Classifications

• • 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
  • 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
  • B01J21/063—Titanium; 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
• • 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
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
  • B01J37/033—Using Hydrolysis
• • 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
  • B01J37/04—Mixing
• • 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
  • B01J37/08—Heat treatment
• • 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
  • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
• • 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
  • 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
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride

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 the titanium-containing silicon oxide produced by the method as a catalyst, and a titanium-containing silicon oxide.
• Patent Document 1 describes a first step of obtaining a solid containing a catalyst component and a mold by mixing a silica source, a titanium source and a mold in a liquid state, and a first step.
• the second step of removing the mold from the obtained solid by a 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 those of the silylating agent used in the fourth step below.
• Titanium-containing obtained by a production method including a third step of substituting with a specifically inert solvent and a fourth step of obtaining a silylated catalyst by subjecting the solid obtained in the third step to a silylation treatment.
• Silicon oxides are listed.
• the present invention relates to, but is not limited to: [Invention 1]
• a method for producing a titanium-containing silicon oxide which comprises the following steps.
• a step of mixing a silicon source, a mold and a solvent to obtain a solid containing a silicon oxide and a mold (raw material mixing step);
• a step of removing a mold from a solid obtained in a raw material mixing step to obtain a solid containing a silicon oxide (mold removal step);
• the process of introducing titanium into the system (titanium introduction process);
• the mold is a mixture of a quaternary ammonium compound having a quaternary ammonium ion represented by the following formula I and a tertiary amine compound represented by the following formula II.
• R 1 represents a hydrocarbon group of C 2 ⁇ 36, R 2, R 3 and R 4 each independently represent a hydrocarbon group of C 1 ⁇ 6)
• NR 5 R 6 R 7 II (In Equation II, R 5 represents a hydrocarbon group of C 2 ⁇ 36, R 6 and R 7 each independently represent a hydrogen atom or a hydrocarbon group of C 1 ⁇ 6)
• the molar ratio of the tertiary amine compound to the quaternary ammonium compound is 0.005 to 0.16.
• R 1 is a hydrocarbon group of C 10 ⁇ 22, a method according to the invention 1.
• R 5 is a hydrocarbon group of C 10 ⁇ 22, a method according to Invention 1 or 2.
• the quaternary ammonium ion is a hexadecyltrimethylammonium ion.
• [Invention 7] The method according to invention 6, wherein the molar ratio of the tertiary amine compound to the quaternary ammonium compound is 0.04 to 0.13.
• [Invention 8] The method according to any one of Inventions 1 to 7, wherein the raw material mixing step is the following step, and the titanium introduction step is carried out in the raw material mixing step: A step of mixing a silicon source, a titanium source, a mold agent, and a solvent to obtain a solid containing a silicon oxide into which titanium has been introduced and a mold agent.
• [Invention 9] A titanium-containing silicon oxide that can be produced by the method according to any one of the inventions 1 to 8.
• invention 10 An epoxide comprising a step of reacting an olefin with a hydroperoxide in the presence of a titanium-containing silicon oxide or the titanium-containing silicon oxide according to invention 9, which can be produced by the method according to any one of inventions 1 to 8. Manufacturing method.
• invention 11 The method according to invention 10, wherein the olefin is an ⁇ -olefin.
• invention 12 The method according to invention 10, wherein the olefin is propylene.
• invention 13 The method according to any one of inventions 10 to 12, wherein the hydroperoxide is cumene hydroperoxide.
• a method for producing an epoxide in a high yield in a reaction for producing an epoxide from an olefin and a hydroperoxide is provided.
• ⁇ -olefin means a hydrocarbon having a carbon-carbon unsaturated double bond at the ⁇ -position.
• hydrocarbon groups of CX to Y means hydrocarbon groups having XY to have carbon atoms.
• description of "lower limit to upper limit” representing a numerical range means “above the lower limit and below the upper limit”. That is, these descriptions represent a numerical range including a lower limit and an upper limit.
