be taken out by filtration or the like.
  • the mixing in step A is preferably carried out in the temperature range of 20 to 200 ° C. over 2 to 1000 hours. Moreover, stirring can also be implemented during mixing.
  • the process B is a process of removing the mold from the solid containing the mold obtained through the process A and the silicon oxide to obtain a solid, and may be referred to as a mold removing process.
  • a mold removing process By performing the step B, a solid which does not contain a mold or substantially does not contain a mold is obtained.
  • the content of the mold in the solid obtained in Step B is preferably 10% by mass or less, and more preferably 1% by mass or less.
  • the removal of the mold can be achieved by firing the solid containing the mold in air at 300 to 800 ° C. or by extracting with a solvent. It is preferable to remove the template by extraction.
  • the solvent is not particularly limited as long as it can dissolve the compound used as the mold, and generally a compound having 1 to 12 carbon atoms that is liquid at room temperature or a mixture of two or more of these compounds can be used.
  • Suitable solvents include alcohols, ketones, acyclic and cyclic ethers and esters. Examples of the alcohol include methanol, ethanol, ethylene glycol, propylene glycol, 1-propanol, 2-propanol, 1-butanol and octanol.
  • Ketones include acetone, diethyl ketone, methyl ethyl ketone and methyl isobutyl ketone.
  • ethers include diisobutyl ether and tetrahydrofuran.
  • Esters include methyl acetate, ethyl acetate, butyl acetate and butyl propionate.
  • the solvent from the viewpoint of the solubility of the mold, for example, when the mold is a salt containing a quaternary ammonium ion, an alcohol is preferable, and methanol is more preferable.
  • the mass ratio of the solvent to the solid containing the mold is usually 1 to 1000, preferably 5 to 300.
  • an acid or a salt thereof may be added to these solvents.
  • the acid used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and odorous acid, or organic acids such as formic acid, acetic acid, and propionic acid.
  • such salts include alkali metal salts, alkaline earth metal salts, and ammonium salts.
  • the concentration of the added acid or salt thereof in the solvent is preferably 30% by mass or less, and more preferably 15% by mass or less.
  • Examples of the method for removing the mold include a method in which the solvent and the solid containing the mold are sufficiently mixed, and then the liquid phase part is separated by a method such as filtration or decantation. This operation may be repeated a plurality of times. It is also possible to extract the mold by filling the solid containing the mold into a container such as a column and circulating the extraction solvent.
  • 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 template in the solution obtained by the extraction treatment can be recovered and reused as the template in step A.
  • the extraction solvent can be purified and reused by a normal distillation operation or the like.
  • Step C is a step of obtaining a solid by bringing a treatment agent containing 0.01 to 20% by mass of water into contact with the solid obtained through Step B, and is sometimes referred to as a water treatment step.
  • the water content in the treating agent is 0.01 to 20% by mass, more preferably 0.02 to 10% by mass, still more preferably 0.02 to 5% by mass, and more preferably 0.1 to Most preferably, it is 2 mass%. If the water content is too high, the catalyst performance of the titanium-containing silicon oxide, particularly the catalyst activity, will be adversely affected.
  • the weight of the treatment agent containing water is usually 1 to 1000, preferably 1 to 500, more preferably 1 to 200, where the weight of the solid obtained through the step B is 1. More preferably, it is ⁇ 100.
  • the treating agent contains, for example, at least one selected from nitrogen-containing basic compounds, alcohols, carboxylic acids, and these compounds.
  • the treating agent is an aprotic polar compound (for example, a nitrogen-containing base compound), a protic polar compound (for example, an alcohol, a carboxylic acid, or a compound thereof), or a mixture of a protic polar compound and an aprotic polar compound. possible.
  • Step C refers to a step of bringing water contained in the treatment agent into contact with the solid by bringing the treatment agent containing 0.01 to 20% by mass of water into contact with the solid.
  • the “treatment agent” used in Step C is distinguished from the “treatment liquid” used in other steps.
  • step C the treatment agent may be brought into contact with the solid obtained through step B one or more times.
  • the treatment agent may be the same or different.
  • step C after bringing the treatment agent containing water into contact with the solid obtained through step B one or more times, Replacement with a treatment solution containing less than 0.01% water containing a protic polar solvent, aprotic polar solvent, a protic polar solvent containing a nonpolar compound, or an aprotic polar solvent containing a nonpolar compound May be.
  • the protic polar solvent include alcohols described below
  • examples of the aprotic polar solvent include ketones, nitriles, and esters described below
  • examples of the nonpolar compound include toluene.
  • R 8 to R 10 are each independently a hydrogen atom, a linear hydrocarbon group having 1 to 18 carbon atoms, a branched hydrocarbon group having 3 to 18 carbon atoms, or carbon Represents a cyclic hydrocarbon group having 5 to 18 atoms.
  • nitrogen-containing base compound represented by the formula (III) include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n- Propylamine, dimethylethylamine, dimethylpropylamine, diethylmethylamine, diethylbutylamine, methylethylpropylamine, methylethylbutylamine, dipropylmethylamine, methylpropylbutylamine, dibutylmethylamine, triethylamine, diethylpropylamine, dipropylethylamine, ethyl Propylbutylamine, dibutylethylamine, tripropylamine, dipropylbutylamine, dibutylpropylamine, tributylamine, pentyla Emissions, hexylamine, and tri -n-
