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WO2013062791A1 - Process for producing olefin oxide - Google Patents

Process for producing olefin oxide Download PDF

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Publication number
WO2013062791A1
WO2013062791A1 PCT/US2012/059945 US2012059945W WO2013062791A1 WO 2013062791 A1 WO2013062791 A1 WO 2013062791A1 US 2012059945 W US2012059945 W US 2012059945W WO 2013062791 A1 WO2013062791 A1 WO 2013062791A1
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Prior art keywords
oxide
metal
catalyst
alkaline
examples
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PCT/US2012/059945
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French (fr)
Inventor
Yoshihiko Ohishi
Fumisato Goto
Anusorn Seubsai
Selim Senkan
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • B01J23/8926—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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/8946—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 alkali or alkaline earth 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
    • 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
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to a process for producing an olefin oxide.
  • Olefin oxides such as propylene oxide
  • the present invention provides:
  • a process for producing an olefin oxide comprising: a first step of contacting a catalyst comprising a copper oxide, and one or both of a ruthenium oxide and one metal oxide other than a copper oxide and a ruthenium oxide, with water and a second step of reacting an olefin with oxygen in the presence of the catalyst obtained in the first step;
  • the present invention provides a process for producing an olefin oxide comprising:
  • the catalyst comprises a copper oxide, and one or both of a ruthenium oxide and one metal oxide other than a copper oxide and a ruthenium oxide.
  • the catalyst preferably comprises a copper oxide and one metal oxide other than copper oxide, and more preferably comprises a copper oxide and a ruthenium oxide and one metal oxide other than copper oxide and ruthenium oxide .
  • the copper oxide is generally composed of an oxygen atom and copper, and examples thereof include Cu 2 0 and CuO, and CuO is preferable.
  • the ruthenium oxide is generally composed of an oxygen atom and ruthenium, and examples thereof include Ru0 4 and Ru0 2 , and Ru0 2 is preferable.
  • metal oxides other than copper oxide and ruthenium oxide examples include manganese oxides, tellurium oxides, bismuth oxides, antimony oxides, chromium oxides, rhenium oxides, cobalt oxides, nickel oxides, osmium oxides, cerium oxides, germanium oxides , tin oxides, tungsten oxides , thallium oxides, indium oxides, iridium oxides, lanthanum oxides, iron oxides, molybdenum oxides , selenium oxides , vanadium oxides and niobium oxides.
  • the tellurium oxide is generally composed of an oxygen atom and tellurium, and examples thereof include TeO, Te0 2 and Te0 3 , and Te0 2 is preferable.
  • the manganese oxide is generally composed of an oxygen atom and manganese, and examples thereof include MnO, Mn0 2 , Mn 2 0 3 and Mn 3 0 4 , and Mn 2 0 3 is preferable.
  • the bismuth oxide is generally composed of an oxygen atom and bismuth, and examples thereof include BiO, Bi0 2 , Bi 2 0 and Bi 2 0 3 .
  • the antimony oxide is generally composed of an oxygen atom and antimony, and examples thereof include Sb0 2 , Sb 2 0 3 , Sb 2 0 4 and Sb 2 0 5 , and Sb0 2 and Sb 2 0 3 are preferable.
  • the chromium oxide is generally composed of an oxygen atom and chromium, and examples thereof include Cr0 3 and Cr 2 0 3 , and Cr0 3 is preferable.
  • the rhenium oxide is generally composed of an oxygen atom and rhenium, and examples thereof include Re0 2 , Re0 3 and Re 2 0 7 , and Re0 2 and Re0 3 are preferable.
  • the cobalt oxide is generally composed of an oxygen atom and cobalt, and examples thereof include CoO, Co 3 0 and Co 2 0 3 , and C0 3 O 4 is preferable.
  • the nickel oxide is generally composed of an oxygen atom and nickel, and examples thereof include NiO .
  • the osmium oxide is generally composed of an oxygen atom and osmium, and examples thereof include 0s0 2 and 0s0 , and 0s0 2 is preferable.
  • the cerium ' oxide is generally composed of an oxygen atom and cerium, and examples thereof include Ce 2 0 3 and Ce0 2 , and Ce0 2 is preferable.
  • the germanium oxide is generally composed of an oxygen atom and germanium, and examples thereof include GeO and Ge0 2 , and Ge0 2 is preferable.
  • the tin oxide is generally composed of an oxygen atom and tin, and examples thereof include Sn0 2 , SnO, Sn 2 0 3 and Sn 3 0 , and Sn0 2 and SnO are preferable.
  • the tungsten oxide is generally composed of an oxygen atom and tungsten, and examples thereof include 3 0, W17O47, W 5 0i 4 , W0 2 and 0 3 , and W0 2 and W0 3 are preferable.
  • the thallium oxide is generally composed of an oxygen atom and thallium, and examples thereof include Tl 2 0, Tl 2 0 3 and T1 4 0 3 , and T1 4 0 3 is preferable.
