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WO2012074033A1 - Procédé de production de moulages d'oxyde de silicium contenant du titane et procédé de production de composés oxiranne - Google Patents

Procédé de production de moulages d'oxyde de silicium contenant du titane et procédé de production de composés oxiranne Download PDF

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Publication number
WO2012074033A1
WO2012074033A1 PCT/JP2011/077738 JP2011077738W WO2012074033A1 WO 2012074033 A1 WO2012074033 A1 WO 2012074033A1 JP 2011077738 W JP2011077738 W JP 2011077738W WO 2012074033 A1 WO2012074033 A1 WO 2012074033A1
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titanium
silicon oxide
precursor
item
molded body
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Japanese (ja)
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純 山本
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • 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
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • 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
    • 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
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • 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
    • B01J2229/34—Reaction with organic or organometallic compounds
    • 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
    • B01J2229/37—Acid treatment
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for producing a titanium-containing silicon oxide molded body and a method for producing an oxirane compound, which can produce an oxirane compound from olefin and hydroperoxide in high yield.
  • a titanium-containing silicon oxide catalyst having a zeolite structure is active in olefin epoxidation using hydrogen peroxide.
  • TO 4 units are successively connected three-dimensionally to form a crystalline porous structure.
  • zeolites with various structures due to the difference in the form of linkage of the TO 4 units are classified by the Structure Commission of the International Zeolite Association (IZA-SC) according to the structure code of the three letters of the alphabet according to the form.
  • IZA-SC Structure Commission of the International Zeolite Association
  • a titanium-containing MWW type zeolite catalyst is known as the catalyst.
  • the titanium-containing MWW-type zeolite is a titanium-containing silicon oxide catalyst having a structure similar to that of MCM-22 zeolite well known as an alkylation catalyst and having a structure code represented by MWW.
  • the titanium-containing MWW-type zeolite catalyst has insufficient activity for olefin epoxidation using hydrogen peroxide.
  • the titanium-containing MWW-type zeolite catalyst has a small pore size, the epoxidation activity is very low when a large olefin or organic hydroperoxide is used.
  • an approach for obtaining an MWW-type zeolite catalyst capable of reacting larger molecules for example, after swelling between layers of a MWW-type zeolite layered precursor with a surfactant or the like, the swollen MWW-type zeolite layered precursor is converted into a swollen MWW-type zeolite layered precursor.
  • a method for producing a catalyst in which an MWW-type zeolite layered precursor is delaminated by sonication and calcination.
  • This catalyst is widely known as ITQ2, which is an analog of MWW type zeolite.
  • JP-T-2003-509479 discloses a method of producing a compact having a predetermined size or more by pressing a powder of ITQ2 obtained by delaminating to obtain a tablet, and crushing and classifying the tablet.
  • JP-T-2003-509479 discloses a method of producing a compact having a predetermined size or more by pressing a powder of ITQ2 obtained by delaminating to obtain a tablet, and crushing and classifying the tablet.
  • JP-T-2003-509479 discloses a method of producing a compact having a predetermined size or more by pressing a powder of ITQ2 obtained by delaminating to obtain a tablet, and crushing and classifying the tablet.
  • JP-T-2003-509479 discloses a method of producing a compact having a predetermined size or more by pressing a powder of ITQ2 obtained by delaminating to obtain a tablet, and crushing and classifying the tablet
  • the problem to be solved by the present invention is to provide a method for producing a titanium-containing silicon oxide molded body and a method for producing an oxirane compound, which can produce an oxirane compound from olefin and hydroperoxide in high yield.
  • this invention relates to the manufacturing method of the titanium containing silicon oxide molded object which has the following 1st process, the following 2nd process, and the following 3rd process.
  • First step A step of obtaining a swollen titanium-containing zeolite layered precursor (2) by bringing the titanium-containing zeolite layered precursor (1) into contact with a solution containing a swelling agent and a solvent.
  • the present invention is a titanium-containing silicon obtained by the above production method
  • the present invention relates to a method for producing an oxirane compound in which an olefin and a hydroperoxide are reacted in the presence of an oxide compact.
  • the manufacturing method of the titanium containing silicon oxide molded object of this invention has the following 1st process, the following 2nd process, and the following 3rd process.