  • R 11 to R 15 are each independently (a) a linear hydrocarbon group having 1 to 6 carbon atoms, a branched hydrocarbon group having 3 to 6 carbon atoms, and carbon.
  • nitrogen-containing base compound represented by the formula (IV) examples include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, and quinoline.
  • Preferred nitrogen-containing base compounds are tertiary amine, ammonia, and pyridine, and tri-n-octylamine, ammonia, and pyridine are more preferred. These nitrogen-containing base compounds may be used alone or in combination of two or more.
  • the treatment agent contains alcohol
  • examples of the alcohol include primary alcohols, secondary alcohols, and tertiary alcohols, alcohols having 1 to 12 carbon atoms are preferred, tertiary alcohols are more preferred, and tert-butyl alcohol is preferred. Further preferred.
  • the carboxylic acid is preferably a carboxylic acid having 1 to 12 carbon atoms, and more preferably formic acid, acetic acid and propionic acid.
  • solvents for dilution include non-polar organic solvents (non-polar compounds) such as hydrocarbons having 1 to 12 carbon atoms and halogenated hydrocarbons that are liquid at room temperature, ketones, ethers, esters, N, N-2 Aprotic polar organic solvents (aprotic polar compounds) such as substituted amides, nitriles and sulfoxides.
  • non-polar organic solvents non-polar compounds
  • hydrocarbons having 1 to 12 carbon atoms such as hydrocarbons having 1 to 12 carbon atoms and halogenated hydrocarbons that are liquid at room temperature
  • ketones, ethers, esters ketones, ethers, esters, N, N-2 Aprotic polar organic solvents (aprotic polar compounds) such as substituted amides, nitriles and sulfoxides.
  • hydrocarbon having 1 to 12 carbon atoms which are liquid at normal temperature include hexane, cyclohexane, benzene, toluene and
  • halogenated hydrocarbon is chloroform.
  • ketone include acetone, diethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone.
  • ethers include diethyl ether, diisobutyl ether, tetrahydrofuran, and dioxane.
  • ester examples include methyl acetate and ethyl acetate.
  • N, N-disubstituted amides include dimethylformamide.
  • a nitrile includes acetonitrile.
  • the sulfoxide include dimethyl sulfoxide.
  • the organic compound is preferably an alcohol having 1 to 12 carbon atoms, a hydrocarbon having 1 to 12 carbon atoms which is liquid at room temperature, a ketone or a nitrile, and tert-butyl alcohol, 2-methyl-2-butanol, acetonitrile, hexane. , Cyclohexane, benzene, toluene, xylene, and acetone are preferred.
  • the contact temperature between the treating agent and the solid after removing the mold material is usually 0 to 200 ° C., more preferably 0 to 150 ° C. Such contact can be performed by, for example, a batch method and a distribution method. When the boiling point of the treatment agent is low, step C may be performed under pressure.
  • Step C After the completion of Step C, it is preferable to reduce the amount of components active against silylation contained in the solid obtained through Step C before the start of Step E below.
  • Examples of a method for reducing the amount of an active component for silylation include liquid replacement and / or drying described later.
  • Step E is a step of replacing the treatment agent and / or treatment liquid contained in the solid obtained through Step C with a liquid that is substantially inert to the silylating agent, and is referred to as a liquid substitution step.
  • the substantially inert liquid include hydrocarbons, haloalkanes, and ethers.
  • the hydrocarbon include aliphatic or aromatic hydrocarbons having 6 to 14 carbon atoms.
  • the haloalkane include dichloromethane and tetrachloroethylene.
  • ethers include diethyl ether and tetrahydrofuran.
  • the substantially inert liquid used in step E is preferably a hydrocarbon, and more preferably toluene.
  • the temperature of the replacement liquid in the liquid replacement is usually 0 to 200 ° C. Liquid replacement can be carried out by a batch method or a flow method.
  • the pressure is preferably normal pressure or reduced pressure.
  • a suitable temperature varies depending on the treatment liquid, it is generally 0 ° C. or higher and 700 ° C. or lower and preferably 0 ° C. or higher and 200 ° C. or lower from the viewpoint of catalyst performance. Drying can be carried out by a batch method or a gas flow method.
  • the drying of the solid is not limited to the drying after the step C.
  • the solid is dried under the same conditions as in the step F after the completion of any of these steps and before the next step. Drying may be performed. Moreover, you may perform either one or both of the process E and the process F before the process D after the process C.
  • Step D is a step of obtaining a solid by bringing the solid obtained through Step C into contact with a silylating agent. By performing Step D, the solid obtained through Step C is silylated.
  • the silylation may be performed by a gas phase method in which a gaseous silylating agent is brought into contact with the solid obtained through Step C and reacted, or the silylating agent and the solid are brought into contact in a solvent to be reacted.
  • the liquid phase method may be used, and in one embodiment of the present invention, the liquid phase method is more preferable.
  • a hydrocarbon is used suitably as a solvent in the process D.
  • drying may be performed thereafter.
  • a silylating agent is a silicon compound that is reactive to a solid, and a hydrolyzable group is bonded to silicon, and the silicon includes an allyl group such as an alkyl group or a vinyl group, a phenyl group, or the like. In which at least one group selected from the group consisting of an aryl group, a halogenated alkyl group, and a siloxy group is bonded.
  • the hydrolyzable group bonded to silicon include hydrogen, halogen, alkoxy group, acetoxy group, and amino group.
