WO2012002408A1 - Procédé de production d'oxyde de propylène - Google Patents

Procédé de production d'oxyde de propylène Download PDF

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WO2012002408A1
WO2012002408A1 PCT/JP2011/064858 JP2011064858W WO2012002408A1 WO 2012002408 A1 WO2012002408 A1 WO 2012002408A1 JP 2011064858 W JP2011064858 W JP 2011064858W WO 2012002408 A1 WO2012002408 A1 WO 2012002408A1
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group
sulfide
production method
noble metal
solvents
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Japanese (ja)
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史一 山下
水野　雅彦
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住友化学株式会社
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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
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
    • 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
    • B01J21/18—Carbon
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0218—Sulfides
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0222—Sulfur-containing compounds comprising sulfonyl groups
    • 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
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation
    • 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 propylene oxide.
  • a palladium-treated TS-1 crystal catalyst is slurried with methanol / water, and liquid propylene and a mixed gas containing hydrogen, oxygen and nitrogen are fed into the slurry to produce propylene oxide. How to do is described.
  • the present invention [1] Noble metal catalyst, crystalline titanosilicate having MFI structure and formula (I): R 1 —S (O) n —R 2 (I) (In the formula, R 1 and R 2 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a substituent and contain a hetero atom. (N represents an integer of 0 to 2)
  • the production method according to [1], wherein the crystalline titanosilicate having an MFI structure is TS-1.
  • the present invention relates to a noble metal catalyst, a crystalline titanosilicate having an MFI structure and the formula (I): R 1 -S (O) n -R 2 (I)
  • n represents an integer of 0-2.
  • the organic sulfur compound represented by the formula (I) include a sulfide compound in which n is 0 in the formula (I), a sulfoxide compound in which n is 1 in the formula (I), and n in the formula (I) 2
  • the sulfone compound which is is mentioned.
  • R 1 And R 2 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a substituent or may contain a hetero atom.
  • a hetero atom includes a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the hydrocarbon group containing a hetero atom means a group in which a part of atoms or atomic groups constituting the hydrocarbon group is replaced with a hetero atom.
  • Examples of the unsubstituted hydrocarbon group include an unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted aryl group having 4 to 20 carbon atoms, and an unsubstituted alkenyl group having 2 to 20 carbon atoms.
  • Examples of the unsubstituted alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl And linear or branched alkyl groups having 1 to 20 carbon atoms such as a group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and icosyl group.
  • the methylene group contained in these alkyl groups may be replaced with a hetero atom.
  • C1-20 such as an alkyl group having 1 to 20 carbon atoms may be referred to as “C1-20”.
  • the aryl group may be a heteroaryl group containing a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom as a ring constituent atom.
  • Examples of the unsubstituted aryl group having 4 to 20 carbon atoms include phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, furanyl group and pyridyl group.
  • Examples of the unsubstituted alkenyl group having 2 to 20 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and 1-hexenyl group. , Heptenyl group, octenyl group, nonenyl group and decenyl group.
  • the methylene group contained in these alkenyl groups may be replaced with a hetero atom.
  • the hydrocarbon group having a substituent means a group in which one or more hydrogen atoms of an unsubstituted hydrocarbon group are replaced with a substituent.
  • An alkyl group having a substituent means a group in which one or more hydrogen atoms of an unsubstituted alkyl group is replaced with a substituent, and an aryl group having a substituent is one or more of an unsubstituted aryl group
  • a alkenyl group having a substituent means a group in which one or more hydrogen atoms of an unsubstituted alkenyl group are replaced with a substituent.
  • substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group (—OH); methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy Group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, An alkoxy group having 1 to 20 carbon atoms such as nonadecyloxy group and icosyloxy group; an aryloxy group having 6 to 20 carbon atoms such as phenoxy group, biphenyloxy group, 1-naphthoxy group and 2-n
  • a sulfide compound in which n is 0 is represented by the formula (1) R 1 -S-R 2 (1) (Wherein R 1 And R 2 Represents the same meaning as described above. ) It is a compound shown by these.