  • First step A step of obtaining a swollen titanium-containing zeolite layered precursor (2) by bringing the titanium-containing zeolite layered precursor (1) into contact with a solution containing a swelling agent and a solvent.
  • Second step precursor ( Step 2) Pressurizing to obtain molded body (3)
  • Third step Step of removing swelling agent contained in molded body (3) What is a titanium-containing zeolite layered precursor used as a raw material in the first step? A zeolite layered precursor in which titanium atoms are introduced.
  • Zeolite layered precursor is a structure that has a structure in which multiple layers of sheet-like silicon oxide are laminated. By firing it, a three-dimensional crystalline porous structure is formed to form zeolite. This is a possible structure.
  • Examples of the structure of the zeolite obtained by calcining the zeolite layered precursor include MWW type, FER type, RRO type, and CDO type defined by the Structure Commission of the International Zeolization Association (IZA-SC). Of these, an MWW-type zeolite layered precursor is preferable.
  • Examples of the method for producing the titanium-containing MWW-type zeolite layered precursor include the method described in JP-A No. 2002-102709.
  • titanium atoms into the zeolite layered precursor when the structure of the zeolite layered precursor is formed by hydrothermal synthesis or the like, a direct introduction method in which titanium atoms are introduced in the presence of a titanium source, zeolite not containing titanium atoms After synthesizing the layered precursor, any of post-introduction methods in which titanium atoms are introduced by a method such as ion exchange, isomorphous substitution, or atom planting may be used, but the introduction of titanium atoms may be performed by a direct introduction method. preferable.
  • the structure of the zeolite layered precursor can be observed by X-ray diffraction (XRD).
  • the titanium-containing MWW-type zeolite layered precursor can be obtained by mixing a silicon compound, a titanium compound, a boron compound, water and a structure directing agent, and then subjecting the obtained mixture to a hydrothermal synthesis reaction.
  • the silicon compound include alkoxysilane and amorphous silica.
  • Examples of the alkoxysilane include tetramethylorthosilicate, tetraethylorthosilicate, and tetrapropylorthosilicate.
  • Examples of the amorphous silica include Examples thereof include fumed silica.
  • Examples of the titanium compound include alkoxy titanium, peroxy titanate, titanium halide, titanium acetate, titanium nitrate, titanium sulfate, and titanium phosphate.
  • Examples of the alkoxy titanium include tetra-n-propyl ortho.
  • Examples thereof include titanate, tetra-isopropyl orthotitanate, tetra-n-butyl orthotitanate, etc., and examples of peroxytitanate include tetra-n-butylammonium peroxytitanate, and examples of titanium halide include, for example, , Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and the like. Examples of the boron compound include boric acid and anhydrous boric acid.
  • the structure directing agent is an organic compound that is used as an aid for forming a structure of zeolite or a precursor thereof.
  • Examples of the structure directing agent suitable for obtaining the MWW-type zeolite layered precursor include piperidine, hexamethyleneimine, and trimethyladamanta ammonium hydroxide. These structure directing agents may be used alone, or two or more structure directing agents having a desired ratio may be mixed and used. Of these, piperidine is preferably used alone.
  • the use ratio of each of the raw materials is based on the number of silicon atoms in the silicon compound, and the titanium compound is 0.01 to 0.2 as titanium atoms.
  • the boron compound is 0.1 to 3 mol times as a boron atom
  • water is 3 to 50 mol times
  • the structure directing agent is 0.1 to 3 mol times.
  • the raw materials are preferably mixed at a temperature of 0 to 60 ° C., more preferably 10 to 50 ° C.
  • the mixing method of the respective raw materials for example, all the raw materials may be mixed at once, or the respective raw materials may be mixed sequentially. In particular, mixing the raw material that is liquid first and then mixing the raw material that is solid can uniformly stir the raw material, and thus avoid the uneven distribution of titanium atoms in the obtained titanium-containing MWW-type zeolite layered precursor. It is preferable because it is possible.
  • the mixture of each raw material is subjected to a hydrothermal synthesis reaction to obtain a titanium-containing MWW-type zeolite layered precursor.
  • the titanium-containing MWW-type zeolite layered precursor is a structure that changes to the structure of the MWW-type zeolite upon firing, and has a structure in and between each layer of titanium-containing silicon oxide. It means the structure in which the directing agent is included.
  • hydrothermal synthesis refers to a synthesis method and crystal growth method of a substance carried out in the presence of high-temperature and high-pressure water (“Iwanami Physical and Chemical Dictionary”, 4th edition, Iwanami Shoten, 1987, p.
  • the raw materials are mixed, and the mixture of raw materials is heated at a temperature of about 100 to 200 ° C. under autoclaving in an autoclave for several hours to several days. It is carried out by stirring or standing the mixture.
