WO2012094121A1 - Procédé de préparation d'un oxyde d'oléfine - Google Patents

Procédé de préparation d'un oxyde d'oléfine Download PDF

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WO2012094121A1
WO2012094121A1 PCT/US2011/065162 US2011065162W WO2012094121A1 WO 2012094121 A1 WO2012094121 A1 WO 2012094121A1 US 2011065162 W US2011065162 W US 2011065162W WO 2012094121 A1 WO2012094121 A1 WO 2012094121A1
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metal
oxide
alkaline
catalyst
copper
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PCT/US2011/065162
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English (en)
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Yoshihiko Ohishi
Anusorn Seubsai
Selim Senkan
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Sumitomo Chemical Company, Limited
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Publication of WO2012094121A1 publication Critical patent/WO2012094121A1/fr

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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
    • C07D301/08—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 gaseous 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and 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
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    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13—Platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8973—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony or bismuth
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten

Definitions

  • the present invention relates to a process for producing an olefin oxide.
  • the present invention provides:
  • a process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising a copper oxide, a ruthenium oxide and a metal component deriving from one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce .
  • a catalyst for production of an olefin oxide which comprises a copper oxide, a ruthenium oxide and a metal component deriving from one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce .
  • the process of the present invention comprises reacting an olefin with oxygen in the presence of a catalyst comprising a copper oxide, a ruthenium oxide and a metal component.
  • the copper oxide, the ruthenium oxide and the metal component are preferably supported on a support, and more preferably on a porous support.
  • This catalyst is valuable for production of olefin oxides, which is one aspect of the present invention.
  • the support may be a porous support, and may be a non-porous support.
  • the porous support has pores capable of supporting the copper oxide, the ruthenium oxide and the metal component.
  • the porous support preferably comprises AI 2 O 3 , Si0 2 , Ti0 2 , or Zr02, more preferably Si0 2 .
  • Examples of the porous support comprising S1O 2 include mesoporous silica.
  • Such porous supports may also comprise zeolites.
  • non-porous support examples include a non-porous support comprising S1O 2 such as CAB-O-SIL (registered trademark) .
  • the support may be in form of powder or may be shaped to a desired structure.
  • olefin oxides can be prepared with good yield and good selectivity.
  • the catalyst comprises one or more kinds of copper oxides .
  • the copper oxide is usually composed of copper and oxygen.
  • Examples of the copper oxide include CU2O and CuO.
  • the copper oxide is preferably CuO.
  • the catalyst comprises one or more kinds of the ruthenium oxide.
  • the ruthenium oxide is usually composed of ruthenium and oxygen. Examples of the ruthenium oxide include RU2O4 , RU2O5 , RU3O5 , RU3O6 , RUC , and RUO2.
  • the ruthenium oxide is preferably Ru0 2 .
  • the catalyst comprises one or more kinds of the metal components.
  • the metal component includes a metal element or ion and a metal oxide, each of which derives from one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce .
  • the metal oxide include a metal oxide composed of oxygen and the metal selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce .
  • the metal oxide composed of an oxygen atom and manganese includes manganese oxides such as MnO, ⁇ 2 , ⁇ 2 ⁇ 3 and ⁇ 3 ⁇ 4 , preferably Mn 2 0 3 .
  • the metal oxide composed of an oxygen atom and germanium includes germanium oxide such as GeO and Ge0 2 , preferably Ge0 2 .
  • the metal oxide composed of an oxygen atom and thallium includes thallium oxide such as T1 2 0, TI 2 O 3 and TI 4 O 3 , preferably TI4O3.
  • the metal oxide composed of an oxygen atom and indium includes indium oxide such as In 2 0 3 .
  • the metal oxide composed of an oxygen atom and iridium includes iridium oxide such as I r0 2 .
  • the metal oxide composed of an oxygen atom and lanthanum includes lanthanum oxide such as La 2 ⁇ 0 3 .