  • the number of hydrolyzable groups bonded to silicon is preferably one.
  • silylating agent examples include organic silane, organic silylamine, organic silylamide and derivatives thereof, and organic silazane.
  • organic silane examples include chlorotrimethylsilane, dichlorodimethylsilane, chlorobromodimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, iododimethylbutylsilane, chlorodimethylphenylsilane, chlorodimethylsilane, dimethyl n-propylchlorosilane, and dimethylisopropyl.
  • organic silylamine examples include N- (trimethylsilyl) imidazole, N- (tert-butyldimethylsilyl) imidazole, N- (dimethylethylsilyl) imidazole, N- (dimethyln-propylsilyl) imidazole, N- (dimethylisopropyl).
  • Silyl) imidazole N- (trimethylsilyl) -N, N-dimethylamine, N- (trimethylsilyl) -N, N-diethylamine, N- (trimethylsilyl) pyrrole, N- (trimethylsilyl) pyrrolidine, N- (trimethylsilyl) piperidine, Examples thereof include 1-cyanoethyl (diethylamino) dimethylsilane and pentafluorophenyldimethylsilylamine.
  • organic silylamides and derivatives examples 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 (diethyl Hydrosilyl) trifluoroacetamide.
  • organic silazane examples 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-tetra And methyl disilazane.
  • silylating agents include N-methoxy-N, O-bis (trimethylsilyl) trifluoroacetamide, N-methoxy-N, O-bis (trimethylsilyl) carbamate, N, O-bis (trimethylsilyl) sulfamate, Examples include trimethylsilyl trifluoromethanesulfonate and N, N′-bis (trimethylsilyl) urea.
  • a preferred silylating agent is an organic silazane, more preferably 1,1,1,3,3,3-hexamethyldisilazane.
  • Titanium may be introduced into the solid during any of steps A to F. Between step A and step B, between step B and step C, between step C and step E, between step C and step F, between step E and step D, or between step F and step D. In between, titanium may be introduced into the solid.
  • the introduction of titanium into the solid may be performed both during and between the steps described above.
  • titanium is introduced into a solid is expressed by —Si—O—Ti in the silicon oxide contained in the solid by mixing the solid containing the silicon oxide and the titanium source. Means that a bond is introduced.
  • titanium is introduced into the solid before the start of step D, and at least one selected from the group consisting of step A, step B and step C, and step C and step D. In the above, it is more preferable that titanium is introduced into the solid, and it is further preferable that titanium is introduced into the solid within the step A.
  • a silicon source, a titanium source and a mold agent are mixed in the process A.
  • titanium may be introduced into the solid by bringing the solid obtained through step A into contact with the titanium source.
  • titanium may be introduced into the solid by contacting the solid obtained through step B with a titanium source.
  • titanium may be introduced into the solid by bringing the solid obtained through step C into contact with the titanium source.
  • Titanium may be introduced into the solid by contacting the solid into which the titanium is introduced and the titanium source in a liquid phase, and the titanium containing the titanium is brought into contact with the solid into which titanium is introduced by contacting the solid. It may be introduced into a solid.
  • titanium source examples include titanium alkoxide, chelate-type titanium complex, titanium halide, and sulfate containing titanium.
  • titanium alkoxide examples include tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra (2-ethylhexyl) titanate, and tetraoctadecyl titanate.
  • examples of the chelate-type titanium complex include titanium (IV) oxyacetylacetonate and titanium (IV) diisopropoxybisacetylacetonate.
  • titanium halide examples include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide.
  • the sulfate containing titanium examples include titanyl sulfate.
  • the produced titanium-containing silicon oxide 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 the production of an epoxide in which an olefin and a hydroperoxide are reacted.
  • the olefin to be subjected to the epoxidation reaction may be an acyclic olefin, a monocyclic olefin, a bicyclic olefin, a tricyclic or higher polycyclic olefin, or a monoolefin, a diolefin, or a polyolefin.
  • these double bonds may be conjugated bonds or non-conjugated bonds.
  • Olefins having 2 to 60 carbon atoms are preferred.
  • the olefin may have a substituent.
  • olefins examples include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 2-hexene, 3-hexene, 1-octene, 1-decene, styrene, and cyclohexene.
  • olefin there may be a substituent containing an oxygen atom, a sulfur atom, or a nitrogen atom together with a hydrogen atom or a carbon atom, or both.
  • examples of such an olefin include allyl alcohol, crotyl Alcohol and allyl chloride are mentioned.
  • diolefins examples include butadiene and isoprene.
  • Particularly preferred olefins include propylene.
  • An organic hydroperoxide is mentioned as an example of a hydroperoxide.
  • the organic hydroperoxide has the formula (V) R—O—O—H (V) (In the formula (V), R is a hydrocarbon group.) It is a compound which has this.
  • Organic hydroperoxides react with olefins to produce epoxides and hydroxyl compounds.
  • R in the formula (V) 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 the organic hydroperoxide include tert-butyl hydroperoxide, 1-phenylethyl hydroperoxide, and cumene hydroperoxide. Cumene hydroperoxide may hereinafter be abbreviated as CMHP.
  • CMHP When CMHP is used as the organic hydroperoxide, the resulting hydroxyl compound is 2-phenyl-2-propanol.
  • This 2-phenyl-2-propanol produces cumene through a dehydration reaction and a hydrogenation reaction.
  • cumene may be abbreviated as CUM.
  • CUM cumene
  • CHMP is obtained again. From such a viewpoint, it is preferable to use CMHP as the organic hydroperoxide used in the epoxidation reaction.