  • Solids generated by hydrothermal synthesis may contain compounds other than titanium-containing MWW-type zeolite layered precursors, and solids containing titanium-containing MWW-type zeolite layered precursors usually require filtration of the reaction mixture and residue. Depending on the case, it can be obtained by washing with an organic solvent such as water or methanol and then drying.
  • the drying method is preferably, for example, a method in which the residue is heated at 10 to 200 ° C.
  • the titanium-containing MWW-type zeolite layered precursor produced by hydrothermal synthesis is preferably treated with an acid before being subjected to the first step described later to remove unnecessary Ti that does not function as a reactive site.
  • acids used for removing unnecessary Ti include inorganic acids and organic acids.
  • inorganic acids include hydrochloric acid, sulfuric acid, and nitric acid.
  • organic acids include formic acid and acetic acid.
  • An inorganic acid is preferable.
  • the acid is used as a solution obtained by diluting the acid with a solvent.
  • the concentration of the acid in the solution is preferably 0.5 to 10 N, and an organic solvent such as alcohol or ketone and water can be used as the solvent.
  • a swollen titanium-containing zeolite layered precursor (2) can be obtained by bringing the titanium-containing MWW-type zeolite layered precursor (1) obtained by the above operation into contact with a solution containing a swelling agent and a solvent. Examples of the method of bringing the precursor (1) into contact with the solution include a method of immersing the precursor (1) in the solution.
  • the swelling of the titanium-containing MWW-type zeolite layered precursor is that the peak of the precursor (2) derived from the 002 plane of the MWW structure in the X-ray diffraction method (XRD) is lower than the peak of the precursor (1). It can be confirmed from the difference in the amount of organic substances contained in the precursor (1) and the precursor (2) by elemental analysis or ignition loss analysis.
  • the swelling agent used in the first step is a compound having a characteristic of entering the interlayer of the titanium-containing MWW-type zeolite layered precursor to increase the interlayer distance.
  • a surfactant can be suitably used, and among them, a compound containing a quaternary ammonium ion represented by the following general formula (I) is preferable.
  • Examples of the quaternary ammonium ion represented by the general formula (I) include hexadecyltrimethylammonium, dodecyltrimethylammonium, benzyltrimethylammonium, dimethyldidodecylammonium, hexadecylpyridinium, and the like. More preferred.
  • the swelling agent may contain only one type of quaternary ammonium ion represented by the general formula (I), or may contain two or more types.
  • Examples of the solvent contained in the solution can dissolve the swelling agent. Examples of the solvent include water, alcohol, and ketone. Examples of the alcohol include methanol, ethanol, 1-propanol, and 2-propanol. Examples of ketones include acetone.
  • the solution is preferably alkaline.
  • alkali source quaternary ammonium hydroxide is preferable, and examples thereof include ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and the like, and the fourth represented by the general formula (I). More preferred is a hydroxide of a quaternary ammonium ion.
  • the temperature at which the precursor (1) is brought into contact with the solution is usually 40 to 120 ° C, more preferably 60 to 100 ° C.
  • the time for bringing the precursor (1) into contact with the solution is usually 5 to 50 hours. Moreover, you may irradiate the solution containing a precursor (1) with an ultrasonic wave as needed, or may adjust pH of the solution containing a precursor (1).
  • a contact product obtained by bringing the precursor (1) into contact with the solution is filtered or centrifuged to obtain a solid. If necessary, the solid is washed with an organic solvent such as water or methanol, and then dried. A swollen titanium-containing zeolite layered precursor (2) can be obtained.
  • the drying method is preferably, for example, a method in which the residue is heated at 10 to 200 ° C.
  • the second step of the present invention is a step of pressing the swollen titanium-containing zeolite layered precursor (2) obtained in the first step to obtain a molded body (3). It is the most important matter of the present invention to pressurize the swollen titanium-containing zeolite layered precursor (2), thereby removing the swelling agent from the molded body (3) in the subsequent third step, thereby providing catalyst physical properties. Can be obtained.
  • any method such as roll press molding (briqueting, compacting), hydraulic press molding, compression molding represented by tableting molding, extrusion molding or the like is used.
  • compression molding is more preferable.
  • organic or inorganic binders can be used.
  • a method using no binder is preferred.
  • the pressure when pressurizing the precursor (2) is usually 0.1 to 10 ton / cm 2 , preferably 0.2 to 5 ton / cm 2 , and more preferably 0.5 ton / cm 2. ⁇ 2 tons / cm 2 .
  • the water content of the solid subjected to compression molding is preferably 15% or less, more preferably 10% or less.
  • Examples of the method for removing the swelling agent include a method of firing the molded product (3) obtained in the second step at a high temperature of 400 to 700 ° C. in air, and a method of extracting the swelling agent with a solvent.