  • the metal oxide composed of an oxygen atom and cerium includes cerium oxide such as Ce0 2 .
  • the metal component preferably includes a metal oxide, specifically manganese oxide, germanium oxide and lanthanum, more preferably manganese oxide and germanium oxide, still more preferably manganese oxide.
  • the metal ion may form a metal-containing salt comprising the metal ion and a halogen ion.
  • the metal component derives from preferably one selected from the group consisting of Mn, Ge, Tl, La and Ce, more preferably one selected from the group consisting of Mn, Ge and La, still more preferably a metal selected from the group consisting of Mn and Ge .
  • the catalyst may comprise one or more kinds of the alkaline metal or alkaline earth metal component.
  • the alkaline metal or alkaline earth metal component may be an alkaline metal-containing compound, an alkaline earth metal-containing compound, an alkaline metal ion or an alkaline earth metal ion.
  • Examples of the alkaline metal-containing compound include compounds containing an alkaline metal such as Na, K, Rb and Cs .
  • Examples of the alkaline earth metal-containing compound include compounds containing an alkaline earth metal such as Ca, Mg, Sr and Ba.
  • Examples of the alkaline metal ion include Na + , K + , Rb + and Cs + .
  • Examples of the alkaline earth metal ion include such as Ca 2+ , Mg 2+ , Sr 2+ and Ba 2+ .
  • the alkaline metal component may be an alkaline metal oxide .
  • Examples of the alkaline metal oxide include Na 2 0, Na 2 0 2 , K 2 0, K 2 0 2 , Rb 2 0, Rb 2 0 2 , Cs 2 0, and Cs 2 0 2 .
  • the alkaline earth metal component may be alkaline earth metal oxide. Examples of the alkaline earth metal oxide include CaO, Ca0 2 , MgO, Mg0 2 , SrO, Sr0 2 , BaO and Ba0 2 .
  • the alkaline metal or alkaline earth metal component is preferably an alkaline metal-containing compound, more preferably a sodium-containing compound.
  • the alkaline metal-containing compound and alkaline earth metal-containing compound are preferably an alkaline metal salt and an alkaline earth metal salt.
  • the alkaline metal salt may comprise the alkaline metal ion as mentioned above with an anion
  • the alkaline earth metal salt may comprise the alkaline earth metal ion as mentioned above with an anion. Examples of anions in such salts include CI “ , Br “ or I “ , F “ , OH “ , N0 3 “ , S0 4 2” and C0 3 2" .
  • Such salts are preferably an alkaline metal salt with a halogen, such as an alkaline metal halide, or an alkaline earth metal-containing salt with a halogen, such as an alkaline earth metal halide, more preferably an alkaline metal salt with a halogen, still more preferably an alkaline metal chloride.
  • the catalyst comprises preferably CuO, Ru0 2 and a metal component deriving from Mn, Ge, Tl, In, Ir, La or Ce; more preferably CuO, Ru0 2 , a metal component deriving from Mn, Ge, Tl, La or Ce and an alkaline metal-containing compound; still more preferably CuO, Ru0 2 , a metal component deriving from Mn, and Ge and a sodium-containing compound, because the olefin oxide yield and selectivity can be improved by adopting such combination to the production of an olefin oxide.
  • the catalyst comprises NaCl, as the alkaline metal or alkaline earth metal component, it can show excellent olefin oxide selectivity.
  • the ruthenium/copper molar ratio in the catalyst is preferably 0.01/1 to 50/1 based on their atoms. When the metal molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved.
  • the lower limit of the molar ratio is more preferably 0.05/1, still more preferably 0.1/1.
  • the upper limit of the molar ratio is more preferably 10/1, still more preferably 5/1.
  • the component/copper] in the catalyst is preferably 0.001/1 to 50/1 based on their atoms.
  • the metal molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved.
  • the lower limit of the molar ratio is more preferably 0.01/1, still more preferably 0.05/1.
  • the upper limit of the molar ratio is more preferably 20/1, still more preferably 5/1.