  • the sulfide compound represented by the formula (1) dialkyl sulfide, alkylaryl sulfide, diaryl sulfide, and sulfide compounds in which the alkyl group and / or aryl group of these sulfide compounds have a substituent are preferable.
  • Di (C1-C20 alkyl) sulfide, (C1-C20 alkyl) (C6-C20 aryl) sulfide, di (C6-C20 aryl) sulfide, and the alkyl group and / or aryl group of these sulfide compounds have a substituent. More preferred are sulfide compounds, such as di (C1-C5 alkyl) sulfide, (C1-C5 alkyl) (C6-C10 aryl) sulfide, di (C6-C10 aryl) sulfide, and alkyl groups and / or aryls of these sulfide compounds.
  • a sulfide compound in which the group has a hydroxy group is particularly preferred.
  • the sulfide compound represented by the formula (1) include dimethyl sulfide, diethyl sulfide, dipropyl sulfide, isopropyl methyl sulfide, diisopropyl sulfide, dibutyl sulfide, tert-butyl methyl sulfide, di-tert-butyl sulfide, bis (methylthio) methane.
  • the sulfoxide compound in which n is 1 is represented by the formula (2) R 1 -S (O) -R 2 (2) (Wherein R 1 And R 2 Represents the same meaning as described above. ) It is a compound shown by these.
  • Examples of the sulfoxide compound represented by the formula (2) include dialkyl sulfoxide, alkylaryl sulfoxide, diaryl sulfoxide, and sulfoxide compounds in which the alkyl group and / or aryl group of these sulfoxide compounds have a substituent.
  • (C1-C20 alkyl) sulfoxide, (C1-C20 alkyl) (C6-C20 aryl) sulfoxide and di (C6-C20 aryl) sulfoxide are preferred, (C1-C5 alkyl) sulfoxide, (C1-C5 alkyl) (C6- C10 aryl) sulfoxide and di (C6-C10 aryl) sulfoxide are more preferred.
  • Examples of the sulfoxide compound represented by the formula (2) include dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, dibutyl sulfoxide, tetramethylene sulfoxide, diphenyl sulfoxide, methylphenyl sulfoxide, phenyl vinyl sulfoxide, dibenzyl sulfoxide, methyl (methylsulfinyl) methyl.
  • Examples include sulfide and 1,2-bis (phenylsulfinyl) ethane.
  • the sulfone compound in which n is 2 is represented by the formula (3) R 1 -S (O) 2 -R 2 (3) (Wherein R 1 And R 2 Represents the same meaning as described above. ) It is a compound shown by these.
  • the sulfone compound represented by formula (3) include dialkyl sulfone, alkylaryl sulfone, diaryl sulfone, cyclic sulfone having an alkylene structure, and sulfone compounds in which the alkyl group and / or aryl group of these sulfone compounds have a substituent. Can be mentioned.
  • Di (C1-C20 alkyl) sulfone, (C1-C20 alkyl) (C6-C20 aryl) sulfone and di (C6-C20 aryl) sulfone are preferred, and di (C1-C5 alkyl) sulfone, (C1-C5 alkyl) ( More preferred are C6-C10 aryl) sulfone and di (C6-C10 aryl) sulfone.
  • Examples of the sulfone compound represented by the formula (3) include dimethyl sulfone, ethyl methyl sulfone, isopropyl methyl sulfone, dipropyl sulfone, dibutyl sulfone, 2-hydroxymethyl ethyl sulfone, 3-sulfolene, divinyl sulfone, sulfolane, methyl phenyl sulfone, Ethylphenylsulfone, phenylvinylsulfone, diphenylsulfone, bis (vinylsulfonyl) methane, 4,4-dioxo-1,4-oxathiane, 3-methylsulfolane, methylsulfonylacetonitrile, 4-chlorophenylmethylsulfone, (phenylsulfonyl) acetic acid Examples include ethyl and allyl phenyl sulfone
  • dimethyl sulfone, diphenyl sulfone and sulfolane are preferable, and diphenyl sulfone is more preferable.