  • a method of removing the swelling agent is preferred.
  • the solvent used for the extraction is not particularly limited as long as it can dissolve the swelling agent. Generally, oxa and / or oxo substituted hydrocarbons having 1 to 12 carbon atoms and liquid at normal temperature can be used.
  • Suitable solvents of this type include, for example, alcohols, ketones, ethers (acyclic compounds and cyclic compounds), esters, etc.
  • alcohols include, for example, methanol, ethanol, ethylene glycol , Propylene glycol, isopropanol, n-butanol, octanol and the like.
  • ketones include acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone and the like.
  • ethers include diisobutyl ether, tetrahydrofuran and the like.
  • acid salts include alkali metal salts, alkaline earth metal salts, ammonium salts and the like.
  • concentration of the acid or acid salt in the solvent is preferably 10 mol / l or less, and more preferably 5 mol / l or less.
  • the extraction temperature is preferably 0 to 200 ° C, more preferably 20 to 100 ° C.
  • the extraction may be performed under pressure.
  • the titanium-containing silicon oxide molded body obtained after the extraction treatment may be dried.
  • the drying method is preferably a method of heating at 10 to 700 ° C., more preferably 50 to 200 ° C. in an atmosphere of a non-reducing gas such as nitrogen, argon or carbon dioxide or an oxygen-containing gas such as air.
  • the titanium-containing silicon oxide molded body obtained by the above operation may contain titanium-containing MWW-type zeolite and the like, but the content of titanium-containing MWW-type zeolite is preferably 50% or less, 30 % Or less is more preferable.
  • the titanium-containing silicon oxide molded article is suitable as a catalyst in a method for producing an oxirane compound from an olefin and a hydroperoxide.
  • a silylated titanium-containing silicon oxide molded body obtained by silylating a titanium-containing silicon oxide molded body obtained by the above method is also suitable as a catalyst in a method for producing an oxirane compound from an olefin and a hydroperoxide.
  • Silylated titanium-containing silicon oxide compacts are more hydrophobic than titanium-containing silicon oxide compacts. Therefore, an oxirane compound can be produced in high yield from an olefin and a hydroperoxide by using a silylated titanium-containing silicon oxide molded article as a catalyst.
  • Examples of the method for silylating the titanium-containing silicon oxide molded body include a method of bringing the molded body into contact with a silylating agent.
  • Examples of the silylating agent include organic silanes, organic silylamines, organic silylamides and derivatives thereof, organic silazanes, and other silylating agents.
  • organic silane examples include chlorotrimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, chlorodimethylphenylsilane, dimethyl-n-propylchlorosilane, dimethylisopropylchlorosilane, t-butyldimethylchlorosilane, tripropylchlorosilane, dimethyloctylchlorosilane, and tributyl.
  • Examples of the organic silylamine include N-trimethylsilylimidazole, Nt-butyldimethylsilylimidazole, N-dimethylethylsilylimidazole, N-dimethyl-n-propylsilylimidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilyldimethylamine.
  • N-trimethylsilyldiethylamine N-trimethylsilylpyrrole, N-trimethylsilylpyrrolidine, N-trimethylsilylpiperidine, 1-cyanoethyl (diethylamino) dimethylsilane, pentafluorophenyldimethylsilylamine.
  • organic silylamides and derivatives thereof include N, O-bistrimethylsilylacetamide, N, O-bistrimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltriamide.
  • examples include fluoroacetamide, N-methyl-N-trimethylsilylheptafluorobutyramide, N- (t-butyldimethylsilyl) -N-trifluoroacetamide, and N, O-bis (diethylhydrosilyl) trifluoroacetamide.
  • organic silazane examples include hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-bis (chloromethyl) tetramethyldisilazane, 1,3-divinyl- Examples include 1,1,3,3-tetramethyldisilazane and 1,3-diphenyltetramethyldisilazane.
  • silylating agents examples include N-methoxy-N, O-bistrimethylsilyltrifluoroacetamide, N-methoxy-N, O-bistrimethylsilylcarbamate, N, O-bistrimethylsilylsulfamate, trimethylsilyltrifluoromethane. Examples thereof include sulfonate and N, N′-bistrimethylsilylurea.
  • a preferred silylating agent is hexamethyldisilazane.
  • the silylation of the titanium-containing silicon oxide molded body can be performed in either a gas phase or a liquid phase.
  • silylation is usually carried out in a solvent that does not essentially react with the silylating agent, and a hydrocarbon is preferably used as the solvent.
  • a hydrocarbon is preferably used as the solvent.
  • the hydrocarbon solvent include aliphatic hydrocarbons and aromatic hydrocarbons.
  • the aliphatic hydrocarbons include hexane and heptane.
  • the aromatic hydrocarbon include benzene, Examples include toluene and xylene.
  • the silylation temperature is preferably 0 to 300 ° C, more preferably 50 to 150 ° C.
  • the titanium-containing silicon oxide molded body and silylated titanium-containing silicon oxide molded body obtained by the method of the present invention can be suitably used as a catalyst particularly in a method for producing an oxirane compound in which an olefin and a hydroperoxide are reacted.