  • metal/copper in the catalyst is preferably 0.001/1 to 50/1 based on their atoms.
  • the lower limit of the molar ratio is more preferably 0.05/1, still more preferably 0.1/1.
  • the upper limit of the molar ratio is more preferably 20/1, still more preferably 10/1.
  • the lower limit of the total content is more preferably 0.05 weight parts, still more preferably 0.1 weight parts relative to 100 weight parts of a porous support.
  • the upper limit of the total content is more preferably 50 weight parts, still more preferably 30 weight parts relative to 100 weight parts of a porous support.
  • the catalyst may comprise a halogen component besides the copper oxide, the ruthenium oxide, the metal component and the alkaline or alkaline earth metal component.
  • the halogen component is generally a halogen-containing compound.
  • halogen examples include chlorine, fluorine, iodine and bromine .
  • halogen-containing compound examples include halides of copper or ruthenium, metal halides containing the metal components, oxyhalides of copper or ruthenium, and oxyhalides containing the metal components. If the catalyst comprises a halogen component, the component may be supported on the porous support as mentioned above.
  • halogen-containing compound examples include copper halides such as CuCl and CuC ⁇ 2 , ruthenium halides such as RuC ⁇ 3 and copper oxyhalides such as CuOC ⁇ 2 , CUCIO 4 ,
  • the component may be supported on the porous support as mentioned above.
  • the catalyst may further comprise a composite oxide including those composed of copper, ruthenium and oxygen; those composed of copper, sodium and oxygen; those composed of sodium, ruthenium and oxygen; those composed of sodium, oxygen and any one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce; those composed of oxygen, any of copper and ruthenium, and any one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce .
  • the component may be supported on the porous support or any of the other components as mentioned above.
  • the molar ratio of V, Mo or W to ruthenium metal in the catalyst is preferably less than 0.25, and more preferably less than 0.1, and it is still more preferable that the catalyst substantially contains no V, Mo or W.
  • Production of the catalyst is not restricted to a specific process, and examples of which include the conventional methods such as an impregnation method, a precipitation method, a deposition precipitation method, a chemical vapour deposition method, a mechnano-chemical method, and a solid state reaction method, and an impregnation method is preferable.
  • the catalyst can be obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion and a metal ion to prepare a composition, followed by calcining the composition, said metal ion deriving from one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce .
  • the porous support can be in form of powder, or shaped to a desired stucture as necessary.
  • the composition obtained by impregnating the porous support with the solution or the suspension is preferably aged with stirring at a temperature of 5°C to 100°C, and more preferably 10°C to 50°C.
  • the composition can be used as it is, and is preferably aged for some time. Aging time is preferably in the range from 0.5 to 48 hours, and more preferably 1 to 25 hours .
  • the porous support can be in form of powder, or shaped to a desired structure as necessary.
  • the catalyst comprises the alkaline metal or alkaline earth metal component, it can be obtained in the same procedure as mentioned above except that solution or a suspension contains copper ion, a ruthenium ion, a metal compound or ion, an alkaline metal or alkaline earth metal ion.
  • the catalyst can be obtained in the same procedure as mentioned above except that solution or a suspension contains copper ion, a ruthenium ion, the above-mentioned metal compound or ion, an alkaline metal or alkaline earth metal ion and a halogen ion.
  • the solution or a suspension containing a copper ion, a ruthenium ion and the above-mentioned metal compound or ion can be prepared by mixing a copper metal salt, a ruthenium metal salt and a metal-containing salt as mentioned below in a solvent .
  • Examples of the copper metal salt include copper acetate, copper ammonium chloride, copper bromide, copper carbonate, copper ethoxide, copper hydroxide, copper iodide, copper isobutyrate, copper isopropoxide, copper oxalate, copper oxychroride, copper oxide, copper nitrates, and copper chlorides, and copper nitrates and copper chlorides are preferable.
  • Examples of the metal-containing salt include the following ones.