  • the organic sulfur compound represented by the formula (I) is dissolved in a solvent described later.
  • a method in which the organic sulfur compound represented by the formula (I) is supported on a noble metal catalyst described later and supplied.
  • the sulfide compound, the sulfoxide compound, or the compound converted into the sulfone compound by being oxidized with oxygen or reduced with hydrogen in the reaction system may be supplied into the reaction system.
  • the amount of the organic sulfur compound represented by formula (I) in the reaction of hydrogen, oxygen and propylene is usually in the range of 0.1 ⁇ mol / kg to 500 mmol / kg, preferably 1 ⁇ mol / kg to 1 kg of the solvent.
  • the range is 50 mmol / kg, and more preferably 1 ⁇ mol / kg to 5 mmol / kg.
  • the noble metal catalyst include catalysts containing noble metals such as palladium, platinum, ruthenium, rhodium, iridium, osmium, gold and the like.
  • the noble metal catalyst may contain one kind of noble metal or may contain two or more kinds of noble metals. An alloy or a mixture of two or more kinds of noble metals may be included.
  • a mixture of noble metals other than palladium such as platinum, gold, rhodium, iridium, osmium, and palladium, and other noble metals and palladium
  • noble metal at least one noble metal selected from the group consisting of palladium, platinum and gold is preferable, and palladium, a mixture of palladium and gold, and a mixture of palladium and platinum are more preferable.
  • a noble metal colloid such as a palladium colloid may be used as a noble metal catalyst.
  • noble metal colloids commercially available ones may be used, or those prepared by dispersing noble metal particles with a dispersing agent such as citric acid, polyvinyl alcohol, polyvinyl pyrrolidone, sodium hexametaphosphate or the like may be used.
  • a dispersing agent such as citric acid, polyvinyl alcohol, polyvinyl pyrrolidone, sodium hexametaphosphate or the like
  • a noble metal catalyst a catalyst in which a noble metal is supported on a carrier is preferably used.
  • Examples of the carrier include crystalline titanosilicate having an MFI structure, which will be described later, silica, alumina, titania, zirconia, niobia and other oxides; niobic acid, zirconium acid, tungstic acid, titanic acid and other hydroxides; and activated carbon , Carbon such as carbon black, graphite and carbon nanotubes. Two or more kinds of carriers may be used. Preferable carriers include crystalline titanosilicate having an MFI structure and carbon described later, and activated carbon is more preferable.
  • Examples of the compound containing a noble metal include tetravalent palladium compounds such as sodium hexachloropalladium (IV) tetrahydrate and potassium hexachloropalladium (IV); and palladium (II) chloride, palladium (II) bromide, acetic acid Palladium (II), palladium acetylacetonate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichloro (bis (diphenylphosphino) ethane) palladium (II), dichlorobis (tri Phenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dibromotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium trifluoroacetate Divalent palladium compound
  • the noble metal compound supported on the carrier is preferably reduced.
  • a method of reducing in a liquid phase or a gas phase using a reducing agent can be mentioned.
  • a reducing agent includes hydrogen.
  • a preferable reaction temperature (reduction temperature) in the gas phase reduction is in the range of 0 to 500 ° C.
  • the noble metal compound is supported on a carrier. Thereafter, heat treatment may be performed in an inert gas atmosphere.
  • the reduction temperature varies depending on the type of the noble metal compound.
  • the reduction temperature when dichlorotetraamminepalladium (II) is used as the noble metal compound is preferably in the range of 100 to 500 ° C., more preferably in the range of 200 to 350 ° C.
  • the reducing agent include hydrogen, hydrazine monohydrate, formaldehyde, and sodium borohydride.
  • reduction may be performed by adding an alkali.
  • the reaction conditions for the liquid phase reduction can be selected appropriately depending on the types of the noble metal compound and the carrier and the type and amount of the reducing agent used.