  • the olefin may be an acyclic, monocyclic, bicyclic or polycyclic compound, and may be a monoolefin, diolefin or polyolefin. If there are two or more olefinic bonds, this may be a conjugated bond or a non-conjugated bond. Olefins having 2 to 60 carbon atoms are generally preferred.
  • the olefin may have a substituent, and the substituent is preferably a relatively stable group.
  • the monoolefin include ethylene, propylene, butene-1, isobutylene, hexene-1, hexene-2, hexene-3, octene-1, decene-1, styrene, cyclohexene, and propylene is preferable.
  • the diolefin include butadiene and isoprene.
  • the substituent include various substituents containing a halogen atom, an oxygen atom, a sulfur atom, or a nitrogen atom together with hydrogen and / or a carbon atom.
  • Examples of the olefin having a substituent include Saturated alcohols, olefins substituted with a halogen atom, and the like.
  • Examples of unsaturated alcohols include allyl alcohol and crotyl alcohol.
  • Examples of olefins substituted with a halogen atom include allyl chloride.
  • Examples of the hydroperoxide suitably used in the present invention include hydrogen peroxide and organic hydroperoxide, and organic hydroperoxide is more preferable.
  • Organic hydroperoxides have the general formula R—O—O—H (Where R is a monovalent hydrocarbyl group.) Which reacts with an olefin to produce an oxirane compound and a compound R—OH.
  • R is preferably a hydrocarbyl group having 3 to 20 carbon atoms, more preferably a hydrocarbyl group having 3 to 10 carbon atoms, and still more preferably a secondary or tertiary alkyl group having 3 to 10 carbon atoms.
  • Examples of the tertiary alkyl group having 3 to 10 carbon atoms include a tertiary butyl group and a third pentyl group.
  • Examples of the tertiary aralkyl group having 8 to 10 carbon atoms include 2-phenylpropyl. -2 groups and the like.
  • various tetranylyl groups generated by removing hydrogen atoms from the aliphatic side chain of the tetralin molecule are also exemplified as R.
  • the organic hydroperoxide is preferably cumene hydroperoxide, and in that case, the method for producing an oxirane compound of the present invention can be suitably used as part of the propylene oxide single production process described in JP-A-2008-266304. .
  • the oxirane compound can be produced in a liquid phase using a solvent.
  • the solvent is preferably a liquid under the temperature and pressure during the reaction, and is substantially inert to the reactants and products.
  • the solvent may be a substance present in the hydroperoxide solution used.
  • the cumene hydroperoxide solution is a mixture of cumene hydroperoxide and cumene, which is a raw material thereof, this solution can be used as a substitute for the solvent without particularly adding a solvent.
  • the reaction temperature is generally 0 to 200 ° C., but a temperature of 25 to 200 ° C. is preferred.
  • the pressure may be any pressure that can keep the reaction mixture in a liquid state. In general, the pressure is preferably 100 to 10,000 kPa.
  • the liquid mixture containing the oxirane compound can be easily separated from the catalyst.
  • the liquid mixture may then be purified by an appropriate method. Purification includes fractional distillation, selective extraction, filtration, washing and the like.
  • the solvent, catalyst, unreacted olefin and unreacted hydroperoxide can be recycled and reused.
  • Manufacture of an oxirane compound may be performed with a slurry and may be performed using a fixed bed. In the case of large-scale industrial operation, a method using a fixed bed is preferable.
  • the pressure loss before and after the reaction tube is smaller than when powder is used.
  • the catalyst is less likely to flow out downstream, and is excellent in handling properties during filling.
  • Example 1 Preparation of Titanium-containing Zeolite Layered Precursor 171 g of ion exchange water and 60 g of piperidine were placed in a 1 liter separable flask and stirred, and 5 g of tetra-n-butyl orthotitanate was added dropwise thereto at room temperature. After stirring these for 0.5 hour, 42 g of boric acid was added and further stirred for 0.5 hour. Subsequently, 30 g of fumed silica (Cabot-O-Sil M-7D manufactured by Cabot) was added, followed by stirring for 1 hour.
  • Cabot-O-Sil M-7D manufactured by Cabot
  • Step of obtaining swollen titanium-containing zeolite layered precursor (first step) 4 g of a solid containing a titanium-containing zeolite layered precursor obtained by the method (1) (700 ° C.
  • Example 2 The same operation as in Example 1 was performed except that the swelling agent was removed in the third step not by solvent extraction but by firing the molded body for 5 hours at 540 ° C. in an air stream of 100 ml / min. The catalyst analysis results and reaction results are shown in Table 1.
  • Comparative Example 1 The same operation as in Example 1 was performed except that the order of the second step and the third step in Example 1 was changed and molding was performed after removal of the swelling agent (solvent extraction).
  • Example 2 The same operation as in Example 2 was performed except that the order of the second step and the third step in Example 2 was changed and molding was performed after removing (sintering) the swelling agent.
  • the catalyst analysis results and reaction results are shown in Table 1.
  • an oxirane compound can be produced from olefin and hydroperoxide in high yield.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)