  • the epoxidation reaction can be performed 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 during the reaction and be substantially inert to the reactants and product.
  • CUM can be used as a solvent without particularly adding a solvent.
  • the epoxidation reaction temperature is generally 0 to 200 ° C., preferably 25 to 200 ° C.
  • the epoxidation reaction pressure may be a pressure sufficient to keep the reaction phase in a liquid state, and is generally preferably 100 to 10,000 kPa.
  • the liquid mixture containing the desired product can be separated from the catalyst composition.
  • the liquid mixture can then be purified by a suitable method. Examples of the purification method include distillation, extraction, and washing.
  • the solvent and unreacted olefin can be recycled and reused.
  • the reaction using the titanium-containing silicon oxide produced according to one embodiment of the present invention as a catalyst can be performed in the form of a slurry or a fixed bed, and in the case of a large-scale industrial operation, it is preferable to use a fixed bed.
  • the titanium-containing silicon oxide produced according to one embodiment of the present invention may be a powder or a molded body.
  • the reaction is performed on a fixed bed, the titanium-containing silicon oxide is preferably a molded body. This reaction can be carried out by a batch method, a semi-continuous method or a continuous method.
  • Hexadecyltrimethylammonium hydroxide, tetramethylorthosilicate, and tetraisopropyl titanate are the mold, silicon source, and titanium source, respectively.
  • Step B Subsequent to Step B, first, 53 g of pyridine containing 0.3% by mass of water as a treating agent was passed at a column temperature of 60 ° C. upward from the bottom of the column at a flow rate of 3.2 g / min. Thereafter, 170 g of the treatment agent was passed at a rate of 3.2 g / min while raising the column temperature to 95 ° C. Thereafter, the treating agent in the column was extracted from the lower part of the column.
  • the column temperature is equal to the contact temperature between the treating agent and the solid after removing the mold material.
  • a treating agent in which 272 g of tert-butyl alcohol, 48 g of acetone and 0.96 g of water were mixed was passed through the column at a column temperature of 45 ° C. from the bottom of the column upward at a flow rate of 2.6 g / min. .
  • Water contained in the treatment agent was 0.3% by mass.
  • the amount of treatment agent supplied to the column was 270 g.
  • the mixed solution of tert-butyl alcohol, acetone and water in the column was extracted from the lower part of the column.
  • Step C 47 g of toluene is passed through the column at a column temperature of 50 ° C. at a flow rate of 2.8 g / min, and then 157 g of toluene is passed while the column temperature is raised to 100 ° C. Liquid. Thereby, the mixed liquid remaining in the column at the end of Step C was replaced with toluene. Thereafter, toluene in the column was extracted from the bottom of the column.
  • Step E a mixed solution of 8 g of 1,1,1,3,3,3-hexamethyldisilazane (hereinafter also referred to as HMDS) and 93 g of toluene was added at a column temperature of 100 ° C. and a flow rate of 3.9 g.
  • the liquid was passed from the bottom of the column at / min.
  • the liquid passed through the column was collected by a receiver and continuously circulated through the column for 3 hours by a pump. Thereby, silylation of the molded body in the column was performed. Thereafter, the toluene and HMDS mixed solution in the column was extracted from the lower part of the column.
  • Life performance evaluation was performed by a series of methods described in (F) to (H) below.
  • TBA is an abbreviation for
  • TAA (230 g) / ACT (40 g) refers to a mixture of 230 g of tert-butyl alcohol and 40 g of acetone.
  • ATN is an abbreviation for acetonitrile
  • AMA is an abbreviation for tert-amyl alcohol (2-methyl-2-butanol).
  • Examples 2 to 9 For Examples 2 to 8, the methods described in (A), (B) and (E) were carried out in the same manner as in Example 1. The methods described in (C) and (D) were performed in the same manner as in Example 1 except that the treatment liquid and the treatment conditions were changed as shown in Tables 1 to 4.
  • Example 9 about the method as described in (A) and (B), it implements by the method similar to Example 1, and about the method as described in (E), the total time of the distribution
  • the procedure was the same as in Example 1 except that.
  • the life performance evaluation of Examples 2 to 9 was performed by the method described in (F) to (H) of Example 1. The evaluation results are shown in Tables 1 to 3.
  • Example 10 The tetraisopropyl titanate is not added in (A), and (B) and (C) are carried out in the same manner as in Example 1. Subsequent to (C), at a column temperature of about 120 ° C., nitrogen gas is flowed upward from the bottom of the column into the column to dry the molded body. Thereafter, nitrogen gas containing 50% by volume of titanium tetrachloride is allowed to flow upwardly from the bottom of the column at a column temperature of about 200 ° C. at a flow rate of about 10 NmL / min, and is brought into contact with the molded body for about 2 hours. Thereafter, nitrogen gas is allowed to flow upward from the bottom of the column into the column at a column temperature of about 500 ° C. at a flow rate of about 100 NmL / min. Thereafter, (E) is carried out in the same manner as in Example 1, whereby a titanium-containing silicon oxide catalyst can be obtained.
  • the method for producing a titanium-containing silicon oxide according to one embodiment of the present invention can be applied to the production of a catalyst used in a reaction for producing an epoxide from an olefin and a hydroperoxide, and titanium obtained by the method.
  • the contained silicon oxide can be used, for example, as a catalyst for the production of propylene oxide.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Catalysts (AREA)
  • Epoxy Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

