WO2012133934A1 - Process for producing noble metal catalyst supported on carbon and its use with a titanosilicate for the oxidation of olefins to alkylene oxides - Google Patents

Process for producing noble metal catalyst supported on carbon and its use with a titanosilicate for the oxidation of olefins to alkylene oxides Download PDF

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Publication number
WO2012133934A1
WO2012133934A1 PCT/JP2012/059292 JP2012059292W WO2012133934A1 WO 2012133934 A1 WO2012133934 A1 WO 2012133934A1 JP 2012059292 W JP2012059292 W JP 2012059292W WO 2012133934 A1 WO2012133934 A1 WO 2012133934A1
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noble metal
titanosilicate
catalyst
resin
mixture
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PCT/JP2012/059292
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French (fr)
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Fumikazu Yamashita
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Sumitomo Chemical Company, Limited
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Publication of WO2012133934A1 publication Critical patent/WO2012133934A1/en

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    • 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
    • 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
    • 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
    • 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
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0242—Coating followed by impregnation
    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support

Definitions

  • the present invention relates to a process for producing a noble metal catalyst.
  • the present invention also relates to a process for producing an alkylene oxide in which the noble metal catalyst is used.
  • a noble metal catalyst, and a tltanosilicate catalyst are used in a process in which hydrogen, oxygen and propylene are reacted to produce propylene oxide.
  • a noble metal catalyst a catalyst obtained by supporting palladium on activated carbon, and then calcining the resultant is known from JP 2010-168358 A, for example.
  • the present invention provides the followings:
  • a process for producing a noble metal catalyst comprising the .steps of:
  • the noble metal is at least one metal selected from the group consisting of palladium, platinum, ruthenium, rhodium, iridium, osmium and gold.
  • a catalyst for producing an alkylene oxide comprising a titanosilicate catalyst and a noble metal catalyst produced by the process according to any one of the above items [1] to [3] .
  • titanosilicate catalyst is at least one catalyst selected from the group consisting of a titanosilicate having an M W structure and a precursor thereof.
  • a catalyst capable of producing an alkylene oxide in a high yield can be provided.
  • the process of the present invention is a process for producing a noble metal catalyst, comprising the steps of: 1) mixing a carbon material with a resin in a solvent to prepare a mixture ;
  • the noble metal catalyst produced by the present process is capable of generating hydrogen peroxide from oxygen and hydrogen.
  • the noble metal catalyst in combination with a titanosilicate catalyst, the noble metal catalyst becomes useful as a catalyst to be used in the production of an alkylene oxide (hereinafter, the production of an alkylene oxide is sometimes referred to as "the present production") .
  • the step 1 is a step in which a carbon material and a resin are mixed in a solvent to prepare a mixture.
  • the carbon material is a material which consists mainly of carbon.
  • Examples of the carbon material include activated carbon, carbon black, graphite and carbon nanotube . Among them, activated carbon is preferable because it has a larger surface area.
  • the raw materials of the activated carbon and the activation method thereof are not particularly limited, and the activated carbon having a large pore volume is preferable.
  • the raw materials of the activated carbon include wood, sawdust, palm shell, coal and petroleum materials.
  • the activated carbons which are activated by the aforementioned methods are preferable because their pore volume and average pore size become larger.
  • the form of the activated carbon is not particularly limited, and powdery activated carbon, granular activated carbon, crushed activated carbon, fibrous activated carbon, honeycomb activated carbon or the like may be used.
  • the resin used in the process of the present invention is not particularly limited and any known resin may be used. It is preferable to use a resin soluble in a solvent used in the step 1.
  • Examples of the resin include polyethylene,
  • polypropylene polybutadiene, polystyrene,
  • polymethylmethacrylate polyacrylonitrile, polyacrylic acid, polyethylene glycol, polyvinylpyrrolidone, polyurea, polyester, polyurethane , polyimide, polyethyleneimine, polyvinyl alcohol, polyvinyl chloride, polyvinyl acetate, polyvinylidene fluoride, polycarbonate, Nylon 6, Nylon 66 and a silicone resin.
  • polyvinyl alcohol, polyvinyl acetate, and polymethylmethacrylate are preferable, and polyvinyl alcohol is more preferable.
  • a solvent capable of dissolving the aforementioned resin is preferable.
  • the solvent can be properly selected depending on the kind of a resin to be used. Examples of such a solvent include water, alcohol solvents, ketone solvents, nitrile solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ester solvents, glycol solvents, and amide solvents.
  • alcohol solvent examples include methanol, ethanol, isopropanol, tert-butanol , 1-hexanol, cyclohexanol, and 2-ethylhexanol .
  • ketone solvent examples include acetone, 2-butanone, 2-heptanone, and cyclohexanone .
  • nitrile solvent examples include acetonitrile and benzonitrile .
  • ether solvent examples include diethyl ether, tetrahydrofuran, and anisole.
  • Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, heptane, and cyclohexane.
  • aromatic hydrocarbon solvent examples include benzene, toluene, and xylene.
  • halogenated hydrocarbon solvent examples include dichloromethane, chloroform, carbon tetrachloride, and dichloroethane .
  • ester solvent examples include ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, ethyl lactate, and ethyl pyruvate.
  • glycol solvent examples include ethylene glycol, diethylene glycol, and propylene glycol.
  • amide solvent examples include formamide, acetamide, N, -dimethylformamide, N, N-dimethylacetamide .
  • These solvents may be used alone or as a mixture of two or more kinds thereof.
  • a carbon material and a resin are mixed in a solvent to prepare. a mixture.
  • the amount of the carbon material in the mixture is preferably from 1 to 10,000 parts by mass> more preferably from 2 to 1, 000 parts by mass, based on one part by mass of the resin.
  • the amount of the resin in the mixture is preferably from 0.001 to 50% by mass, more preferably from 0.01 to 20% by mass, based on the total amount of the resin and the solvent .
  • the temperature for mixing the carbon material with the resin is preferably from 10°C to 200°C, more preferably from 20°C to 150°C.
  • the time of mixing is preferably from 10 minutes to 30 hours, more preferably from 1 hour to 24 hours.
  • the order of mixing is not particularly limited, and it is preferable that the resin is dissolved in the solvent and then the carbon - material is added thereto.
  • the mixing may be carried out under a nitrogen atmosphere or an .air.
  • the step 2 is a step in which a carbon material treated with a resin from the mixture prepared in the step 1.
  • the mixture prepared in the step 1 is cooled (i.e., a cooling process is employed). Cooling the mixture tends to increase an adhesion of the carbon material to the resin, even where an affinity between the carbon material and the resin is low.
  • the mixture is preferably cooled to a temperature of from 0°C to 50°C, more preferably from 0°C to 30°C.
  • the mixture is preferably cooled to a temperature which is lower by preferably 10°C to 200°C, more preferably 20°C to 150°C, and still more preferably 30°C to 120°C than the mixing temperature of the step 1.
  • the time of cooling the mixture is preferably from 30 minutes to 36 hours, more preferably from 1 hour to 24 hours.
  • the cooling may be carried out under a nitrogen atmosphere or an air.
  • a carbon material treated with a resin can be taken out from the mixture by filtration, for example.
  • the obtained carbon material treated with the resin may be dried as necessary.
  • the temperature is preferably from 30°C to 200°C. It is preferable to dry the mixture under a reduced pressure or under an atmosphere of an inert gas.
  • the step 3 is a step in which the carbon material treated with the resin, which is obtained in the step 2, is heated to obtain a carrier.
  • the heating temperature is preferably from 250°C to 800°C, more preferably from 250°C to 600°C.
  • the time of heating is preferably from 30 minutes to 24 hours, more preferably from 1 hour to 12 hours.
  • the heating may be carried out under an atmosphere of an inert gas or an air.
  • the heating is preferably carried out an atmosphere of an inert gas.
  • the inert gas include nitrogen gas and a noble gas such as argon gas.
  • the step 4 is a step in which a noble metal is supported on the carrier obtained by the step 3 (hereinafter, the carrier obtained by the step 3 is sometimes referred to as "carrier (A)").
  • the noble metal for example, palladium, platinum, ruthenium, osmium, rhodium, iridium and gold may be used.
  • the noble metal may be used alone, or as an alloy or mixture of two or more kinds thereof.
  • the noble metal is preferably palladium, platinum, gold and an alloy orTnixture thereof, more preferably palladium, an alloy or mixture of palladium and gold, or an alloy or mixture of palladium and platinum, still more preferably palladium.
  • the noble metal catalyst produced using such a noble metal is used in the present production, generation of hydrogen peroxide in the system tends to increase and yield of an alkylene oxide tends to increase in the present production.