• the method for producing a titanium-containing silicon oxide according to one aspect of the present invention includes a raw material mixing step, a mold removing step, a silylation step, and a titanium introduction step.
• the titanium-containing silicon oxide is a compound in which a part of Si of the porous silicate (SiO 2 ) is replaced with Ti.
• the compound has a bond represented by —Si—O—Ti.
• the raw material mixing step is a step of mixing a silicon source, a mold and a solvent to obtain a solid containing a silicon oxide and a mold, and is sometimes referred to as step A.
• Silicon source refers to silicon oxide and silicon oxide precursors.
• the silicon oxide precursor refers to a compound in which a part or all of the silicon oxide precursor becomes silicon oxide by reacting the silicon oxide precursor with water.
• Amorphous silica can be mentioned as the silicon oxide.
• the silicon oxide precursor include alkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and 1,2-bis (trialkoxysilyl) alkane.
• Alkoxysilanes include tetramethyl orthosilicates, tetraethyl orthosilicates, and tetrapropyl orthosilicates.
• Examples of the alkyltrialkoxysilane include trimethoxy (methyl) silane.
• the dialkyldialkoxysilane include dimethoxydimethylsilane.
• the silicon source a single one may be used, or several kinds may be used in combination.
• silicon oxide precursor When a silicon oxide precursor is used as the silicon source, it is preferable to use water as part or all of the solvent in step A. When the silicon oxide precursor is mixed with water, the silicon oxide precursor is partially or wholly changed to silicon oxide.
• the mold agent refers to a substance capable of forming a pore structure in a titanium-containing silicon oxide.
• the mold is a mixture of a quaternary ammonium compound having a quaternary ammonium ion represented by the following formula I and a tertiary amine compound represented by the following formula II.
• R 1 represents a hydrocarbon group of C 2 to 36 , and R 2 to R 4 independently represent a hydrocarbon group of C 1 to 6 ).
• NR 5 R 6 R 7 II (Wherein II, R 5 represents a hydrocarbon group of C 2 - 36, a hydrocarbon group of R 6 and R 7 a hydrogen atom or a C 1 are each independently 1-6.)
• R 1 is a hydrocarbon group of C 2 ⁇ 36, it may be linear or branched and may be aliphatic or aromatic.
• R 2 to R 4 are independent hydrocarbon groups of C 1 to 6 , and may be linear or branched. It is preferred that all of R 2 ⁇ R 4 are methyl groups.
• quaternary ammonium ion represented by the formula I include tetraethylammonium, tetrapropylammonium, tetrabutylammonium, decyltrimethylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, and eicosyltrimethylammonium. Examples thereof include cations such as behenyltrimethylammonium and benzyltrimethylammonium.
• the compound containing the quaternary ammonium ion represented by the formula I include tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, decyltrimethylammonium hydroxide, decyltrimethylammonium chloride, and decyltrimethyl.
• Ammonium bromide dodecyltrimethylammonium hydroxide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium hydroxide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium hydroxide, octadecyltrimethylammonium chloride, octadecyl Examples thereof include trimethylammonium bromide, eicosyltrimethylammonium hydroxide, eicosyltrimethylammonium chloride, eicosyltrimethylammonium bromide, behenyltrimethylammonium hydroxide, behenyltrimethylammonium chloride, and behenyltrimethylammonium bromide.
• R 5 is a hydrocarbon group of C 2 ⁇ 36, may be branched may be linear, aliphatic or aromatic. Preferably a hydrocarbon group of C 10 ⁇ 22.
• R 6 and R 7 are independently hydrogen atoms or C 1 to 6 hydrocarbon groups, and may be linear or branched. It is preferable that R 6 and R 7 are methyl groups.
• amine represented by the formula II examples include ethylamine, propylamine, butylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, and the like.