La présente invention concerne un procédé de production d'un oxyde de silicium contenant du titane qui est capable de maintenir une activité catalytique élevée sur une longue durée dans les cas où l'oxyde de silicium contenant du titane est utilisé comme catalyseur pour une réaction dans laquelle un époxyde est produit à partir d'une oléfine et d'un hydroperoxyde. L'invention concerne également un procédé de production d'un oxyde de silicium contenant du titane, qui comprend l'étape A, l'étape B, l'étape C et l'étape D, tout en comprenant additionnellement une étape d'introduction de titane.
PCT/JP2018/014753 2017-04-07 2018-04-06 Procédé de production d'oxyde de silicium contenant du titane, procédé de production d'époxyde, et oxyde de silicium contenant du titane Ceased WO2018186491A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201880022900.2A CN110475748B (zh) 2017-04-07 2018-04-06 含钛的硅氧化物的制造方法、环氧化物的制造方法、和含钛的硅氧化物
JP2019511321A JP6970739B2 (ja) 2017-04-07 2018-04-06 チタン含有珪素酸化物の製造方法、エポキシドの製造方法、及びチタン含有珪素酸化物
KR1020197032490A KR102493560B1 (ko) 2017-04-07 2018-04-06 티탄 함유 규소 산화물의 제조 방법, 에폭사이드의 제조 방법, 및 티탄 함유 규소 산화물