  • Examples of the method for supporting a noble metal on the carrier (A) include a method of supporting a noble metal compound on the carrier (A) and then reducing the noble metal, and a method of mixing a noble metal colloid and the carrier. (A) .
  • a noble metal compound is firstly supported on the carrier (A) by an impregnation method, and then, the noble metal compound is reduced to form zero valent noble metal.
  • the noble metal compound examples include noble metal chlorides.
  • the palladium compound include tetravalent palladium compounds such as sodium hexachloropalladate (IV) tetrahydrate and potassium hexachloropalladate (IV); and divalent palladium compounds such as palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II),
  • dichloro bis (diphenylphosphino) ethane
  • dichlorobis triphenylphosphine
  • the impregnation method may be performed, for example, by impregnating a solution of the noble metal compound (e.g., an aqueous solution of the aforementioned noble metal compound) with the carrier (A) at room temperature for 10 minutes to 30 hours.
  • a solution of the noble metal compound e.g., an aqueous solution of the aforementioned noble metal compound
  • a noble metal catalyst may be obtained by reducing the noble metal compound which the carrier (A) supporting the noble metal contains.
  • the noble metal compound may be reduced by a method of reduction using a reductant in a liquid phase or a gas phase.
  • a gas-phase reduction a method in which hydrogen is used as the reductant and the reduction is carried out at a temperature of from 0°C to 500°C may be used.
  • the noble metal compound which has been supported on a carrier may be subjected to thermal treatment under an atmosphere of an inert gas.
  • ammonia gas generated from the noble metal compound serves as a reductant.
  • the temperature of the thermal treatment may vary depending on the kind of the noble metal compound used, and the like.
  • dichlorotetraamminepalladium (II) is used as the noble metal compound, the temperature is preferably from 100°C to 500°C, more preferably from 200°C to 350°C.
  • liquid-phase reduction When the reduction is performed in a liquid phase (liquid-phase reduction), hydrogen, hydrazine ' monohydrate, formaldehyde and sodium borohydride may be used as a reductant. When hydrazine monohydrate or formaldehyde is used, it may be used in combination with an alkali. Conditions of the liquid-phase reduction may be appropriately adjusted depending on the kind and amount of the noble metal compound, the carrier and the reductant to be used.
  • the noble metal catalyst is prepared by a process in which a noble metal colloid and the carrier (A) are mixed, for example, the noble metal colloid and the carrier (A) are mixed in a solvent (e.g., water), and then, the mixture is filtrated to obtain a solid.
  • a solvent e.g., water
  • a dispersion media of the noble metal colloid may be used as it is.
  • the temperature of mixing is not particularly limited, and it is preferably from 0°C to 100°C, more preferably from 15°C to 40°C.
  • the time of mixing is not particularly limited, and it is. preferably 10 minutes to 30 hours, more preferably 30 minutes to 18 hours.
  • the noble metal colloid a commercially available product may be used, and also, a noble metal colloid prepared by dispersing noble metal particles with a dispersant such as citric acid, polyvinyl alcohol, polyvinylpyrrolidone and sodium hexametaphosphate may be used.
  • a dispersant such as citric acid, polyvinyl alcohol, polyvinylpyrrolidone and sodium hexametaphosphate
  • the content of the noble metal is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the mass of the carbon material supporting the noble metal.
  • the catalyst of the present invention comprising the noble metal catalyst produced by the process of the present invention and titanosilicate catalyst is useful for production of an alkylene oxide.
  • An alkylene oxide can be produced by reacting hydrogen, oxygen and an olefin in the presence of a titanosilicate catalyst and the noble metal catalyst prepared by the process of the present invention.
  • the titanosilicate catalyst is a catalyst which consists mainly of titanosilicate and has an ability of olefin epoxidation. 1
  • titanosilicate catalyst is composed will be described in detail.
  • Titanosilicate is a generic name for a silicate having tetra-coordinated Ti (titanium atom) , and it has a porous configuration.
  • the titanosilicate of which the titanosilicate catalyst is composed refers to a titanosilicate substantially having tetra-coordinated Ti, in which a maximum absorption peak of an ultraviolet-visible absorption spectrum in a wavelength range of 200 nm to 400 nm appears in a wavelength range of 210 nm to 230 nm (see, for example, "Chemical Communications" 1026-1027, (2002), Figs. 2(d) and (e) ) .
  • the titanosilicate of which the titanosilicate catalyst is composed refers to a titanosilicate substantially having tetra-coordinated Ti, in which a maximum absorption peak of an ultraviolet-visible absorption spectrum in a wavelength range of 200 nm to 400 nm appears in a wavelength range of 210 nm
  • ultraviolet-visible- absorption spectrum can be measured by using an ultraviolet-visible spectrophotometer equipped with a diffuse reflector in accordance with a diffuse reflection method.
  • titanosilicate having fine pores of not less than 10-membered oxygen ring is preferable, because such titanosilicate has a high olefin epoxidation ability.
  • the fine pore herein refers to a pore formed with a Si-0 bond and/or a Ti-0 bond. The fine pore may be in the state of a half cup called as a side pocket, and does not have to penetrate through the primary particle of
  • titanosilicate not less than 10-membered oxygen ring
  • the term "not less than 10-membered oxygen ring” means that the number of oxygen atoms is 10 or more in either (a) a cross-section of the narrowest part of the fine pore or (b) a ring structure at the fine pore entrance.
  • the fact that a titanosilicate catalyst has fine pores of not less than 10-membered oxygen ring is generally confirmed by an analysis of an X-ray diffraction pattern.
  • the catalyst has a known structure, the structure can be easily confirmed by comparison of its X-ray diffraction pattern with the known one.
  • titanosilicate catalyst is composed include titanosilicates [1] to [7] described below.
  • TS-1 having the MFI structure (for example, US 4, 410, 501)
  • TS-2 having the MEL structure
  • Ti-ZSM-48 having the MRE structure
  • Ti-FER having the FER structure
  • IZA IZA
  • Ti-Beta having a BEA structure (for example, Journal of Catalysis 199, 41-47, (2001)), Ti-ZSM-12 having an MTW structure (for example, Zeolites 15, 236-242, (1995)), Ti-MOR. having an MOR structure (for example, The Journal of Physical Chemistry B 102, 9297-9303, (1998)), Ti-ITQ-7 having an ISV structure (for example, Chemical Communications
  • Ti-MCM-68 having an MSE structure for example, Chemical Communications 6224-6226, (2008)
  • Ti-MWW having an MWW structure for example, Chemistry Letters 774-775, (2000)
  • Ti-UTD-1 having a DON structure for example, Studies in Surface Science and Catalysis 15, 519-525, (1995)),. and the like.
  • Ti-ITQ-6 for example, Angewandte Chemie International Edition 39, 1499-1501, ' (2000), and the like.
  • a Ti-MWW precursor for example, EP-1731515-A1 .
  • Ti-MCM-41 for example, Microporous Materials 10, 259-271, (1997)
  • Ti-MCM-48 for example, Chemical
  • 12-membered oxygen ring means a ring structure having 12 oxygen atoms in either region (a) or (b) mentioned in the description regarding "10-membered oxygen ring".
  • 14-membered oxygen ring means a ring structure having 14 oxygen atoms in either region (a) or (b) mentioned above.
  • the titanosilicate may be a titanosilicate having a layered structure, such as a layered precursor of a crystalline titanosilicate, a titanosilicate in which spaces between layers in a crystalline titanosilicate are expanded. Whether a titanosilicate has a layered structure or not can be confirmed by electron microscopy or measurement of an X-ray diffraction pattern.
  • the layered precursor refers to a titanosilicate which forms a crystalline titanosilicate by a treatment such as dehydration condensation. It can be easily determined from the structure of a corresponding crystalline titanosilicate that a layered titanosilicate has fine pores of not less than 12-membered oxygen ring.
  • the Ti-MWW precursor refers to a titanosilicate having a layered structure, which forms a Ti-MWW by a
  • the dehydration-condensation may be carried out by heating the Ti-MWW precursor usually at a temperature of greater than 200°C to 1000°C or less, preferably at a temperature within the range of 300°C to 650°C.
  • the titanosilicates of [1] to [5] and [7] have fine pores with a pore size of 0.5 to 1.0 ran.
  • the pore size refers to the longest distance of in (a) a cross-section of the narrowest part of the fine pore and (b) a fine pore entrance.
  • the pore size refers to. a diameter in the above-mentioned regions (a) and (b) .
  • the pore size can be determined by an analysis of an X-ray diffraction pattern.
  • a mesoporous titanosilicate which has regular mesofine pores is preferable.
  • the regular mesofine pore refers to a structure in which mesopores are regularly and repeatedly arranged.