  • the indium oxide is generally composed of an oxygen atom and indium, and examples thereof include ln 2 0 3 .
  • the iridium oxide is generally composed of an oxygen atom and iridium, and examples thereof include Ir0 2 .
  • the lanthanum oxide is generally composed of an oxygen atom and lanthanum, and examples thereof include La 2 0 3 .
  • the iron oxide is generally composed of an oxygen atom and lanthanum, and examples thereof include FeO, Fe 2 0 3 and Fe 3 0 4 , and Fe 2 0 3 is preferable.
  • the molybdenum oxide is generally composed of an oxygen atom and molybdenum, and examples thereof include Mo0 2 or Mo0 3 .
  • the selenium oxide is generally composed of an oxygen atom and selenium, and examples thereof include Se0 2 and Se0 3 , and Se0 2 is preferable.
  • the vanadium oxide is generally composed of an oxygen atom and vanadium, and examples thereof include VO, V0 2 , V 2 0 3 , V e 0 13 and V 2 0 5 , and V 2 0 5 is preferable.
  • the niobium oxide is generally composed of an oxygen atom and niobium, and examples thereof include NbO, Nb0 2 and Nb 2 0 5 .
  • the catalyst preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide, manganese oxide, tellurium oxide, bismuth oxide, antimony oxide, chromium oxide, rhenium oxide, cobalt oxide, nickel oxide, osmium oxide, cerium oxide, germanium oxide , tin oxide, tungsten oxide , thallium oxide , indium oxide, iridium oxide, lanthanum oxide, iron oxide, molybdenum oxide, selenium oxide, vanadium oxide and niobium oxide.
  • the catalyst more preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide, tellurium oxide, manganese oxide, bismuth oxide, antimony oxide, cerium oxide, germanium oxide and tin oxide.
  • the catalyst still more preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide , tellurium oxide, manganese oxide and tin oxide.
  • the catalyst especially preferably consists of copper oxide and one or both of ruthenium oxide and tellurium oxide.
  • the catalyst may comprise a composite metal oxide.
  • the composite metal oxide include those composed of copper, ruthenium and oxygen; those composed of copper, sodium and oxygen; those composed of sodium, ruthenium and oxygen; those composed of copper, ruthenium, sodium and any other metals and oxygen; those composed of copper, any other metals and oxygen; and those composed of ruthenium, any other metals and oxygen; those composed of sodium and any other metals and oxygen. If the catalyst comprises the composite metal oxide, it may be supported on the support or any of the other components .
  • the catalyst preferably contains a support, such as a porous support and a non-porous support .
  • a support such as a porous support and a non-porous support .
  • One or both of a copper oxide and a ruthenium oxide are preferably supported on a support, more preferably supported on a porous support.
  • the non-porous support include a non-porous support comprising Si0 2 such as CAB-O-SIL (registered trademark) .
  • the catalyst containing a support is valuable for production of olefin oxides , which is one aspect of the present invention.
  • the porous support has pores capable of supporting one or both of a copper oxide and a ruthenium oxide .
  • the porous support preferably comprises Al 2 0 3 , Si0 2 , Ti0 2 , or Zr0 2 , more preferably Si0 2 .
  • Examples of the porous support comprising Si0 2 include mesoporous silica.
  • Such porous supports may also comprise zeolites.
  • the support may be in form of powder, or shaped to a desired structure as necessary.
  • the catalyst preferably comprises one or more selected from the group consisting of an alkaline metal component and an alkaline earth metal component.
  • the alkaline metal component may be an alkaline metal-containing compound, and may be an alkaline metal ion.
  • the alkaline earth metal component may be an alkaline earth metal-containing compound, and may be 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 .
  • the alkaline metal component may be an alkaline metal oxide.
  • Example of the alkaline metal oxide include Na 2 0, Na 2 0 2 , K 2 0, K0 2 , K 2 0 2 , Rb 2 0, Rb 2 0 2 , Cs 2 0, Cs 2 0 2 , Cs0 2 , Cs0 3 , Cs 2 0 3 , Cs u 0 3 , Cs0 and Cs 7 0.
  • Examples of the alkaline metal ion include 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.
  • the alkaline earth metal component may be an alkaline metal earth oxide.
  • Examples of the alkaline earth metal oxide include CaO, Ca0 2 , MgO, Mg0 2 , SrO, Sr0 2 , BaO and Ba0 2 .
  • Examples of the alkaline earth metal ion include Ca 2+ , Mg 2+ , Sr 2+ and Ba 2+ .
  • the alkaline metal-containing compound is preferable, and a sodium- containing compound is more preferable.
  • the alkaline metal-containing compound is preferably an alkaline metal salt.
  • the alkaline earth metal-containing compound is preferably an alkaline earth metal salt.
  • the alkaline metal salt comprises the alkaline metal ion as mentioned above and an anion.