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-076970 2017-04-07
JP2017076970 2017-04-07

Publications (1)

Publication Number Publication Date
WO2018186491A1 true WO2018186491A1 (fr) 2018-10-11

Family

ID=63712676

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/014753 Ceased WO2018186491A1 (fr) 2017-04-07 2018-04-06 Procédé de production d'oxyde de silicium contenant du titane, procédé de production d'époxyde, et oxyde de silicium contenant du titane

Country Status (4)

Country Link
JP (1) JP6970739B2 (fr)
KR (1) KR102493560B1 (fr)
CN (1) CN110475748B (fr)
WO (1) WO2018186491A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020241052A1 (fr) * 2019-05-29 2020-12-03
RU2805109C2 (ru) * 2019-05-29 2023-10-11 Сумитомо Кемикал Компани, Лимитед Способ получения содержащего титан оксида кремния, способ получения эпоксида и содержащий титан оксид кремния

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001286768A (ja) * 2000-02-02 2001-10-16 Sumitomo Chem Co Ltd 触媒成型体、該触媒成型体の製造方法及びオキシラン化合物の製造方法
US20020164283A1 (en) * 2000-12-22 2002-11-07 Jones Christopher W. Synthesis of molecular sieves by hydrothermal treatment with acid
JP2003200056A (ja) * 2002-01-10 2003-07-15 Sumitomo Chem Co Ltd チタン含有珪素酸化物触媒の製造方法及び触媒
JP2004195379A (ja) * 2002-12-19 2004-07-15 Sumitomo Chem Co Ltd チタン含有珪素酸化物触媒の製造方法及び触媒
JP2006159057A (ja) * 2004-12-06 2006-06-22 Sumitomo Chemical Co Ltd チタン含有珪素酸化物触媒の製造方法及び触媒
JP2010179279A (ja) * 2009-02-09 2010-08-19 Sumitomo Chemical Co Ltd Ｔｉ−ＭＷＷ前駆体の活性化方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE320851T1 (de) * 2001-08-01 2006-04-15 Dow Global Technologies Inc Verfahren zur standzeitverlängerung eines hydro- oxidationskatalysators
CN104437450B (zh) * 2013-09-24 2017-12-15 中国石油化工股份有限公司 含钛二氧化硅催化剂、制备方法及其用途
CN105272945A (zh) * 2014-07-03 2016-01-27 中国石油化工股份有限公司 环氧氯丙烷的生产方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001286768A (ja) * 2000-02-02 2001-10-16 Sumitomo Chem Co Ltd 触媒成型体、該触媒成型体の製造方法及びオキシラン化合物の製造方法
US20020164283A1 (en) * 2000-12-22 2002-11-07 Jones Christopher W. Synthesis of molecular sieves by hydrothermal treatment with acid
JP2003200056A (ja) * 2002-01-10 2003-07-15 Sumitomo Chem Co Ltd チタン含有珪素酸化物触媒の製造方法及び触媒
JP2004195379A (ja) * 2002-12-19 2004-07-15 Sumitomo Chem Co Ltd チタン含有珪素酸化物触媒の製造方法及び触媒
JP2006159057A (ja) * 2004-12-06 2006-06-22 Sumitomo Chemical Co Ltd チタン含有珪素酸化物触媒の製造方法及び触媒
JP2010179279A (ja) * 2009-02-09 2010-08-19 Sumitomo Chemical Co Ltd Ｔｉ−ＭＷＷ前駆体の活性化方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020241052A1 (fr) * 2019-05-29 2020-12-03
WO2020241052A1 (fr) * 2019-05-29 2020-12-03 住友化学株式会社 Procédé de production d'oxyde de silicium contenant du titane, procédé de production d'époxyde et oxyde de silicium contenant du titane
CN113905987A (zh) * 2019-05-29 2022-01-07 住友化学株式会社 含钛的硅氧化物的制造方法、环氧化物的制造方法和含钛的硅氧化物
KR20220014870A (ko) * 2019-05-29 2022-02-07 스미또모 가가꾸 가부시끼가이샤 티탄 함유 규소 산화물의 제조 방법, 에폭시드의 제조 방법, 및 티탄 함유 규소 산화물
RU2805109C2 (ru) * 2019-05-29 2023-10-11 Сумитомо Кемикал Компани, Лимитед Способ получения содержащего титан оксида кремния, способ получения эпоксида и содержащий титан оксид кремния
JP7539876B2 (ja) 2019-05-29 2024-08-26 住友化学株式会社 チタン含有珪素酸化物の製造方法、エポキシドの製造方法、及びチタン含有珪素酸化物
KR102811135B1 (ko) 2019-05-29 2025-05-21 스미또모 가가꾸 가부시끼가이샤 티탄 함유 규소 산화물의 제조 방법, 에폭시드의 제조 방법, 및 티탄 함유 규소 산화물