  • the titanosilicate is a mesoporous titanosilicate
  • the mesoporous titanosilicate which has mesofine pores having an average pore size of, 2 nm to 10 nm is more preferable.
  • Silylating of the titanosilicates can be carried out by a method in ' which the titanosilicate is brought into contact with a silylating agent or a method described in EP 1488853 Al .
  • the silylating agent include
  • Ti-MWW and Ti-MWW precursor are preferably used, and Ti-MWW precursor is more preferably used as a titanosilicate of which the titanosilicate catalyst is composed.
  • the silylated Ti-MWW or Ti-MWW precursor may be used- for a titanosilicate catalyst.
  • the Ti-MWW or Ti-MWW precursor shaped by using a known method may be used for a titanosilicate catalyst.
  • the content of titanium atom is preferably from 0.001 to 0.1 mol, more preferably from 0.005 to 0.05 mol, based on one mol of silicon atoms contained.
  • the noble metal catalyst obtained by the process of the present invention is preferably used in an amount of 0.01 to 100 parts by mass, more preferably 0.1 to 100 parts by mass, based on one part by mass of the titanosilicate catalyst used.
  • the present production is preferably carried out in a solvent.
  • a solvent water, an organic solvent and mixtures thereof are preferable.
  • the organic solvent include alcohol solvents, ketone solvents, nitrile solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ester solvents, glycol solvents and mixtures thereof.
  • nitrile solvents are preferable.
  • nitrile solvent examples include linear or branched saturated aliphatic nitriles and aromatic nitriles.
  • the specific examples of the nitrile solvent include
  • Acetonitrile is preferable.
  • the solvent is preferably a mixed solvent of water and nitrile.
  • a mass ratio of water and nitrile (water : nitrile) is preferably from 90 : 10 to 0.01 : 99.99, more preferably from 50 : 50 to 0.1 : 99.9, still more preferably 40 : 60 . to 5 : 95.
  • oxygen may be a molecular oxygen such as an oxygen gas.
  • the oxygen gas may be an oxygen gas produced by a pressure swing method or an oxygen gas having a high purity produced by cryogenic separation.
  • air may be used as oxygen.
  • a hydrogen gas is usually used as hydrogen.
  • the oxygen gas and/or the hydrogen gas used in the present production may be diluted with an inert gas which does not obstruct the progress of the present production.
  • the inert gas include nitrogen, argon, carbon dioxide, methane, ethane, and propane.
  • the amounts of the oxygen gas and the hydrogen gas supplied to the present production and the concentration of the inert gas used for diluting the gases may be appropriately adjusted according to an amount of the olefin to be used, the scale of the reaction and the like.
  • the molar ratio of oxygen and hydrogen supplied to the reactor is, for example, preferably from 1 : 50 to 50 : 1, more preferably from 1 : 5 to 5 : 1.
  • Examples of an olefin used in the present production include linear or branched olefins having 2 to 10 carbon atoms and cyclic olefins having 4 to 10 carbon atoms.
  • linear or branched olefin having 2 to 10 carbon atoms examples include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, 'decene, 2-butene, isobutene, 2-pentene, 3-pentene, 2-hexene, 3-hexene, 4-methyl-l-pentene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene, 3-nonene, 2-decene, and 3-decene.
  • a preferable olefin is a linear or branched olefin having 2 to 6 carbon atoms, and more preferable olefin is propylene.
  • the olefin is preferably used in an amount of 0.2 to 5 mol based on one mole of oxygen.
  • the olefin is preferably used in an amount of 0.01 to 1000 g, based on 1 kg of the solvent used in the present production.
  • Examples of the reactor used in the present production include a flow-through fixed bed reactor and a flow-through slurry complete mixing apparatus.
  • the reaction temperature of the present production is preferably from 0°C to 150°C, more preferably from 40°C to 90°C.
  • the pressure is. preferably 0.1
  • MPa to 20 MPa more preferably 1 MPa to 10 MPa as a gauge pressure.
  • the alkylene oxide may be brought out by distillation to separate a substance from the liquid phase or gas phase taken out of the reactor.
  • polycyclic compound examples include anthracene, tetracene, 9-methylanthracene, naphthalene, diphenyl ether, anthraquinone, 9, 10- phenanthraquinone, benzoquinone, 2-ethylanthraquinone, as well as the compounds described in JP 2009-23998 A and JP 2008-106030 A.
  • a condensed polycyclic aromatic compound such as anthracene, tetracene, 9-methylanthracene, naphthalene, anthraquinone, 9, 10- phenanthraquinone and 2-ethylanthraquinone are preferable, and anthraquinone is more preferable.
  • the polycyclic compound is preferably used in an amount of 0.001 to 500 mmol, more preferably 0.01 to 50 mmol, based on 1 kg of the solvent used in the present production.
  • a salt with an ammonium ion, an alkylammonium ion or an alkylarylammonium ion (hereinafter, the salt is sometimes collectively referred to as “ammonium salt”) may be used as an additive.
  • ammonium salt When the ammonium salt is used in the present production, the hydrogen efficiency tends to be improved.
  • ammonium salts of an inorganic acid such as ammonium sulfate, ammonium hydrogen sulfate, ammonium hydrogen carbonate, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium hydrogen
  • ammonium pyrophosphate ammonium pyrophosphate, ammonium halides and ammonium nitrate; and ammonium salts of an organic acid, such as ammonium acetate.
  • diammonium hydrogen phosphate is preferable.
  • the ammonium salt is preferably used in " an amount of 0.001 to 100 mmol based on 1 kg of the solvent used in the present production.
  • the reaction mixture obtained by reacting hydrogen, oxygen and an olefin in the presence of a noble metal catalyst prepared by the process of the present invention and a titanosilicate catalyst contains an objective alkylene oxide, an unreacted olefin and an alkane as a by-product.
  • the objective alkylene oxide can be taken out from the reaction mixture by a known purifying means such as separation by distillation.
  • a powder X-ray diffraction pattern of the sample was determined by using the following device under the following conditions.
  • Radiation Source Cu K-a radiation
  • the sample was thoroughly pulverized in an agate mortar, and formed into pellets (7 ⁇ ) to prepare a sample for measurement.
  • An ultraviolet-visible absorption spectrum of the sample was determined by using the following device under the following conditions.
  • a diffusion reflector (Praying Mantis manufactured by HARRICK)
  • a I L eggplant flask was charged with 1.8 g of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., degree of polymerization: 500) and 600 mL of water under a nitrogen atmosphere, and the temperature of the mixture was elevated to 90°C with stirring. After the mixture was kept at that temperature for 1 hour, 9.0 g of activated carbon (manufactured by Japan Enviro Chemicals, Ltd., Special Order Shirasagi) and 50 mL of water were added thereto to obtain a suspension, and then the suspension was kept at that temperature for 4 hours. Then, the heat was removed and the suspension was cooled to room temperature. After the suspension was filtered, the obtained solid was washed with 200 mL of water, and then was dried in vacuum at 80°C for 10 hours to obtain 10.3 g of an activated carbon treated with a resin.
  • polyvinyl alcohol manufactured by Wako Pure Chemical Industries, Ltd., degree of polymerization: 500
  • activated carbon manufactured by Japan Enviro
  • a I L eggplant flask was charged with 9.5 g of activated carbon (manufactured by Japan Enviro Chemicals, Ltd., Special Order Shirasagi) and 900 mL of water under an air atmosphere, and the mixture was stirred at room temperature to obtain a suspension. Then, 80 mL of aqueous dispersion containing 0.90 mmol of palladium (Pd) colloid (manufactured by JGC Catalysts and Chemicals Ltd.) was slowly added dropwise to the obtained suspension at room temperature under an air atmosphere. After the completion of the dropwise addition, the suspension was stirred at room temperature for further 6 hours under an air atmosphere.
  • activated carbon manufactured by Japan Enviro Chemicals, Ltd., Special Order Shirasagi
  • the mixture was filtered, and the obtained solid was washed with water until its pH reached near-neutral, and then the obtained product was dried in vacuum at 150°C until weight loss thereof was no longer observed to obtain 61 g of a White Powder (a) .
  • the X-ray diffraction pattern and the ultraviolet-visible absorption spectrum of the White Powder (a) were measured. As a result, it was confirmed that the White Powder (a) was a Ti-MWW precursor.
  • the temperature of the gel was elevated to 160°C over 4 hours with stirring, and the gel was kept at that temperature for 24 hours to obtain a suspension.
  • the obtained suspension was filtered, the filtrate was washed with water until its pH reached about 9. The obtained solid was dried at 150°C until weight loss thereof was no longer observed to obtain 141 g of white Powder (b) .