  • Manganese metal salt such as manganese carbonate, manganese nitrate, manganese sulfate, manganese bromide, manganese chloride, manganese iodide, manganese perchlorate, manganese acetate, and manganese acetylacetonate.
  • Germanium metal salt such as germanium bromide, germanium chloride, germanium iodide, germanium isopropoxide, germanium ethoxide, and germanium methoxide.
  • Thallium metal salt such as thallium sulfate, thallium nitrate, thallium bromide, thallium chloride, thallium iodide, thallium acetate, thallium carbonate, and thallium oxalate.
  • Indium metal salt include halides such as InBr, InBr 3 , InCl, InCla, Inl, Inl 3 , InF 3 , In (OH) 3, In (OCH (CH 3 ) 2) 3, In(N0 3 ) 3 , In(C10 4 ) 3 , In 2 (S0 4 ) 3 , and In(OOCCH 3 ) 3 .
  • Iridium metal salt includes IrBr 3 , IrBr 4 , IrCl 3 , IrCl 4 and IrI4.
  • Lanthanum metal salt include La (NO 3 ) 3, La (OH) 3 , La2 (CO 3 ) 3, La 2 (S0 4 ) 3 , LaBr 3 , LaCl 3 , LaF 3 , Lal 3 , La(C10 4 ) 3 , La2(C20 4 ) 3 , La(OC 3 H7) 3 and La(C 2 H 5 0) 3 .
  • Cerium metal salt include Ce(N0 3 ) 3 , Ce 2 (C0 3 ) 3 , Ce(S0 4 ) 2 , Ce 2 (S0 4 ) 3 , CeBr, CeCl 3 , CeF 3 , Cel 2 , Ce(C10 4 ) 3 , (CH 3 COO) 3 Ce and Ce 2 (C 2 0 4 ) 3 .
  • the alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the alkaline metal or alkaline earth metal component.
  • the alkaline metal salt and the alkaline earth metal salt include alkaline metal nitrates, alkaline earth metal nitrates, alkaline metal halides, alkaline earth metal halides , alkaline metal acetates , alkaline earth metal acetates, alkaline metal butyrates, alkaline earth metal butyrates, alkaline metal benzoates, alkaline earth metal benzoates, alkaline metal alkoxides, alkaline earth metal alkoxides, alkaline metal carbonates, alkaline earth metal carbonates, alkaline metal citrates, alkaline earth metal citrates, alkaline metal formates, alkaline earth metal formates, alkaline metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, alkaline metal hydroxides, alkaline earth
  • At least one of the materials for the solvent i.e., copper metal salt, a ruthenium metal salt and a metal containing salt as mentioned above, alkaline metal and alkaline earth metal salt, contains preferably a halogen ion, more preferably a chloride ion.
  • a halogen ion may form the alkaline metal or alkaline earth metal component such as NaCl and the halogen component such as halides and oxyhalides of Cu, Ru or the above-mentioned metals.
  • the solution may contain acidic or basic compounds in order to control its pH.
  • the solvent examples include water, alcohols such as methanol or ethanol, and ethers.
  • the amount of the solvent is preferably 0.01 to 2000 parts by weight per part by weight of copper salt. If the catalyst contains the support, the amount of the solvent is preferably 0.01 to 500 parts by weight per part by weight of the support, and more preferably 0.1 to 100 parts by weight.
  • the composition as prepared by the impregnation is usually dried, and examples of the drying method include evaporation to dryness, spray drying, drum drying and flash drying.
  • the composition as prepared by the impregnation is preferably dried at a temperature of 10°C to 250°C, and more preferably 40 ° C to 200 ° C before calcining the composition. Drying may be performed under an atmosphere of air or also under an inert gas atmosphere (for example, Ar, N 2 , He) at standard pressure or reduced pressure.
  • a drying time is preferably in the range from 0.5 to 24 hours. After drying, the composition can be shaped to a desired structure as necessary.