Also Published As

Publication number Publication date
KR20190138653A (ko) 2019-12-13
CN110475748B (zh) 2022-12-30
KR102493560B1 (ko) 2023-01-30
JP6970739B2 (ja) 2021-11-24
JPWO2018186491A1 (ja) 2020-02-27
CN110475748A (zh) 2019-11-19

Similar Documents

Publication Publication Date Title
CN1219596C (zh) 含钛的硅氧化物催化剂的制造方法
JP4251666B2 (ja) 改良された不均一触媒組成物を用いるエポキシ化法
EP3096879B1 (fr) Procédé de fabrication de catalyseurs d'époxydation
JP4265212B2 (ja) チタン含有珪素酸化物触媒の製造方法
JP7539876B2 (ja) チタン含有珪素酸化物の製造方法、エポキシドの製造方法、及びチタン含有珪素酸化物
JP6970739B2 (ja) チタン含有珪素酸化物の製造方法、エポキシドの製造方法、及びチタン含有珪素酸化物
CN1396843A (zh) 模制催化剂、制造模制催化剂的方法及制造环氧乙烷化合物的方法
JP3797107B2 (ja) 触媒成型体、該触媒成型体の製造方法及びオキシラン化合物の製造方法
CN1492780A (zh) 含钛氧化硅催化剂的制备方法
JP4834982B2 (ja) チタン含有珪素酸化物触媒の製造方法及び触媒
KR101254352B1 (ko) 티탄 함유 규소 산화물 촉매의 제조 방법, 상기 촉매 및상기 촉매를 사용하는 올레핀옥시드 화합물의 제조 방법
WO2023210199A1 (fr) Procédé de production d'oxyde de silicium contenant du titane, procédé de production d'époxyde et oxyde de silicium contenant du titane
JP3731384B2 (ja) チタン含有珪素酸化物触媒、該触媒の製造方法及びプロピレンオキサイドの製造方法
RU2805109C2 (ru) Способ получения содержащего титан оксида кремния, способ получения эпоксида и содержащий титан оксид кремния
KR102672200B1 (ko) 티탄 함유 규소 산화물 성형체의 제조 방법, 및 티탄 함유 규소 산화물 성형체
JP2006255586A (ja) チタン含有珪素酸化物触媒の製造方法及び触媒
JP4495272B2 (ja) オキシラン化合物の製造方法
WO2024262456A1 (fr) Oxyde de silicium contenant du titane
JP2009248033A (ja) チタン含有珪素酸化物触媒の製造方法、プロピレンオキサイド製造用触媒及びプロピレンオキサイドの製造方法
JP2006159058A (ja) チタン含有珪素酸化物触媒の製造方法及び触媒

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18780490

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019511321

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20197032490

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 18780490

Country of ref document: EP

Kind code of ref document: A1