  • the X-ray diffraction ' pattern and the ultraviolet-visible absorption spectrum of the White Powder (b) were measured.
  • the X-ray diffraction pattern of Powder (b) showed a similar pattern to that of Ti-MWW precursor, and it was confirmed that the White Powder (b) had a structure having fine pores of 12-membered oxygen ring.
  • the White Powder (b) was titanosilicate .
  • the titanium (Ti) content measured by ICP emission spectrometry was 1.61% by mass.
  • a 0.3 L autoclave was used as a reactor.
  • the reactor was charged with 2.28 g of Titanosilicate Catalyst A and 0.75 g. of Noble Metal Catalyst A, and then the autoclave was sealed.
  • Example 2 The procedure of Example 2 was repeated except that 0.63 g of Pd/AC Catalyst obtained in Preparation Example 1 was used instead of 0.75 g of Noble Metal Catalyst A.
  • a product amount of propylene oxide and selectivity of by-product propane were analyzed in the same manner as in Example 2. As a result, the product amount of propylene oxide was 137.1 mmol/Hr and selectivity of by-product propane was 9.5%.
  • Example 2 The procedure of Example 2 was repeated except that 0.63 g of Calcined Pd/AC Catalyst obtained in Preparation Example 2 was used instead of 0.75 g of Noble Metal Catalyst A.
  • a product amount of propylene oxide and selectivity of by-product propane were analyzed in the same manner as in Example 2. As a result, the product amount of propylene oxide was 139.7 mmol/Hr and selectivity of by-product propane was 18.5%.
  • a 0.3 L autoclave was used as a reactor.
  • the reactor was charged with 2.28 g of Titanosilicate Catalyst A and 1.06 g of Calcined Pd/AC Catalyst obtained in Preparation Example 2, and then the autoclave was sealed.
  • a catalyst capable of producing an alkylene oxide in a high yield can be provided.

Abstract

The present invention relates to a process for producing a noble metal catalyst, comprising the steps of: 1) mixing a carbon material with a resin in a solvent to prepare a mixture; 2) taking out a carbon material treated with the resin from the mixture prepared in the step 1; 3) heating the carbon material treated with the resin taken out in the step 2 to obtain a carrier; and 4) supporting a noble metal on the carrier obtained in the step 3. According to the present process, a catalyst capable of producing an alkylene oxide in a high yield can be provided.

Description

DESCRIPTION
PROCESS FOR PRODUCING NOBLE METAL CATALYST SUPPORTED ON CARBON AND ITS USE WITH A TITANOSILICATE FOR THE OXIDATION OF OLEFINS TO ALKYLENE OXIDES
TECHNICAL FIELD
[0001]
The present application is filed, claiming the priority based on the Japanese Patent Application No . 2011-078750 (filed on March 31, 2011) , the entire content'of which is incorporated herein by reference.
The present invention relates to a process for producing a noble metal catalyst. The present invention also relates to a process for producing an alkylene oxide in which the noble metal catalyst is used.
BACKGROUND ART
[0002]
A noble metal catalyst, and a tltanosilicate catalyst are used in a process in which hydrogen, oxygen and propylene are reacted to produce propylene oxide. As such a noble metal catalyst, a catalyst obtained by supporting palladium on activated carbon, and then calcining the resultant is known from JP 2010-168358 A, for example. SUMMARY OF INVENTION PROBLEM TO BE SOLVED BY THE INVENTION
[0003]
There has been a demand for a catalyst capable of producing an alkylene oxide in a high yield.
MEANS FOR SOLVING THE PROBLEM
[0004]
The present invention provides the followings:
[1] A process for producing a noble metal catalyst, comprising the .steps of:
1) mixing a carbon material with a resin in a solvent to prepare a mixture;
2) taking out a carbon material treated with the resin from the mixture prepared in the step 1;
3) heating the carbon material treated with the resin taken out in the step 2 to obtain a carrier; and
4 ) ' supporting a noble metal .on the carrier obtained in the step 3.
[2] The process according to the above item [1], wherein the resin is at least one resin selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, and
polymethylmethacrylate.
[3] The process according to the above item [1] or [2] , wherein the noble metal is at least one metal selected from the group consisting of palladium, platinum, ruthenium, rhodium, iridium, osmium and gold.
[4] A catalyst for producing an alkylene oxide, comprising a titanosilicate catalyst and a noble metal catalyst produced by the process according to any one of the above items [1] to [3] .
[5] A process for producing an alkylene oxide, comprising reacting hydrogen, oxygen and an olefin in the presence of the catalyst produced by the process according to the above item [4].
[6] The process according to the above item [5], wherein the olefin is propylene.
[7] The process according to the above item 5 or 6, wherein the titanosilicate catalyst is at least one catalyst selected from the group consisting of a titanosilicate having an M W structure and a precursor thereof.
EFFECT OF THE INVENTION
[0005]
According to the present, invention, a catalyst capable of producing an alkylene oxide in a high yield can be provided.
MODES FOR CARRYING OUT THE INVENTION
[0006] .
The process of the present invention is a process for producing a noble metal catalyst, comprising the steps of: 1) mixing a carbon material with a resin in a solvent to prepare a mixture ;
2) taking out a carbon material treated with the resin from the mixture prepared in the step 1;
3) heating the carbon material treated with the resin taken out in the step 2 to obtain a carrier; and
4) supporting a noble metal on the carrier obtained in the step 3-
The noble metal catalyst produced by the present process is capable of generating hydrogen peroxide from oxygen and hydrogen. In addition, by using the noble metal catalyst in combination with a titanosilicate catalyst, the noble metal catalyst becomes useful as a catalyst to be used in the production of an alkylene oxide (hereinafter, the production of an alkylene oxide is sometimes referred to as "the present production") .
[0007]
The step 1 is a step in which a carbon material and a resin are mixed in a solvent to prepare a mixture.
[0008]
The carbon material is a material which consists mainly of carbon. Examples of the carbon material include activated carbon, carbon black, graphite and carbon nanotube . Among them, activated carbon is preferable because it has a larger surface area.
The raw materials of the activated carbon and the activation method thereof are not particularly limited, and the activated carbon having a large pore volume is preferable. Examples of the raw materials of the activated carbon include wood, sawdust, palm shell, coal and petroleum materials. Activated carbon obtained by a method in which charcoal obtained from the aforementioned raw materials is activated by being subjected to a high-temperature treatment using water vapor, carbon dioxide, air or the like, or a method in which charcoal is activated by using chemicals such as zinc chloride, is preferable. Among them, the activated carbon obtained by the latter method is more preferable. The activated carbons which are activated by the aforementioned methods are preferable because their pore volume and average pore size become larger. The form of the activated carbon is not particularly limited, and powdery activated carbon, granular activated carbon, crushed activated carbon, fibrous activated carbon, honeycomb activated carbon or the like may be used.
[0009]
The resin used in the process of the present invention is not particularly limited and any known resin may be used. It is preferable to use a resin soluble in a solvent used in the step 1.
Examples of the resin include polyethylene,
polypropylene, polybutadiene, polystyrene,
polymethylmethacrylate, polyacrylonitrile, polyacrylic acid, polyethylene glycol, polyvinylpyrrolidone, polyurea, polyester, polyurethane , polyimide, polyethyleneimine, polyvinyl alcohol, polyvinyl chloride, polyvinyl acetate, polyvinylidene fluoride, polycarbonate, Nylon 6, Nylon 66 and a silicone resin. Among them, polyvinyl alcohol, polyvinyl acetate, and polymethylmethacrylate are preferable, and polyvinyl alcohol is more preferable. These resins are readily available. When the noble metal catalyst produced using such a resin is used in the present production, yield of an alkylene oxide tends to increase and generation of an alkane as a by-product tends to reduce.
[0010]
As a solvent used in the process of the present invention, - a solvent capable of dissolving the aforementioned resin is preferable. The solvent can be properly selected depending on the kind of a resin to be used. Examples of such a solvent include water, alcohol solvents, ketone solvents, nitrile solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ester solvents, glycol solvents, and amide solvents.
[0011]
Examples of the alcohol solvent include methanol, ethanol, isopropanol, tert-butanol , 1-hexanol, cyclohexanol, and 2-ethylhexanol .
Examples of the ketone solvent include acetone, 2-butanone, 2-heptanone, and cyclohexanone .
Examples of the nitrile solvent include acetonitrile and benzonitrile .
Examples of the ether solvent include diethyl ether, tetrahydrofuran, and anisole.
Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, heptane, and cyclohexane.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, and xylene.
Examples of the halogenated hydrocarbon solvent include dichloromethane, chloroform, carbon tetrachloride, and dichloroethane .
Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, ethyl lactate, and ethyl pyruvate.
Examples of the glycol solvent include ethylene glycol, diethylene glycol, and propylene glycol.
Examples of the amide solvent include formamide, acetamide, N, -dimethylformamide, N, N-dimethylacetamide .
These solvents may be used alone or as a mixture of two or more kinds thereof.
[0012]
In the step 1, a carbon material and a resin are mixed in a solvent to prepare. a mixture.
In the mixture, the amount of the carbon material in the mixture is preferably from 1 to 10,000 parts by mass> more preferably from 2 to 1, 000 parts by mass, based on one part by mass of the resin. The amount of the resin in the mixture is preferably from 0.001 to 50% by mass, more preferably from 0.01 to 20% by mass, based on the total amount of the resin and the solvent .
[0013]
The temperature for mixing the carbon material with the resin is preferably from 10°C to 200°C, more preferably from 20°C to 150°C. The time of mixing is preferably from 10 minutes to 30 hours, more preferably from 1 hour to 24 hours. The order of mixing is not particularly limited, and it is preferable that the resin is dissolved in the solvent and then the carbon - material is added thereto. The mixing may be carried out under a nitrogen atmosphere or an .air.
[0014]
The step 2 is a step in which a carbon material treated with a resin from the mixture prepared in the step 1.
Preferably, the mixture prepared in the step 1 is cooled (i.e., a cooling process is employed). Cooling the mixture tends to increase an adhesion of the carbon material to the resin, even where an affinity between the carbon material and the resin is low.
The mixture is preferably cooled to a temperature of from 0°C to 50°C, more preferably from 0°C to 30°C. In addition, the mixture is preferably cooled to a temperature which is lower by preferably 10°C to 200°C, more preferably 20°C to 150°C, and still more preferably 30°C to 120°C than the mixing temperature of the step 1. The time of cooling the mixture is preferably from 30 minutes to 36 hours, more preferably from 1 hour to 24 hours. The cooling may be carried out under a nitrogen atmosphere or an air.
[0015]
In the step 2, a carbon material treated with a resin can be taken out from the mixture by filtration, for example.
The obtained carbon material treated with the resin may be dried as necessary. When the carbon material is dried, the temperature is preferably from 30°C to 200°C. It is preferable to dry the mixture under a reduced pressure or under an atmosphere of an inert gas.
[0016]
The step 3 is a step in which the carbon material treated with the resin, which is obtained in the step 2, is heated to obtain a carrier.
[0017]
The heating temperature is preferably from 250°C to 800°C, more preferably from 250°C to 600°C. The time of heating is preferably from 30 minutes to 24 hours, more preferably from 1 hour to 12 hours.
The heating may be carried out under an atmosphere of an inert gas or an air. The heating is preferably carried out an atmosphere of an inert gas. Examples of the inert gas include nitrogen gas and a noble gas such as argon gas.
[0018]
The step 4 is a step in which a noble metal is supported on the carrier obtained by the step 3 (hereinafter, the carrier obtained by the step 3 is sometimes referred to as "carrier (A)").
[.0019]
As the noble metal, for example, palladium, platinum, ruthenium, osmium, rhodium, iridium and gold may be used. The noble metal may be used alone, or as an alloy or mixture of two or more kinds thereof. In particular, the noble metal is preferably palladium, platinum, gold and an alloy orTnixture thereof, more preferably palladium, an alloy or mixture of palladium and gold, or an alloy or mixture of palladium and platinum, still more preferably palladium. When the noble metal catalyst produced using such a noble metal is used in the present production, generation of hydrogen peroxide in the system tends to increase and yield of an alkylene oxide tends to increase in the present production.
[0020]
Examples of the method for supporting a noble metal on the carrier (A) include a method of supporting a noble metal compound on the carrier (A) and then reducing the noble metal, and a method of mixing a noble metal colloid and the carrier. (A) .
[0021]
In the method of supporting a noble metal compound on the carrier (A) and then reducing the noble metal compound, for example, a noble metal compound is firstly supported on the carrier (A) by an impregnation method, and then, the noble metal compound is reduced to form zero valent noble metal.
Examples of the noble metal compound include noble metal chlorides. When palladiunvis used as the noble metal compound, examples of the palladium compound include tetravalent palladium compounds such as sodium hexachloropalladate (IV) tetrahydrate and potassium hexachloropalladate (IV); and divalent palladium compounds such as palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II),
dichloro (bis (diphenylphosphino) ethane) palladium (II) , dichlorobis (triphenylphosphine) palladium (II),
dichlorotetraamminepalladium (II) ,
dibromotetraamminepalladium (II),
dichloro (cycloocta-1, 5-diene) palladium (II), and palladium (II) trifluoroacetate .
[0022]
The impregnation method may be performed, for example, by impregnating a solution of the noble metal compound (e.g., an aqueous solution of the aforementioned noble metal compound) with the carrier (A) at room temperature for 10 minutes to 30 hours.
[0023]
A noble metal catalyst may be obtained by reducing the noble metal compound which the carrier (A) supporting the noble metal contains. For example, the noble metal compound may be reduced by a method of reduction using a reductant in a liquid phase or a gas phase. As a gas-phase reduction, a method in which hydrogen is used as the reductant and the reduction is carried out at a temperature of from 0°C to 500°C may be used.
When a noble metal compound which generates ammonia gas at the time of thermal decomposition under an atmosphere of an inert gas is used as the noble metal compound, the noble metal compound which has been supported on a carrier may be subjected to thermal treatment under an atmosphere of an inert gas. In this case, ammonia gas generated from the noble metal compound serves as a reductant. The temperature of the thermal treatment may vary depending on the kind of the noble metal compound used, and the like. When dichlorotetraamminepalladium (II) is used as the noble metal compound, the temperature is preferably from 100°C to 500°C, more preferably from 200°C to 350°C.
[0024]
When the reduction is performed in a liquid phase (liquid-phase reduction), hydrogen, hydrazine 'monohydrate, formaldehyde and sodium borohydride may be used as a reductant. When hydrazine monohydrate or formaldehyde is used, it may be used in combination with an alkali. Conditions of the liquid-phase reduction may be appropriately adjusted depending on the kind and amount of the noble metal compound, the carrier and the reductant to be used.
[0025]
When the noble metal catalyst is prepared by a process in which a noble metal colloid and the carrier (A) are mixed, for example, the noble metal colloid and the carrier (A) are mixed in a solvent (e.g., water), and then, the mixture is filtrated to obtain a solid. As the solvent, a dispersion media of the noble metal colloid may be used as it is.
The temperature of mixing is not particularly limited, and it is preferably from 0°C to 100°C, more preferably from 15°C to 40°C. The time of mixing is not particularly limited, and it is. preferably 10 minutes to 30 hours, more preferably 30 minutes to 18 hours.
As the noble metal colloid, a commercially available product may be used, and also, a noble metal colloid prepared by dispersing noble metal particles with a dispersant such as citric acid, polyvinyl alcohol, polyvinylpyrrolidone and sodium hexametaphosphate may be used.
[0026] In "the noble metal catalyst prepared by the present process, the content of the noble metal is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the mass of the carbon material supporting the noble metal.
[0027]
The catalyst of the present invention comprising the noble metal catalyst produced by the process of the present invention and titanosilicate catalyst is useful for production of an alkylene oxide.
An alkylene oxide can be produced by reacting hydrogen, oxygen and an olefin in the presence of a titanosilicate catalyst and the noble metal catalyst prepared by the process of the present invention.
[0028]
. The titanosilicate catalyst is a catalyst which consists mainly of titanosilicate and has an ability of olefin epoxidation. 1
Hereinafter, the titanosilicate of which the
titanosilicate catalyst is composed will be described in detail.
[0029]
Titanosilicate is a generic name for a silicate having tetra-coordinated Ti (titanium atom) , and it has a porous configuration. The titanosilicate of which the titanosilicate catalyst is composed refers to a titanosilicate substantially having tetra-coordinated Ti, in which a maximum absorption peak of an ultraviolet-visible absorption spectrum in a wavelength range of 200 nm to 400 nm appears in a wavelength range of 210 nm to 230 nm (see, for example, "Chemical Communications" 1026-1027, (2002), Figs. 2(d) and (e) ) . The
ultraviolet-visible- absorption spectrum can be measured by using an ultraviolet-visible spectrophotometer equipped with a diffuse reflector in accordance with a diffuse reflection method.