  • the content of the noble metal in the supported noble metal catalyst is usually in the range of 0.01 to 20% by mass, and preferably in the range of 0.1 to 10% by mass.
  • the amount of the noble metal catalyst used in the reaction of hydrogen, oxygen and propylene is preferably 0.00001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, based on the solvent.
  • the organic sulfur compound represented by the formula (I) may be further supported on the noble metal catalyst supported on the support.
  • the noble metal catalyst on which the organic sulfur compound represented by the formula (I) is supported can be prepared, for example, according to the method described in Advanced Synthesis and Catalysis 350, 406-410 (2008).
  • the obtained solid is washed with alcohol and, if necessary, other organic solvents. Can be obtained.
  • the supported amount of the organic sulfur compound represented by the formula (I) is preferably in the range of 0.01 to 25% by mass in terms of sulfur atom. More preferably, it is in the range of 0.01 to 5% by mass.
  • the reaction of hydrogen, oxygen and propylene is carried out in the presence of a crystalline titanosilicate having an MFI structure in addition to the noble metal catalyst and the organic sulfur compound represented by the formula (I).
  • Titanosilicate is a general term for silicates having tetracoordinate Ti (titanium atoms), and has a porous structure.
  • the titanosilicate used in the production method of the present invention substantially means a titanosilicate having tetracoordinated Ti, and the ultraviolet-visible absorption spectrum in the wavelength region of 200 nm to 400 nm is maximum in the wavelength region of 210 nm to 230 nm. (See, for example, Chemical Communications 1026-1027, (2002) FIGS. 2D and 2E).
  • the ultraviolet-visible absorption spectrum can be measured by a diffuse reflection method using an ultraviolet-visible spectrophotometer equipped with a diffuse reflection device.
  • the crystalline titanosilicate having an MFI structure means a crystalline titanosilicate having an MFI structure as a structure code of IZA (International Zeolite Society), and specifically includes TS-1.
  • a general method for synthesizing crystalline titanosilicate having an MFI structure is to hydrolyze a titanium compound and a silicon compound using a surfactant as a mold agent or a structure-directing agent, and hydrothermal synthesis as necessary. In this method, the surfactant is removed by calcination or extraction after crystallization or pore regularity is improved.
  • a crystalline titanosilicate having a preferred MFI structure is TS-1.
  • a crystalline titanosilicate having an MFI structure activated by pretreatment with a hydrogen peroxide solution can also be used.
  • a method in which a hydrogen peroxide solution having a hydrogen peroxide concentration in the range of 0.0001% by mass to 50% by mass and a crystalline titanosilicate having an MFI structure are brought into contact is preferably a mixed solvent of water and an organic solvent.
  • the mass ratio of noble metal catalyst to crystalline titanosilicate having MFI structure in the reaction of hydrogen, oxygen and propylene is 0.01 to 100 mass. % Is preferable, and a range of 0.1 to 100% by mass is more preferable.
  • the reaction of hydrogen, oxygen and propylene is usually carried out in a solvent.
  • the solvent water, an organic solvent or a mixed solvent thereof is preferable.
  • the organic solvent include alcohol solvents, ketone solvents, nitrile solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ester solvents, and glycol solvents, and alcohol solvents are preferable. Two or more organic solvents can be used in combination.
  • Alcohol solvents include linear or branched saturated aliphatic alcohols and aromatic alcohols.
  • alkyl alcohols having 1 to 4 carbon atoms such as methanol, ethanol, isopropanol, and tert-butanol
  • aryl alcohols having 6 to 10 carbon atoms preferably alkyl alcohols having 1 to 4 carbon atoms, More preferred.
  • the ketone solvent include aliphatic ketones having 3 to 6 carbon atoms such as acetone, 2-butanone, 3-methyl-2-butanone, and 3-pentanone, and acetophenone.
  • nitrile solvent include aliphatic nitriles having 2 to 4 carbon atoms such as acetonitrile, propionitrile, isobutyronitrile, butyronitrile, and benzonitrile.