• Heptadecylamine, octadecylamine, nonadecylamine, eikosylamine, behenylamine, and benzylamine, and methylalkylamine and dimethylalkylamine in which at least one hydrogen atom in these amines is substituted with a methyl group can be mentioned. it can.
• the molar ratio of the tertiary amine compound to the quaternary ammonium compound is 0.005 to 0.16, and in one embodiment 0.005 to 0.15, 0.005 to 0.14. , 0.005 to 0.13, 0.01 to 0.16, 0.01 to 0.15, 0.01 to 0.14, 0.01 to 0.13, 0.02 to 0.15, 0 .02 to 0.14, 0.02 to 0.13, 0.03 to 0.16, 0.03 to 0.15, 0.03 to 0.14, 0.03 to 0.13, 0.04 It may be ⁇ 0.16, 0.04 to 0.15, 0.04 to 0.14, or 0.04 to 0.13.
• a method for adjusting the molar ratio of the tertiary amine compound to the quaternary ammonium compound in the mixture for example, A method for adjusting the mixing ratio of a quaternary ammonium compound and a tertiary amine compound, In a mixture of a quaternary ammonium compound and a tertiary amine compound, the tertiary amine compound is reacted with an alkylating agent to convert a part of the tertiary amine compound into a quaternary ammonium compound, and then A method for adjusting the molar ratio of a tertiary amine compound to a quaternary ammonium compound by exchanging ions as necessary.
• a quaternary amine compound relative to a quaternary ammonium compound by distillation, extraction, recrystallization, chromatography or a combination of two or more of these methods on a mixture of the quaternary ammonium compound and the tertiary amine compound.
• the alkylating agent include methyl chloride, methyl bromide, and methyl iodide.
• Mixing of the silicon source and mold is carried out in the presence of a solvent.
• a solvent include water, alcohol and the like.
• the alcohol include methanol, ethanol, 1-propanol and 2-propanol. Two or more kinds of solvents may be mixed and used.
• step A By going through step A, a solid containing a silicon oxide and a mold agent can be obtained.
• step A includes a solvent removing step.
• the obtained solid containing the silicon oxide and the mold can be taken out by filtration, decantation, drying, centrifugation, a combination thereof, or the like.
• the mixing of step A is preferably carried out at 0 to 300 ° C. for 30 minutes to 1000 hours. In one embodiment, the mixing may be carried out at 20 to 100 ° C., the mixing at the boiling point of the solvent, the mixing may be carried out at 20 to 60 ° C., or the mixing may be carried out at 20 to 40 ° C. You may. In one embodiment, the mixing may be carried out over 30 minutes to 24 hours, or the mixing may be carried out over 2 to 24 hours. It is also possible to carry out stirring during mixing.
• the mold removal step is a step of removing a mold from the solid obtained in step A to obtain a solid containing a silicon oxide, and is sometimes referred to as step B. By carrying out step B, a solid containing no mold agent or substantially no mold agent is obtained.
• the content of the mold agent in the solid obtained in step B is preferably 10% by mass or less, and more preferably 1% by mass or less.
• Removal of the mold release can be achieved by calcining the solid containing the mold release in air at 300 to 800 ° C. or by extracting with a solvent. It is preferable to remove the mold agent by extraction.
• the solvent may be any one that can dissolve the compound used as the mold agent, and generally, a compound of C1 to 12 which is liquid at room temperature or a mixture of two or more kinds 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.
• Examples of the ketone include acetone, diethyl ketone, methyl ethyl ketone and methyl isobutyl ketone.
• Examples of the ether include diisobutyl ether and tetrahydrofuran.
• Examples of the ester 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 compound containing a quaternary ammonium ion, 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.
• Acids or salts thereof may be added to these solvents to improve the extraction effect.
• the acid used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and odorous acid, and organic acids such as formic acid, acetic acid and propionic acid.
• examples of such salts include alkali metal salts, alkaline earth metal salts, and ammonium salts.
• the concentration of the added acid or a salt thereof in the solvent is preferably 30% by mass or less, more preferably 15% by mass or less.