[0030]
As the titanosilicate of which the titanosilicate catalyst is composed, titanosilicate having fine pores of not less than 10-membered oxygen ring is preferable, because such titanosilicate has a high olefin epoxidation ability. When the fine pores are too small, a contact between olefins which have entered into the fine pores and active points in the fine pores may be inhibited, or mass transfer of olefins in the fine pores may be restricted. The fine pore herein refers to a pore formed with a Si-0 bond and/or a Ti-0 bond. The fine pore may be in the state of a half cup called as a side pocket, and does not have to penetrate through the primary particle of
titanosilicate. The term "not less than 10-membered oxygen ring" means that the number of oxygen atoms is 10 or more in either (a) a cross-section of the narrowest part of the fine pore or (b) a ring structure at the fine pore entrance. The fact that a titanosilicate catalyst has fine pores of not less than 10-membered oxygen ring is generally confirmed by an analysis of an X-ray diffraction pattern. In addition, if the catalyst has a known structure, the structure can be easily confirmed by comparison of its X-ray diffraction pattern with the known one.
[0031]
Examples of the titanosilicate of which the
titanosilicate catalyst is composed include titanosilicates [1] to [7] described below.
[1] Crystalline titanosilicate having fine pores with a 10-membered oxygen ring:
TS-1 having the MFI structure (for example, US 4, 410, 501) , TS-2 having the MEL structure (for example, Journal of Catalysis 130, 440-446, (1991)), Ti-ZSM-48 having the MRE structure (for example, Zeolites 15, 164-170, (1995)), Ti-FER having the FER structure (for example, Journal of Materials Chemistry 8, 1685-1686 (1998)), and the like, in terms of the IZA
(International Zeolite Association) structure code.
[0032]
[2] Crystalline titanosilicate having fine pores with a 12-membered oxygen ring:
Ti-Beta having a BEA structure (for example, Journal of Catalysis 199, 41-47, (2001)), Ti-ZSM-12 having an MTW structure (for example, Zeolites 15, 236-242, (1995)), Ti-MOR. having an MOR structure (for example, The Journal of Physical Chemistry B 102, 9297-9303, (1998)), Ti-ITQ-7 having an ISV structure (for example, Chemical Communications
761-762, (2000) ) , Ti-MCM-68 having an MSE structure (for example, Chemical Communications 6224-6226, (2008)), Ti-MWW having an MWW structure (for example, Chemistry Letters 774-775, (2000)), and the like.
[0033]
[3] Crystalline titanosilicate having fine pores with a 14-membered oxygen ring:
Ti-UTD-1 having a DON structure (for example, Studies in Surface Science and Catalysis 15, 519-525, (1995)),. and the like.
[4] Layered titanosilicate having fine pores with a 10-membered oxygen ring:
Ti-ITQ-6 (for example, Angewandte Chemie International Edition 39, 1499-1501, '(2000)), and the like.
[5] Layered titanosilicate having fine pores with a 12-membere'd oxygen ring:
A Ti-MWW precursor (for example, EP-1731515-A1 ) ,
Ti-YNU-1 (for example, Angewandte Chemie International Edition 43, 236-240, (2004) ) , Ti-MCM-36 (for example, Catalysis Letters 113, 160-164, (2007)), Ti-MCM-56 (for example, Microporous and Mesoporous Materials 113, 435-444, (2008)), and the like. - [0034] [6] Mesoporous titanosilicate:
Ti-MCM-41 (for example, Microporous Materials 10, 259-271, (1997)), Ti-MCM-48 (for example, Chemical
Communications 145-146, (1996)), Ti-SBA-15 (for example, Chemistry of Materials 14, 1657-1664, (2002)), and the like.
[7] Silylated titanosilicate:
Compounds obtained by silylating the titanosilicates [1] to [4] described above, such as silylated Ti-MWW.
[0035]
The term "12-membered oxygen ring" means a ring structure having 12 oxygen atoms in either region (a) or (b) mentioned in the description regarding "10-membered oxygen ring".
Likewise, the term "14-membered oxygen ring" means a ring structure having 14 oxygen atoms in either region (a) or (b) mentioned above.
[0036]
The titanosilicate may be a titanosilicate having a layered structure, such as a layered precursor of a crystalline titanosilicate, a titanosilicate in which spaces between layers in a crystalline titanosilicate are expanded. Whether a titanosilicate has a layered structure or not can be confirmed by electron microscopy or measurement of an X-ray diffraction pattern.. The layered precursor refers to a titanosilicate which forms a crystalline titanosilicate by a treatment such as dehydration condensation. It can be easily determined from the structure of a corresponding crystalline titanosilicate that a layered titanosilicate has fine pores of not less than 12-membered oxygen ring.
The Ti-MWW precursor refers to a titanosilicate having a layered structure, which forms a Ti-MWW by a
dehydration-condensation. The dehydration-condensation may be carried out by heating the Ti-MWW precursor usually at a temperature of greater than 200°C to 1000°C or less, preferably at a temperature within the range of 300°C to 650°C.
[0037]
The titanosilicates of [1] to [5] and [7] have fine pores with a pore size of 0.5 to 1.0 ran. The pore size refers to the longest distance of in (a) a cross-section of the narrowest part of the fine pore and (b) a fine pore entrance. Preferably, the pore size refers to. a diameter in the above-mentioned regions (a) and (b) . The pore size can be determined by an analysis of an X-ray diffraction pattern.
[0038]
Among the aforementioned titanosilicates, a mesoporous titanosilicate which has regular mesofine pores is preferable. The regular mesofine pore refers to a structure in which mesopores are regularly and repeatedly arranged. When the titanosilicate is a mesoporous titanosilicate, the mesoporous titanosilicate which has mesofine pores having an average pore size of, 2 nm to 10 nm is more preferable. [0039]
Silylating of the titanosilicates can be carried out by a method in' which the titanosilicate is brought into contact with a silylating agent or a method described in EP 1488853 Al . Examples of the silylating agent include
1 , 1 , 1 , 3 , 3 , 3-hexamethyl disilazane and trimethylchlorosilane .
[0040] . · "
Among the aforementioned titanosilicates of [1] to [7], Ti-MWW and Ti-MWW precursor are preferably used, and Ti-MWW precursor is more preferably used as a titanosilicate of which the titanosilicate catalyst is composed. The silylated Ti-MWW or Ti-MWW precursor may be used- for a titanosilicate catalyst. The Ti-MWW or Ti-MWW precursor shaped by using a known method may be used for a titanosilicate catalyst.
[0041]
In the titanosilicate catalyst used in the present production, the content of titanium atom is preferably from 0.001 to 0.1 mol, more preferably from 0.005 to 0.05 mol, based on one mol of silicon atoms contained.
[0042] '
In the present production, the noble metal catalyst obtained by the process of the present invention is preferably used in an amount of 0.01 to 100 parts by mass, more preferably 0.1 to 100 parts by mass, based on one part by mass of the titanosilicate catalyst used. [0043]
The present production is preferably carried out in a solvent. As the solvent, water, an organic solvent and mixtures thereof are preferable. Examples of the organic solvent include alcohol solvents, ketone solvents, nitrile solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ester solvents, glycol solvents and mixtures thereof. Among them, nitrile solvents are preferable.
[0044]
Examples of the nitrile solvent include linear or branched saturated aliphatic nitriles and aromatic nitriles. The specific examples of the nitrile solvent include
acet nitrile, propionitrile, isobutyronitrile and
benzonitrile . Acetonitrile is preferable.
The solvent is preferably a mixed solvent of water and nitrile. In the mixed solvent , a mass ratio of water and nitrile (water : nitrile) is preferably from 90 : 10 to 0.01 : 99.99, more preferably from 50 : 50 to 0.1 : 99.9, still more preferably 40 : 60. to 5 : 95.
[0045]
In the present production, oxygen may be a molecular oxygen such as an oxygen gas. The oxygen gas may be an oxygen gas produced by a pressure swing method or an oxygen gas having a high purity produced by cryogenic separation. Alternatively, air may be used as oxygen.'
[0046]
In the present production, a hydrogen gas is usually used as hydrogen.
The oxygen gas and/or the hydrogen gas used in the present production may be diluted with an inert gas which does not obstruct the progress of the present production. Examples of the inert gas include nitrogen, argon, carbon dioxide, methane, ethane, and propane.
The amounts of the oxygen gas and the hydrogen gas supplied to the present production and the concentration of the inert gas used for diluting the gases may be appropriately adjusted according to an amount of the olefin to be used, the scale of the reaction and the like.
The molar ratio of oxygen and hydrogen supplied to the reactor (oxygen : hydrogen) is, for example, preferably from 1 : 50 to 50 : 1, more preferably from 1 : 5 to 5 : 1.
[0047]
Examples of an olefin used in the present production include linear or branched olefins having 2 to 10 carbon atoms and cyclic olefins having 4 to 10 carbon atoms.