  • ether solvent examples include alkyl ethers having 3 to 8 carbon atoms such as diethyl ether, diisopropyl ether, dimethoxymethane, trimethyl orthoformate, and anisole.
  • aliphatic hydrocarbon solvent examples include aliphatic hydrocarbon solvents having 5 to 10 carbon atoms such as hexane and heptane.
  • aromatic hydrocarbon solvent examples include aromatic hydrocarbon solvents having 6 to 15 carbon atoms such as benzene, toluene and xylene.
  • halogenated hydrocarbon solvent examples include halogenated aliphatic hydrocarbons having 1 to 4 carbon atoms such as dichloromethane, 1,2-dichloroethane, chloroform, and carbon tetrachloride.
  • ester solvent examples include carboxylic acid alkyl esters having 3 to 6 carbon atoms such as ethyl acetate, ethyl propionate, propyl acetate, and methyl isobutyrate.
  • glycol solvent examples include alkylene glycols having 2 to 4 carbon atoms such as ethylene glycol, propylene glycol, and diethylene glycol. Of these, a mixed solvent of water and an alcohol solvent is preferable.
  • the ratio of water and alcohol solvent (water: alcohol solvent) in the mixed solvent of water and alcohol is preferably in the range of 90:10 to 0.01: 99.99, and is in the range of 50:50 to 0.1: 99.9. The range is more preferable, and the range of 40:60 to 5:95 is particularly preferable. It is preferable to carry out the reaction in a state where the organic sulfur compound represented by the formula (I) is dissolved in a solvent.
  • oxygen include molecular oxygen such as oxygen gas.
  • the oxygen gas may be an oxygen gas produced by a pressure swing method, or may be a high-purity oxygen gas produced by cryogenic separation or the like. Moreover, air may be used as oxygen.
  • hydrogen hydrogen gas is generally used.
  • Oxygen gas and hydrogen gas can be diluted with an inert gas that does not hinder the progress of the reaction.
  • Inert gases include nitrogen, argon, carbon dioxide, methane, ethane and propane.
  • the flow rate of oxygen gas, the flow rate of hydrogen gas, and the concentration of the inert gas that dilutes these gases may be appropriately adjusted according to other conditions such as the amount of propylene used and the reaction scale.
  • propylene is preferably at a concentration of 0.01 to 1000 g with respect to 1 L of the solvent used for the reaction.
  • the reactor used for the reaction include a flow-type fixed bed reactor and a flow-type slurry complete mixing reactor.
  • the reaction temperature is usually in the range of 0 to 150 ° C., preferably in the range of 40 to 90 ° C.
  • the reaction pressure is a gauge pressure and is usually in the range of 0.1 MPa to 20 MPa, preferably in the range of 1 MPa to 10 MPa.
  • propylene oxide can be taken out by distillation separation of the liquid phase or gas phase taken out from the reactor.
  • the reaction it is preferable to carry out the reaction in the presence of an additive exhibiting an effect of suppressing the by-production of propane such as a polycyclic compound and a quinoid compound in the reaction system.
  • an additive exhibiting an effect of suppressing the by-production of propane such as a polycyclic compound and a quinoid compound in the reaction system.
  • the propylene oxide selectivity based on hydrogen hereinafter sometimes referred to as hydrogen-based selectivity
  • the additive include polycyclic compounds such as anthracene, tetracene, 9-methylanthracene, naphthalene, tetracene, and diphenyl ether (see, for example, JP-A-2009-23998), anthraquinone, and 9,10-phenanthraquinone.
  • Quinoid compounds such as benzoquinone and 2-ethylanthraquinone (for example, see JP-A-2008-106030).
  • condensed polycyclic aromatic compounds such as anthracene, tetracene, 9-methylanthracene, naphthalene, tetracene, anthraquinone, 9,10-phenanthraquinone, and 2-ethylanthraquinone are preferable, and anthraquinone is more preferable.