• Examples of the method for removing the mold agent include a method in which the solvent and the solid containing the mold agent are sufficiently mixed, and then the liquid phase portion is separated by a method such as filtration, decantation, drying, centrifugation, or a combination thereof. .. This operation may be repeated a plurality of times. It is also possible to extract the mold by a method in which a solid containing the mold is filled in a container such as a column and an extraction solvent is circulated.
• the extraction temperature is preferably 0 to 200 ° C, more preferably 20 to 100 ° C. If the boiling point of the extraction solvent is low, the extraction may be carried out under pressure.
• the mold release in the solution obtained by the extraction treatment can be recovered and reused as the mold release in step A by carrying out treatments such as ion exchange as necessary.
• the extraction solvent can also be purified and reused by a normal distillation operation or the like.
• the silylation step is a step of obtaining a solid containing a silylated silicon oxide by contacting the solid obtained in step B with a silylating agent, and is sometimes referred to as step C.
• step C the silicon oxide contained in the solid obtained in step B is silylated.
• Cyrilization may be carried out by a vapor phase method in which a gaseous silylating agent is brought into contact with the solid obtained in step B to react, or a liquid in which the silylating agent is brought into contact with the solid in a solvent to react. It may be done by the phase method. In one aspect of the invention, the liquid phase method is more preferred. Usually, when silylation is carried out by the liquid phase method, a hydrocarbon is preferably used as a solvent in step C. When silylation is performed by the liquid phase method, drying may be performed after that.
• the silylating agent is a silicon compound that is reactive with a solid, and a hydrolyzable group is bonded to silicon.
• the hydrolyzable group bonded to silicon include hydrogen, halogen, alkoxy group, acetoxy group and amino group.
• the silylating agent preferably has one hydrolyzable group bonded to silicon. Further, at least one or more groups selected from the group consisting of an allyl group such as an alkyl group and a vinyl group, an aryl group such as a phenyl group, an alkyl halide group, and a siloxy group are bonded to silicon.
• silylating agent examples include organic silane, organic silylamine, organic silylamide and its derivative, and organic silazane.
• organic silane examples include chlorotrimethylsilane, dichlorodimethylsilane, chlorobromodimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, iododimethylbutylsilane, chlorodimethylphenylsilane, chlorodimethylsilane, dimethyln-propylchlorosilane, and dimethylisopropyl.
• organic silylamine examples include N- (trimethylsilyl) imidazole, N- (tert-butyldimethylsilyl) imidazole, N- (dimethylethylsilyl) imidazole, N- (dimethyln-propylsilyl) imidazole, and N- (dimethylisopropyl).
• Cyril) 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.
• Examples of the organic silylamide and the derivative 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) heptafluorobutylamide, N- (tert-butyldimethylsilyl) -N-trifluoroacetamide, and N, O-bis (diethyl) Hydrosilyl) Trifluoroacetamide can be mentioned.
• organic silazane examples include 1,1,1,3,3,3-hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyldisilazane and 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 Methyl disilazane can be mentioned.
• silylating agent examples include N-methoxy-N, O-bis (trimethylsilyl) trifluoroacetamide, N-methoxy-N, O-bis (trimethylsilyl) carbamate, N, O-bis (trimethylsilyl) sulfamate, Examples thereof include trimethylsilyl trifluoromethanesulfonate and N, N'-bis (trimethylsilyl) urea.
• the preferred silylating agent is organic silazane, more preferably 1,1,1,3,3,3-hexamethyldisilazane.
• the silicon oxide is silylated by contacting the solid containing the silicon oxide obtained in step B with the silylating agent. It is presumed that a silyl group is introduced into the OH group on the surface of at least a part of the solid containing a silicon oxide to make it hydrophobic, but the present invention is not limited to this theory.
• Titanium introduction process is a process of introducing titanium into the system.