Examples of the linear or branched olefin having 2 to 10 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, 'decene, 2-butene, isobutene, 2-pentene, 3-pentene, 2-hexene, 3-hexene, 4-methyl-l-pentene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene, 3-nonene, 2-decene, and 3-decene.
Examples of the cyclic olefin having 4 to 10 carbon atoms include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, and cyclodecene.
A preferable olefin is a linear or branched olefin having 2 to 6 carbon atoms, and more preferable olefin is propylene.
[0048]
In the present production, the olefin is preferably used in an amount of 0.2 to 5 mol based on one mole of oxygen. When the present production is performed in the continuous manner, the olefin is preferably used in an amount of 0.01 to 1000 g, based on 1 kg of the solvent used in the present production.
[0049]
Examples of the reactor used in the present production include a flow-through fixed bed reactor and a flow-through slurry complete mixing apparatus.
The reaction temperature of the present production is preferably from 0°C to 150°C, more preferably from 40°C to 90°C.
In the present production, the pressure is. preferably 0.1
MPa to 20 MPa, more preferably 1 MPa to 10 MPa as a gauge pressure.
After completion of the present production, the alkylene oxide may be brought out by distillation to separate a substance from the liquid phase or gas phase taken out of the reactor.
[0050] It is preferable to carry out the present production in the presence of a -polycyclic compound as an additive. It is preferable to use the polycyclic compound in the present production because generation of propane as a by-product tends to be suppressed and hydrogen efficiency tends to be improved. The hydrogen efficiency herein refers to a product amount of propylene oxide relative to the amount of hydrogen consumed.
The specific examples of the polycyclic compound include anthracene, tetracene, 9-methylanthracene, naphthalene, diphenyl ether, anthraquinone, 9, 10- phenanthraquinone, benzoquinone, 2-ethylanthraquinone, as well as the compounds described in JP 2009-23998 A and JP 2008-106030 A. Among them, a condensed polycyclic aromatic compound such as anthracene, tetracene, 9-methylanthracene, naphthalene, anthraquinone, 9, 10- phenanthraquinone and 2-ethylanthraquinone are preferable, and anthraquinone is more preferable.
[0051]
In the present production, the polycyclic compound is preferably used in an amount of 0.001 to 500 mmol, more preferably 0.01 to 50 mmol, based on 1 kg of the solvent used in the present production.
[0052]
In the present production, a salt with an ammonium ion, an alkylammonium ion or an alkylarylammonium ion (hereinafter, the salt is sometimes collectively referred to as "ammonium salt") may be used as an additive. When the ammonium salt is used in the present production, the hydrogen efficiency tends to be improved.
Examples of the ammonium salt include ammonium salts of an inorganic acid, such as ammonium sulfate, ammonium hydrogen sulfate, ammonium hydrogen carbonate, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium hydrogen
pyrophosphate, ammonium pyrophosphate, ammonium halides and ammonium nitrate; and ammonium salts of an organic acid, such as ammonium acetate. Among them, diammonium hydrogen phosphate is preferable.
In the present production, the ammonium salt is preferably used in" an amount of 0.001 to 100 mmol based on 1 kg of the solvent used in the present production.
[0053]
The reaction mixture obtained by reacting hydrogen, oxygen and an olefin in the presence of a noble metal catalyst prepared by the process of the present invention and a titanosilicate catalyst contains an objective alkylene oxide, an unreacted olefin and an alkane as a by-product. The objective alkylene oxide can be taken out from the reaction mixture by a known purifying means such as separation by distillation. EXAMPLES
[0054]
Hereinafter, the present invention will be described in more detail by way of Examples. Analyzers and analysis methods used in the following examples are as follows.
[0055]
(Elemental Analysis)
(1) Content of Pd (palladium atoms) in the activated carbon supporting Pd or the noble metal catalyst was measured by the microwave decomposition/ICP emission spectrometry (the detection limit is 0.01 % by mass or less) .
(2) Contents of Ti (titanium atoms) and Si (silicon atoms) in the titanosilicate catalyst were measured by the alkali fusion/dissolution in nitric acid/ ICP emission spectrometry.
[0056]
(Powder X-ray diffractometry)
A powder X-ray diffraction pattern of the sample was determined by using the following device under the following conditions.
Device: RINT 2500 V manufactured by Rigaku Denki Co., Ltd.
Radiation Source: Cu K-a radiation
Output 40 kV-300 mA
Scanning Field: 2Θ = 0.75° to 30°
Scanning Speed: l°/minute
When the measured X-ray diffraction pattern was equal to that disclosed in Fig.l of EP 1731515, it was concluded that the sample measured was Ti-MWW precursor. When the measured X-ray diffraction pattern was equal to that disclosed in Fig.2 of EP 1731515, it was concluded that the sample measured was Ti-MWW.
[0057]
(Ultraviolet-Visible Absorption Spectrum)
The sample was thoroughly pulverized in an agate mortar, and formed into pellets (7 πιπιφ) to prepare a sample for measurement. An ultraviolet-visible absorption spectrum of the sample was determined by using the following device under the following conditions.
Device: a diffusion reflector (Praying Mantis manufactured by HARRICK)
Device Accessory: an ultraviolet-visible spectrophotometer
(V-7100 manufactured by JASCO Corporation)
Pressure: atmospheric pressure
Measured Value: reflectance
Data Acquisition Time: 0.1 second
Band Width: 2 nm
Measurement Wavelength: 200 to 900 nm
Height of Slit: semi-open
Data Acquisition Interval: 1 nm
Baseline Correction (Reference) : BaS04 pellets (7 ΐΐΐιτιφ)
When, the maximum absorption in a wavelength range of 200 nm to 400 nm appeared in a wavelength range of 210 nm to 230 nm, it was concluded that the sample measured was
titanosilicate .
[0058]
Example 1
(Production of carrier)
A I L eggplant flask was charged with 1.8 g of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., degree of polymerization: 500) and 600 mL of water under a nitrogen atmosphere, and the temperature of the mixture was elevated to 90°C with stirring. After the mixture was kept at that temperature for 1 hour, 9.0 g of activated carbon (manufactured by Japan Enviro Chemicals, Ltd., Special Order Shirasagi) and 50 mL of water were added thereto to obtain a suspension, and then the suspension was kept at that temperature for 4 hours. Then, the heat was removed and the suspension was cooled to room temperature. After the suspension was filtered, the obtained solid was washed with 200 mL of water, and then was dried in vacuum at 80°C for 10 hours to obtain 10.3 g of an activated carbon treated with a resin.
3.5 g of the obtained activated carbon treated with . a resin was heated to 300°C over 2 hours under a nitrogen atmosphere, and then was kept at 300°C for 6 hours. After that, the heat was removed and the activated carbon treated with a resin was cooled to room temperature to obtain 3.0 g of Carrier A.
[0059]
(Production of noble metal catalyst)
A 500 mL eggplant flask was charged with 2.7 g of Carrier A and 270 mL of water under a nitrogen atmosphere, and the mixture was stirred at room temperature. After that, 50 mL of aqueous dispersion containing 0.27 mmol of palladium (Pd) colloid (manufactured by JGC Catalysts and Chemicals Ltd. ) was slowly added dropwise to the obtained suspension at room temperature under a nitrogen atmosphere. After the completion of the dropwise addition, the suspension was stirred at room temperature for further 6 hours under a nitrogen atmosphere. After that, water was removed from the suspension by using a rotary evaporator and the residue was dried in vacuum at 80°C for 10 hours to obtain 2.9 g of Noble Metal Catalyst A. The palladium . ( Pd) content in the Noble Metal Catalyst A, measured by ICP emission spectrometry, was 0.80% by mass.
[0060]
Preparation Example 1
(Preparation of noble metal catalyst)
A I L eggplant flask was charged with 9.5 g of activated carbon (manufactured by Japan Enviro Chemicals, Ltd., Special Order Shirasagi) and 900 mL of water under an air atmosphere, and the mixture was stirred at room temperature to obtain a suspension. Then, 80 mL of aqueous dispersion containing 0.90 mmol of palladium (Pd) colloid (manufactured by JGC Catalysts and Chemicals Ltd.) was slowly added dropwise to the obtained suspension at room temperature under an air atmosphere. After the completion of the dropwise addition, the suspension was stirred at room temperature for further 6 hours under an air atmosphere. After that, the water was removed from the suspension by using a rotary evaporator and the residue was dried in vacuum at 80°C for 10 hours to obtain 9.5 g of Pd/AC Catalyst. The palladium (Pd) content in the Pd/AC Catalyst, measured by ICP emission spectrometry, was 0.95% by mass.