  • the amount of the additive used is preferably in the range of 0.001 mmol / kg to 500 mmol / kg, more preferably in the range of 0.01 mmol / kg to 50 mmol / kg per 1 kg of the solvent used in the reaction.
  • the reaction may be carried out in the presence of a salt containing ammonium ion, alkylammonium ion or alkylarylammonium ion (hereinafter, these salts may be referred to as “ammonium salt”) in the reaction system.
  • ammonium salt containing ammonium ion, alkylammonium ion or alkylarylammonium ion
  • ammonium salt ammonium sulfate salt, ammonium hydrogen sulfate salt, ammonium hydrogen carbonate salt, ammonium phosphate salt, ammonium hydrogen phosphate salt, ammonium dihydrogen phosphate, ammonium hydrogen pyrophosphate, ammonium pyrophosphate, ammonium halide
  • ammonium salts of inorganic acids such as salts and ammonium nitrate
  • ammonium salts of organic acids such as ammonium acetate.
  • diammonium hydrogen phosphate is preferable.
  • the amount of ammonium salt used is usually in the range of 0.001 mmol / kg to 100 mmol / kg per kg of the solvent used in the reaction.
  • the production method of the present invention is excellent in propylene oxide selectivity based on hydrogen (hydrogen-based selectivity). In addition, the amount of propylene oxide produced per hour per weight of the crystalline titanosilicate having an MFI structure is excellent.
  • the reaction mixture contains by-products such as unreacted propylene and propane in addition to the target propylene oxide, and the target propylene oxide is removed from the reaction mixture by known separation means and purification means. Can be separated.
  • separation means and purification means include distillation separation.
  • Example 1 The autoclave having a capacity of 0.3 L was charged with TS-1 (Catalyst Society Reference Catalyst, ARC-TS1AS (1)) and the Pd / AC catalyst obtained in Reference Example 1, and then the autoclave was sealed.
  • TS-1 Catalyst Society Reference Catalyst, ARC-TS1AS (1)
  • a raw material gas having a volume ratio of propylene / oxygen / hydrogen / nitrogen of 7.2 / 4.0 / 4.2 / 85.6 is supplied at an feeding rate of 20 L / hour and anthraquinone 0.07 mmol / kg.
  • a liquid phase and a gas phase were continuously extracted from the autoclave through a filter.
  • the residence time in the autoclave was 90 minutes.
  • the temperature of the mixture in the autoclave was adjusted to 60 ° C. and the pressure was adjusted to 0.8 MPa (gauge pressure).
  • the amount of TS-1 and Pd / AC catalyst used is adjusted so that the amount of TS-1 is 1.2g and the amount of Pd / AC catalyst is 0.08g with respect to 133g of solvent supplied in the autoclave. did.
  • the propylene oxide (PO) production activity per unit mass of titanosilicate was 5.2 mmol-PO / g-tita.
  • the S (sulfur) content in the Pd / AC catalyst determined by ICP emission analysis was 0.041% by mass.
  • 0.6 g of the obtained Pd / AC catalyst and 8 mL of a methanol solution containing 0.021 g of diphenyl sulfide were charged into a 10 mL two-necked eggplant flask. The resulting mixture was stirred at room temperature for 5 days under air atmosphere. The obtained suspension was filtered, washed with methanol and diethyl ether, and vacuum-dried at 50 ° C. for 2 hours to obtain diphenyl sulfide-containing Pd / AC catalyst (Pd / AC catalyst carrying diphenyl sulfide). .
  • Example 2 In Example 1, instead of a water / methanol solution containing 0.07 mmol / kg of anthraquinone and 5.4 ⁇ mol / kg of diphenyl sulfide, a water / methanol solution containing 0.07 mmol / kg of anthraquinone and not containing diphenyl sulfide was used.
  • the reaction was conducted in the same manner as in Example 1 except that the Pd / AC catalyst obtained in Reference Example 2 was used instead of the Pd / AC catalyst obtained in Reference Example 1.
  • the liquid phase and gas phase extracted from the autoclave 5 hours after the start of the reaction were analyzed by gas chromatography.