  • Calcining the composition is not limited, but preferably may be performed under a gas atmosphere containing oxygen and/or inert gas such as nitrogen, helium and argon.
  • a gas atmosphere containing oxygen and/or inert gas such as nitrogen, helium and argon.
  • gases include air, an oxygen gas, nitrous oxide, and other oxidizing gases.
  • the gas may be used after being mixed at an appropriate ratio with a diluting gas such as nitrogen, helium, argon, and water vapor.
  • An optimal temperature for calcination varies depending on the kind of the gas and the composition, however, a too high temperature may cause agglomeration of the ruthenium component and copper oxide. Accordingly, the calcination temperature is typically 200 to 800°C, preferably 400 to 600°C.
  • the calcining time is preferably in the range from 0.5 hour to 24 hours.
  • the catalyst can be used as powder, but it is usual to shape it into desired structures such as spheres, pellets, cylinders, rings, hollow cylinders or stars.
  • the catalyst can be shaped by a known procedure such as extrusion, ram extrusion, and tableting.
  • the calcination is normally performed after shaping into the desired structures, but it can also be performed before shaping them.
  • the olefin may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms .
  • the olefin may be amonoolefin or a diolefin .
  • Examples of the monoolefin include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, and decene.
  • the diene include butadiene such as 1 , 3-butadiene or 1 , 2-butadiene .
  • olefin examples include preferably monoolefin, more preferably ethylene, propylene, butene, pentene, hexene, heptene and octene, still more preferably ethylene, propylene and butene, most preferably propylene.
  • the reaction is generally performed in the gas phase.
  • the olefin and oxygen may be fed respectively in the form of a gas.
  • Olefin and oxygen gases can be fed in the form of their mixed gas.
  • Olefin and oxygen gases may be fed with diluent gases. Examples of diluent gases include nitrogen, methane, ethane, propane, carbon dioxide, or rare gases, such as argon and helium.
  • oxygen source pure oxygen may be used, or a mixed gas containing a gas inactive to the reaction, such as air, may be used.
  • the amount of oxygen used varies depending on the reaction type, the catalyst, the reaction temperature or the like.
  • the amount of oxygen is typically 0.01 to 100 mol, and preferably 0.03 to 30 mol, and more preferably 0.25 to 10 mol, with respect to 1 mol of the olefin.
  • the reaction is performed at a temperature generally of
  • 100 to 350 C preferably of 120 to 330°C, more preferably of 170 to 310 ° C.
  • the reaction is usually carried out under reaction pressure in the range of reduced pressure to increased pressure .
  • Reduced pressure means a pressure lower than atmospheric pressure.
  • Increased pressure means a pressure higher than atmospheric pressure.
  • the pressure is typically in the range of 0.01 to 3 MPa, and preferably in the range of 0.02 to 2 MPa, in the absolute pressure.
  • the gaseous hourly space velocity (Liters of gas at standard temperature and pressure passing over the one liter of packed catalyst per hour) is generally in the range of from 100 Nl/(l.h) to 100000 Nl/(l.h), preferably 500 Nl/(l.h) to 50000 Nl/ (l.h) .
  • the linear velocity is generally in the range of from 0.0001 m/s to 500 m/s, and preferably in range of 0.001 to 50 m/s.
  • the reaction may be carried out as a batch reaction or a continuous flow reaction, preferably as a continuous flow reaction for industrial application.
  • the reaction of the present invention may be carried out by mixing an olefin and oxygen and then contacting the mixture with the catalyst under reduced pressure to the increased pressure.
  • the reactor type is not limited. Examples of the reactor type are fluid bed reactor, fixed bed reactor, moving bed reactor, and the like, preferably fixed bed reactor. In the case of using fixed bed reactor, single tube reactor or multi tube reactor can be employed. One or more reactors can be used for the reaction. If the number of reactors is large, small reactors, for example microreactors , can be used. The reactors each can have multiple channels.
  • the catalyst can be packed into the reactor or coated on the surface of the reactor wall.