[0061]
Preparation Example 2
(Preparation of calcined Pd/AC catalyst)
Under a nitrogen atmosphere, 2.4 g of the Pd/AC Catalyst obtained in Preparation Example 1 was calcined at 300°C for 6 hours to obtain 2.4 g of Calcined Pd/AC Catalyst . The palladium (Pd) content in the Calcined Pd/AC Catalyst, measured by ICP emission spectrometry, was 1.03% by mass.
• [0062]
Preparation Example 3.
(Preparation of titanosilicate catalyst)
In an autoclave, 899 g of piperidine, 2402 g of pure water, 112 g of tetra-n-butyl orthotitanate, 565 g of boric acid, and 410 g of fumed silica (cab-o-sil M7D) were stirred under an air atmosphere to obtain a gel. After the obtained gel was aged for 1.5 hours, the autoclave was sealed. Subsequently, the temperature of the gel was elevated to 160°C over .8 hours with stirring, and the gel was kept at that temperature for 120 hours to obtain a suspension.
After the obtained suspension was filtered, the filtrate was washed with water until its pH reached about 10. The obtained solid was dried at 50°C until weight loss thereof was no longer observed to obtain 515 g of Solid (a) . To 75 g of the obtained solid (a) was added 3750 mL of 2 M nitric acid to obtain a mixture, and then the mixture was refluxed for 20 hours .
Subsequently, the mixture was filtered, and the obtained solid was washed with water until its pH reached near-neutral, and then the obtained product was dried in vacuum at 150°C until weight loss thereof was no longer observed to obtain 61 g of a White Powder (a) . The X-ray diffraction pattern and the ultraviolet-visible absorption spectrum of the White Powder (a) were measured. As a result, it was confirmed that the White Powder (a) was a Ti-MWW precursor.
60 g of the obtained White Powder (a) was calcined at 530°C for 6 hours to obtain 54 g of Powder (t) . It was confirmed that the obtained Powder (t) was a Ti-MWW, from the X-ray diffraction pattern, and that the Powder (t) was titanosilicate having tetra-coordinated Ti, from the ultraviolet-visible absorption spectrum. The same manner was repeated two times to obtain a total of 162 g of Powder (t) . An autoclave was charged with 135 g of the obtained Powder (t) at room temperature under an air atmosphere, and 300 g of piperidine and 600 g of pure water were added thereto, and then the mixture was stirred to obtain a gel. After the obtained gel was aged for 1.5 hours, the autoclave was sealed.
Subsequently, the temperature of the gel was elevated to 160°C over 4 hours with stirring, and the gel was kept at that temperature for 24 hours to obtain a suspension.
After the obtained suspension was filtered, the filtrate was washed with water until its pH reached about 9. The obtained solid was dried at 150°C until weight loss thereof was no longer observed to obtain 141 g of white Powder (b) . The X-ray diffraction ' pattern and the ultraviolet-visible absorption spectrum of the White Powder (b) were measured. As a result, the X-ray diffraction pattern of Powder (b) showed a similar pattern to that of Ti-MWW precursor, and it was confirmed that the White Powder (b) had a structure having fine pores of 12-membered oxygen ring. Furthermore, it was confirmed, from the ultraviolet-visible absorption spectrum, that the White Powder (b) was titanosilicate . The titanium (Ti) content measured by ICP emission spectrometry was 1.61% by mass.
The obtained White Powder (b) was stirred in 80 g of a mixed solvent of water/acetonitrile (mass ratio = 20/80) containing 0.1% by mass of hydrogen peroxide for 1 hour, and then the mixture was filtered and the filtrate was washed with 80 g of water to obtain Titanosilicate Catalyst A.
[0063] "
Example 2
(Production of propylene oxide)
A 0.3 L autoclave was used as a reactor. The reactor was charged with 2.28 g of Titanosilicate Catalyst A and 0.75 g. of Noble Metal Catalyst A, and then the autoclave was sealed. To the autoclave were supplied 339 L/Hr of a mixed gas of oxygen/hydrogen/nitrogen (volume ratio = 3.4/3.8/92.8), 135 g/Hr of solution of water/acetonitrile (mass ratio = 30/70) containing 0.7 mmol/kg of anthraquinone, 3.0 mmol/kg of diammonium hydrogen phosphate, and 54 g/Hr of propylene, and the continuous reaction (retention time: 40 min) , in which a solution containing a reaction product ( i . e ., liquid phase ) and a produced gas (i.e., gas phase) were extracted from the reaction mixture and taken out from the reactor through a filter, was carried out. During the reaction, the temperature of the mixture was adjusted to 50°C, and the internal pressure of the reactor was adjusted to 6.0 MPa (gauge pressure) .
" The liquid phase and the gas phase taken out after four hours from the start of the reaction were analyzed by a gas chromatography. As a result, propylene oxide was produced in an amount of 219.7 mmol/Hr, and the selectivity of by-product propane was 6.3%.
[0064] Comparative Example 1
The procedure of Example 2 was repeated except that 0.63 g of Pd/AC Catalyst obtained in Preparation Example 1 was used instead of 0.75 g of Noble Metal Catalyst A. A product amount of propylene oxide and selectivity of by-product propane were analyzed in the same manner as in Example 2. As a result, the product amount of propylene oxide was 137.1 mmol/Hr and selectivity of by-product propane was 9.5%.
[0065]
Comparative Example 2
The procedure of Example 2 was repeated except that 0.63 g of Calcined Pd/AC Catalyst obtained in Preparation Example 2 was used instead of 0.75 g of Noble Metal Catalyst A. A product amount of propylene oxide and selectivity of by-product propane were analyzed in the same manner as in Example 2. As a result, the product amount of propylene oxide was 139.7 mmol/Hr and selectivity of by-product propane was 18.5%.
[0066]
Comparative Example 3
A 0.3 L autoclave was used as a reactor. The reactor was charged with 2.28 g of Titanosilicate Catalyst A and 1.06 g of Calcined Pd/AC Catalyst obtained in Preparation Example 2, and then the autoclave was sealed. To the autoclave were supplied 281 L/Hr of a mixed gas of oxygen/hydrogen/nitrogen (volume ratio = 3.3/3.6/93.1 ) , 90 g/Hr of solution of water/acetonitrile (mass ratio = 30/70) containing 0.7 mmol/kg of anthraquinone, 3.0 mmol/kg of diammonium hydrogen phosphate, and 36 g Hr of propylene, and the continuous reaction (retention time: 60 min) , in which a solution containing a reaction product(i.e., liquid phase) and a produced gas (i.e., gas phase) were extracted from the reaction mixture and taken out from the reactor through a filter, was carried out . During the reaction, the temperature of the mixture was adjusted to 50°C, and the internal pressure of the reactor was adjusted to 4.0 MPa (gauge pressure) .
The liquid phase and the gas phase taken out after 6 hours from the start of the reaction were analyzed by a gas chromatography. As a result, propylene oxide was produced in an amount of 167.7 mmol/Hr, and selectivity of by-product propane was 7.6%.
[0067]
It was confirmed that a high product amount of propylene oxide was attained by using the noble metal catalysts of Example 1 produced by the process of the present invention.
INDUSTRIAL APPLICABILITY
[0068]
According to the present process, a catalyst capable of producing an alkylene oxide in a high yield can be provided.

Claims

1. A process for producing a noble metal catalyst, comprising the steps of:
1) mixing a carbon material with a resin in a solvent to prepare a mixture;
2) taking out a carbon material treated with the resin from the mixture prepared in the step 1;
3) heating the carbon material treated with the resin taken out in the step 2 to obtain a carrier; and ■
4) supporting a noble metal on the carrier obtained in the step 3.
2. The process according to claim 1, wherein the resin is at least one resin selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, and
polymethylmethacrylate.
3. The process according to claim 1 or 2, wherein the noble metal is at least one metal selected from the group consisting of palladium, platinum, ruthenium, rhodium, iridium, osmium and gold.
4. A catalyst for producing an alkylene oxide, comprising a titanosilicate catalyst and a noble metal catalyst produced by the process according to any one of claims 1 to 3.
5. A process for producing an alkylene oxide, comprising reacting hydrogen, oxygen and an olefin in the presence of the catalyst produced by the process according to claim 4.
6. The process according to claim 5, wherein the olefin is propylene .
7. The process according to claim 5 or 6, wherein the titanosilicate catalyst is at least one catalyst selected from the group consisting of a titanosilicate having an MWW structure and a. precursor thereof.
PCT/JP2012/059292 2011-03-31 2012-03-29 Process for producing noble metal catalyst supported on carbon and its use with a titanosilicate for the oxidation of olefins to alkylene oxides WO2012133934A1 (en)

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