Abstract

La présente invention a pour objet un procédé de production de moulages d'oxyde de silicium contenant du titane comprenant les premier, deuxième et troisième procédés. Premier procédé : un procédé d'obtention d'un précurseur de zéolite contenant du titane lamellaire gonflé (2) par la mise en contact d'un précurseur de zéolite contenant du titane lamellaire (1) avec une solution contenant un agent de gonflement et un solvant. Deuxième procédé : un procédé d'obtention d'un moulage (3) par mise sous pression du précurseur (2). Troisième procédé : un procédé d'élimination de l'agent de gonflement contenu dans le moulage (3).
PCT/JP2011/077738 2010-11-30 2011-11-24 Procédé de production de moulages d'oxyde de silicium contenant du titane et procédé de production de composés oxiranne Ceased WO2012074033A1 (fr)

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Cited By (2)

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CN110240176A (zh) * 2019-07-16 2019-09-17 上海纳米技术及应用国家工程研究中心有限公司 一种介孔钛硅分子筛纳米粒子的制备方法
CN111818997A (zh) * 2018-03-15 2020-10-23 住友化学株式会社 含钛的硅氧化物成型体的制造方法以及含钛的硅氧化物成型体

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EP2909141B1 (fr) * 2012-10-18 2016-12-14 Basf Se Post-traitement de zéolite mww dont le bore a été enlevé
HUE043211T2 (hu) * 2014-09-09 2019-08-28 Basf Se Eljárás bórt és titánt tartalmazó MWW zeolitos anyag elõállítására
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

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JP2010159245A (ja) * 2008-09-19 2010-07-22 Sumitomo Chemical Co Ltd 酸化化合物の製造方法

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JP2010159245A (ja) * 2008-09-19 2010-07-22 Sumitomo Chemical Co Ltd 酸化化合物の製造方法

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Publication number Priority date Publication date Assignee Title
CN111818997A (zh) * 2018-03-15 2020-10-23 住友化学株式会社 含钛的硅氧化物成型体的制造方法以及含钛的硅氧化物成型体
CN111818997B (zh) * 2018-03-15 2023-04-04 住友化学株式会社 含钛的硅氧化物成型体的制造方法以及含钛的硅氧化物成型体
CN110240176A (zh) * 2019-07-16 2019-09-17 上海纳米技术及应用国家工程研究中心有限公司 一种介孔钛硅分子筛纳米粒子的制备方法

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