  • the propylene oxide (PO) production activity per unit mass of titanosilicate was 4.8 mmol-PO / g-titano. It was silicate and time, and the hydrogen standard selectivity (molar amount of propylene oxide produced / molar amount of hydrogen consumed) was 20%.
  • Example 1 In Example 1, instead of a water / methanol solution containing 0.07 mmol / kg of anthraquinone and 5.4 ⁇ mol / kg of diphenyl sulfide, a water / methanol solution containing 0.07 mmol / kg of anthraquinone without containing diphenyl sulfide was used. The reaction was performed in the same manner as in Example 1 except that. The liquid phase and gas phase extracted from the autoclave after 5 hours from the start of the reaction were analyzed by gas chromatography. As a result, the propylene oxide (PO) production activity per unit mass of titanosilicate was 4.4 mmol-PO / g-tita. It was no silicate and time, and the hydrogen standard selectivity was 18%.
  • PO propylene oxide

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Abstract

La présente invention a pour objet un procédé de production d'oxyde de propylène, ledit procédé comprenant un processus de réaction d'hydrogène, d'oxygène et de propylène en présence d'un catalyseur de métal précieux, de titanosilicate cristallisé avec une structure MFI et d'un composé soufré organique représenté par la formule (I) : R1-S(O)n-R2 (I) (dans la formule, R1 et R2 représentent chacun indépendamment des groupes hydrocarbures en C1 à C20 et lesdits groupes hydrocarbures peuvent comporter des groupes substituants ou comprendre des hétéroatomes. n représente un nombre entier de 0 à 2.)
PCT/JP2011/064858 2010-06-28 2011-06-22 Procédé de production d'oxyde de propylène WO2012002408A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155653A (zh) * 2022-08-12 2022-10-11 华东理工大学 一种硫助剂修饰的钛硅分子筛固载金催化剂及其制备方法与应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999025666A2 (fr) * 1997-11-14 1999-05-27 Du Pont Pharmaceuticals Company Procede d'oxydation selective de composes organique
JP2005131470A (ja) * 2003-10-28 2005-05-26 Nippon Shokubai Co Ltd 金属微粒子担持体
WO2005092501A2 (fr) * 2004-03-09 2005-10-06 Lyondell Chemical Technology, L.P. Zeolites de titane encapsulees dans un polymere et utilisees pour des reactions d'oxydation
JP2006083152A (ja) * 2004-08-19 2006-03-30 Daikin Ind Ltd ヘキサフルオロプロピレンオキシドの製造方法
WO2007126139A1 (fr) * 2006-04-27 2007-11-08 Sumitomo Chemical Company, Limited Procede de fabrication de compose epoxy
WO2010074315A1 (fr) * 2008-12-26 2010-07-01 Sumitomo Chemical Company, Limited Procédé de production d'oxyde de propylène

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999025666A2 (fr) * 1997-11-14 1999-05-27 Du Pont Pharmaceuticals Company Procede d'oxydation selective de composes organique
JP2005131470A (ja) * 2003-10-28 2005-05-26 Nippon Shokubai Co Ltd 金属微粒子担持体
WO2005092501A2 (fr) * 2004-03-09 2005-10-06 Lyondell Chemical Technology, L.P. Zeolites de titane encapsulees dans un polymere et utilisees pour des reactions d'oxydation
JP2006083152A (ja) * 2004-08-19 2006-03-30 Daikin Ind Ltd ヘキサフルオロプロピレンオキシドの製造方法
WO2007126139A1 (fr) * 2006-04-27 2007-11-08 Sumitomo Chemical Company, Limited Procede de fabrication de compose epoxy
WO2010074315A1 (fr) * 2008-12-26 2010-07-01 Sumitomo Chemical Company, Limited Procédé de production d'oxyde de propylène

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155653A (zh) * 2022-08-12 2022-10-11 华东理工大学 一种硫助剂修饰的钛硅分子筛固载金催化剂及其制备方法与应用

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