• the term “inside the system” means the inside of the reaction system in the method for producing a titanium-containing silicon oxide, and specifically, before step A, in step A, between step A and step B, in step B, in step B. Between and step C, within step C, and after step C.
• the silicon oxide and the titanium source are mixed, and the bond represented by -Si-O-Ti is introduced into the silicon oxide.
• Titanium may be introduced into the silicon oxide by contacting the silicon oxide with the titanium source in the liquid phase, or by contacting the silicon oxide with a gas containing the titanium source, titanium becomes the silicon oxide. It may be introduced.
• examples of the solvent include water, alcohol and the like, and for example, the solvent described above for step A can be used.
• the mixing temperature include 0 to 60 ° C.
• Examples of the mixing time include 1 minute to 24 hours.
• the titanium source When mixing in the gas phase, the titanium source can be gasified and mixed.
• the mixing temperature include 100 to 500 ° C.
• Examples of the mixing time include 1 minute to 24 hours. Mixing may be carried out at normal pressure, for example at 10 to 1000 kPa (absolute pressure).
• Titanium may be introduced at two or more of the above-mentioned timings.
• Titanium is preferably introduced prior to the start of step C, and at least one selected from the group consisting of before step A, within step A, and between step B and step C. It is more preferable that titanium is introduced before or during step A.
• the titanium source is mixed with a silicon source, mold agent, or solvent before mixing in step A.
• step A When titanium is introduced in step A, the silicon source, titanium source and mold agent are mixed in step A.
• Titanium may be introduced by bringing the solid obtained in step A into contact with the titanium source after the end of step A and before the start of step B.
• Titanium may be introduced by bringing the solid obtained in step B into contact with the titanium source after the end of step B and before the start of step C.
• titanium source examples include titanium alcoholide, a chelated titanium complex, titanium halide, and a sulfate containing titanium.
• titanium alcoholides include tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra (2-ethylhexyl) titanate, and tetraoctadecyl titanate.
• examples of the chelated 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 include titanyl sulfate.
• 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 in particular, a production of an epoxide that reacts an olefin with a hydroperoxide. It is preferable to use it for.
• the olefin to be subjected to the epoxidation reaction may be an acyclic olefin, a monocyclic olefin, a bicyclic olefin or a polycyclic olefin having three or more rings, and may be a monoolefin, a diolefin or a polyolefin.
• these double bonds may be conjugated bonds or non-conjugated bonds.
• Olefins C 2 ⁇ 60 is preferable.
• 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.
• the olefin may have a substituent containing an oxygen atom, a sulfur atom, or a nitrogen atom together with a hydrogen atom, a carbon atom, or both, and examples of such an olefin include allyl alcohol and crotyl. Examples include alcohol and allyl chloride.
• diolefins examples include butadiene and isoprene.
• preferred olefins examples include ⁇ -olefins. Particularly preferred olefins include propylene.
• hydroperoxides examples include organic hydroperoxides.
• Organic hydroperoxides are formula III ROOH III (In Formula III, R is a hydrocarbon group.) It is a compound having.
• Organic hydroperoxides react with olefins to produce epoxides and hydroxyl compounds.
• R in formula III is preferably a hydrocarbon group of C 3 ⁇ 20, more preferably, a hydrocarbon group of C 3 ⁇ 10. It may be linear or branched, and may be aliphatic or aromatic.
• Specific examples of the organic hydroperoxide include tert-butyl hydroperoxide, 1-phenylethyl hydroperoxide, and cumene hydroperoxide.
• cumene hydroperoxide may be abbreviated as CMHP.
• CMHP When CMHP is used as the organic hydroperoxide, the obtained hydroxyl compound is 2-phenyl-2-propanol. This 2-phenyl-2-propanol produces cumene by undergoing a dehydration reaction and a hydrogenation reaction.
• cumene may be abbreviated as CUM.
• CUM cumene
• CMHP is obtained again. From this point of view, it is preferable to use CMHP as the organic hydroperoxide used in the epoxidation reaction.