  • the coated type reactor is suitable for microreactors and the packed bed reactor is suitable for a large reactor.
  • reaction mixture can be passed through the packed bed reactor in up-flow mode or in downflow mode.
  • Adiabatic type reactor or heat exchange type reactor may also be used.
  • adiabatic type reactor a part of the reaction mixture from the reactor can be recycled into the reactor after heat-exchanging to control the reaction temperature .
  • the reactors can be arranged in series and/or in parallel.
  • a heat exchanger can be used between the reactors for controling reaction temperature.
  • the olefin oxide may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms.
  • the olefin oxide may have one carbon-carbon double bond when the diolefin is applied for the reaction. Examples of the olefin oxide having one
  • carbon-carbon double bond include 3, 4-epoxy-l-butene .
  • olefin oxides examples include preferably ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide and octene oxide, more preferably ethylene oxide, propylene oxide and butene oxide, still more preferably propylene oxide.
  • the olefin oxide as obtained can be collected by absorption with a suitable solvent such as water and acetonitrile followed by conducting a method known in the art such as separation by distillation.
  • a reaction gas was mixed with ethane (10 Nml/min) as an external standard, and then directly introduced in the TCD-GC equipped with a column of Gaskuropack 54 (2 m) . All products in the reaction gas were collected for 1 hour with double methanol traps connected in series and cooled with an ice bath. The two methanol solutions were mixed together and added to anisole as an external standard, and then analyzed with two FID-GCs equipped with different columns, PoraBOND U (25 m) and PoraBOND Q (25 m) .
  • the detected products were propylene oxide (PO) , acetone (AT), acetaldehyde (AD), CO x (C0 2 and CO), and propanal (PaL) and acrolein (AC) .
  • the metal compostion was prepared by a co- impregnation method.
  • a predetermined weight (1.9 g) of an amorphous silica powder (Si0 2 , Japan Aerosil, 380 m 2 /g) was added to an aqueous solution mixture containing 0.54 g of (NH 4 ) 2 RuCl 6 (Aldrich) , 0.30 g of Cu(N0 3 ) 2 (Wako) , 0.28 g of MnCl 2 (Wako) and 0.10 g of NaCl (Wako) , followed by stirring for 24 hours in the air to impregnate the support with the metal salts.
  • the resulting material was then heated at 100 °C until dried, and calcined at 500 °C for 12 hours in the air to give a catalyst.
  • the catalyst was evaluated by using a fixed-bed reactor. Filling a 1/2-inch reaction tube made of stainless steel with 1 mL of the thus obtained catalyst, the following gases were fed to the reaction tube to carry out the reaction : 7.5 mL/minute of propylene, 15 mL/minute of the air, 16.5 mL/minute of a nitrogen gas. Such a reaction was carried out at the reaction temperature of 270°C under the increased pressure (equivalent to 0.3 MPa in the absolute pressure), with GHSV of 2340hr _1 .
  • Catalysts were prepared in the same manner as Example 1 except that 0.23 g of GeCl 4 (Wako) was used instead of MnCl 2 .
  • the reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
  • Catalysts were prepared in the same manner as Example 1 except that 0.15 g of TICI3 (Wako) was used instead of MnCl 2 .
  • the reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
  • Example 5 Catalysts were prepared in the same manner as Example 1 except that 0.15 g of InCl 3 (Wako) was used instead of MnCl 2 . The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
  • Example 5
  • Catalysts were prepared in the same manner as Example 1 except that 0.03 g of IrCl 3 (Wako) was used instead of MnCl 2 .
  • the reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
  • Catalysts were prepared in the same manner as Example 1 except that 0.03 g of LaCl 3 (Wako) was used instead of MnCl 2 .
  • the reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
  • Catalysts were prepared in the same manner as Example 1 except that 0.05 g of CeCl 3 (Wako) was used instead of MnCl 2 .
  • the reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
  • the metal compostion was prepared by a co-impregnation method.