• the epoxidation reaction can be carried out in a liquid phase using a solvent, a diluent, or a mixture thereof.
• Solvents and diluents must be liquid under the temperature and pressure of the reaction and be substantially inert to the reactants and products.
• CUM can be used as a solvent without 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 10000 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 olefins can be recirculated and reused.
• the reaction using the titanium-containing silicon oxide produced according to one aspect of the present invention as a catalyst can be carried out in the form of a slurry or a fixed bed, and in the case of a large-scale industrial operation, it is preferable to use a fixed bed. ..
• the titanium-containing silicon oxide produced according to one aspect of the present invention may be a powder or a molded product.
• the reaction is carried out on a fixed bed, the titanium-containing silicon oxide is preferably a molded product. This reaction can be carried out by a batch method, a semi-continuous method or a continuous method.
• CTAH Hexadecyltrimethylammonium hydroxide
• CDMA Hexadecyldimethylamine
• Mold removal step 5 g of the white solid obtained in the raw material mixing step was placed in a flask, and 50 mL of methanol was added. The mixture was heated under reflux for 1 hour with stirring, allowed to cool, and then the solid was filtered off. A mixed solution of 48 mL of methanol and 2.6 g of a concentrated hydrochloric acid aqueous solution (content 36% by weight) was added to the obtained solid. The mixture was heated under reflux for 1 hour with stirring, allowed to cool, and then the solid was filtered off. The same operation was repeated once again using a mixed solution of 49 mL of methanol and 1.3 g of a concentrated hydrochloric acid aqueous solution (content 36% by weight) with respect to the obtained solid.
• Cyrilization step 2 g of the white solid obtained in the mold release step, 1.4 g of hexamethyldisilazane, and 20 g of toluene were mixed and heated under reflux with stirring for 1.5 hours. After allowing to cool, the solid was filtered off. The obtained solid was washed with 30 g of toluene and dried under reduced pressure at 120 ° C. and 10 mmHg for 2 hours to obtain a titanium-containing silicon oxide catalyst.
• M PO M 2 - (M ph + M ac + M pg + 2 ⁇ M dpg + 3 ⁇ M tpg))
• M ph Amount of phenol produced
• M ac Amount of acetophenone produced
• M pg Amount of propylene glycol produced
• Example 2 In the material mixing step and the titanium introduction step, the same operation as in Example 1 was performed except that the amount of CDMA added was 1.5 g and the CDMA / CTAH molar ratio was 0.13, and the titanium-containing silicon oxide was prepared. Obtained a catalyst.
• Example 3 In the raw material mixing step and the titanium introduction step, the same operation as in Example 1 was performed except that the amount of CDMA added was 0.5 g and the CDMA / CTAH molar ratio was 0.04, and the titanium-containing silicon oxide was prepared. Obtained a catalyst.
• Example 4 In the raw material mixing step and the titanium introduction step, the same operation as in Example 1 was performed except that the CDMA addition amount was 0.1 g and the CDMA / CTAH molar ratio was 0.01. Obtained a catalyst.
• Comparative Example 1 In the raw material mixing step and the titanium introduction step, the same operation as in Example 1 was carried out except that the CDMA addition amount was 0 g and the CDMA / CTAH molar ratio was 0 to obtain a titanium-containing silicon oxide catalyst. ..
• Comparative Example 2 In the raw material mixing step and the titanium introduction step, the same operation as in Example 1 was performed except that the CDMA addition amount was 2.1 g and the CDMA / CTAH molar ratio was 0.18, and the titanium-containing silicon oxide was prepared. Obtained a catalyst.
• the method for producing a titanium-containing silicon oxide according to one aspect of the present invention can be applied to the production of a catalyst that can be used in a reaction for producing an epoxide from an olefin and a hydroperoxide, and the titanium-containing obtained by the method can be applied.
• the silicon oxide can be used, for example, as a catalyst in the production of propylene oxide.

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• 2020
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