  • a predetermined weight (1.9 g) of an amorphous silica powder (Si0 2 , Japan Aerosil, 380 m /g) was added to an aqueous solution mixture containing 0.54 g of ( H 4 ) 2 RuCl 6 (Aldrich) , 0.30 g of Cu(N0 3 ) 2 (Wako) and 0.10 g NaCl (Wako) , followed by stirring for 24 hours in the air to impregnate the support with the metal salts.
  • the resulting material was then heated at 100 °C until dried, and calcined at 500 °C for 12 hours in the air to give a catalyst .
  • the catalyst as obtained was applied to the same reaction as Example 1 except that the catalyst was changed.

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Abstract

L'invention concerne un procédé de préparation d'un oxyde d'oléfine consistant à faire réagir une oléfine avec de l'oxygène en présence d'un catalyseur comprenant un oxyde de cuivre, un oxyde de ruthénium et un composant métallique dérivé d'un métal choisi dans le groupe constitué par Mn, Ge, Tl, In, Ir, La et Ce.
PCT/US2011/065162 2011-01-05 2011-12-15 Procédé de préparation d'un oxyde d'oléfine WO2012094121A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014003209A1 (fr) * 2012-06-29 2014-01-03 Sumitomo Chemical Company, Limited Procédé de fabrication d'un oxyde d'oléfine

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US4826802A (en) * 1987-02-24 1989-05-02 Nitto Chemical Industry Co., Ltd. Method for preparation of antimony and tellurium-containing metal oxide catalysts
US5504053A (en) * 1989-04-18 1996-04-02 Union Carbide Chemicals & Plastics Technology Corporation Alkylene oxide catalysts having enhanced activity and/or stability
US20010020105A1 (en) * 2000-02-23 2001-09-06 Toshio Hayashi Catalyst for use in production of epoxide, method for producing the catalyst, and method for producing epoxide
US20030017943A1 (en) * 1999-09-07 2003-01-23 Zhiping Shan Mesoporous material and use thereof for the selective oxidation of organic compounds
US20040068128A1 (en) * 2001-02-07 2004-04-08 Teles Joaquim Henrique Method for producing an epoxide
US6765101B1 (en) * 2001-05-01 2004-07-20 Union Carbide Chemicals & Plastics Technology Corporation Synthesis of lower alkylene oxides and lower alkylene glycols from lower alkanes and/or lower alkenes
US20100267969A1 (en) * 2009-04-21 2010-10-21 Dow Technology Investments Llc Rhenium-promoted epoxidation catalysts and methods of making and using them

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Publication number Priority date Publication date Assignee Title
US4826802A (en) * 1987-02-24 1989-05-02 Nitto Chemical Industry Co., Ltd. Method for preparation of antimony and tellurium-containing metal oxide catalysts
US5504053A (en) * 1989-04-18 1996-04-02 Union Carbide Chemicals & Plastics Technology Corporation Alkylene oxide catalysts having enhanced activity and/or stability
US20030017943A1 (en) * 1999-09-07 2003-01-23 Zhiping Shan Mesoporous material and use thereof for the selective oxidation of organic compounds
US20010020105A1 (en) * 2000-02-23 2001-09-06 Toshio Hayashi Catalyst for use in production of epoxide, method for producing the catalyst, and method for producing epoxide
US20040068128A1 (en) * 2001-02-07 2004-04-08 Teles Joaquim Henrique Method for producing an epoxide
US6765101B1 (en) * 2001-05-01 2004-07-20 Union Carbide Chemicals & Plastics Technology Corporation Synthesis of lower alkylene oxides and lower alkylene glycols from lower alkanes and/or lower alkenes
US20100267969A1 (en) * 2009-04-21 2010-10-21 Dow Technology Investments Llc Rhenium-promoted epoxidation catalysts and methods of making and using them

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014003209A1 (fr) * 2012-06-29 2014-01-03 Sumitomo Chemical Company, Limited Procédé de fabrication d'un oxyde d'oléfine

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