  • the alkaline earth metal salt comprises the alkaline earth metal ion as mentioned above and an anion. Examples of anions in such salts include F “ , CI “ , Br ⁇ , I " , OH “ , N0 3 ⁇ , S0 4 2 ⁇ , C0 3 2" , HC0 3 " and S0 3 2" .
  • Such salt is preferably an alkaline metal salt containing a halogen such as an alkaline metal halide, or an alkaline earth metal-containing salt containing a halogen such as an alkaline earth metal halide, and an alkaline metal salt containing a halogen is more preferable, and an alkaline metal chloride is still more preferable.
  • the alkaline metal component or the alkaline earth metal component may be supported on the support as mentioned above.
  • the catalyst may contain a halogen component .
  • the halogen component is generally a halogen- containing compound . Examples of the halogen include chlorine, fluorine, iodine and bromine.
  • halogen-containing compound examples include halides of copper, ruthenium or any other metals of metal oxides and oxyhalides of copper, ruthenium or any other metals of metal oxides. If the catalyst comprises the halogen component, the component may be supported on the porous support as mentioned above .
  • the total content of these components is preferably 0.01 to 80 parts by weight relative to 100 parts of support.
  • the lower limit of the total content is more preferably 0.05 part by weight, still more preferably 0.1 part by weight relative to 100 parts by weight of a support .
  • the upper limit of the total content is more preferably 50 parts by weight, still more preferably 30 parts by weight relative to 100 parts by weight of a support .
  • the ruthenium/copper molar ratio in the catalyst is preferably 0.01/1 to 50/1 based on their atoms.
  • the lower limit of the molar ratio is more preferably 0.1/1, still more preferably 0.2/1
  • the upper limit of the molar ratio is more preferably 5/1, still more preferably 1/1.
  • alkaline metal or alkaline earth metal/copper molar ratio 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 0.01/1 , still more preferably 0.1/1.
  • the upper limit of the molar ratio is more preferably 10/1, still more preferably 5/1.
  • the other component/copper molar ratio 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 0.01/1, still more preferably 0.05/1.
  • the upper limit of the molar ratio is more preferably 10/1, still more preferably 5/1.
  • the catalyst can be produced according to the conventional methods.
  • the catalyst can be obtained by impregnating a support with a solution containing a copper ion and one or both of a ruthenium ion and other metal ion other than a copper ion and a ruthenium ion to prepare a composition, followed by calcining the composition .
  • the catalyst comprises an alkaline metal or alkaline earth metal component or any other components as mentioned above
  • the catalyst can be obtained in the same procedure as mentioned above except that solution further contains an alkaline metal or alkaline earth metal-containing ion, a halogen ion or an metal ion of any other metal which forms any of the metal oxides as mentioned above .
  • the solution containing a copper ion and one of both of a ruthenium ion and one metal ion other than a copper ion and a ruthenium ion can be prepared by dissolving a copper metal salt and one or both of a ruthenium metal salt and one metal salt other than a copper metal salt and a ruthenium metal salt in a solvent .
  • 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 nitrates, and copper chlorides.
  • tellurium salt or compound examples include, for example, a halide such as TeF s , TeBr 4 , TeCl 4 and Tel 4 , an oxyhalide, oxide such as TeO, Te0 2 and Te0 3 , an alkoxide such as Te(OC 2 H 5 ) 4 , ammonium tellurate, a tellurate such as H 2 Te0 3 , H s Te0 6 , Na 2 Te0 3 and Na 2 Te0 , preferably halide and oxide, more preferably oxide, still more preferably Te0 2 .
  • a halide such as TeF s , TeBr 4 , TeCl 4 and Tel 4
  • an oxyhalide, oxide such as TeO, Te0 2 and Te0 3
  • an alkoxide such as Te(OC 2 H 5 ) 4
  • ammonium tellurate a tellurate such as H 2 Te0 3 , H s Te0 6 , Na 2 Te0 3 and Na 2 Te0
  • manganese metal salt examples include manganese carbonate, manganese nitrate, manganese sulfate, manganese bromide, manganese chloride, manganese iodide, manganese perchlorate, manganese acetate, and manganese acetylacetonate .
  • bismuth metal salt examples include bismuth carbonate, bismuth nitrate, bismuth sulfate, bismuth bromide, bismuth chloride, bismuth iodide, bismuth oxychloride and bismuth acetate.
  • rhenium metal salt such as rhenium carbonyl, rhenium chloride, rhenium pentacarbonyl bromide, and rhenium pentacarbonyl chloride .
  • chromium metal salt such as chromium nitrate, chromium bromide, chromium chloride, chromium perchlorate, chromium sulfate, chromium acetate, and chromium acetylacetonate .
  • iron metal salt such as FeO(OH) , Fe(N0 3 ) 3 , FeS0 4 , Fe 2 (S0 4 ) 3 , FeC 2 0 4 , Fel 2 , FeBr 2 , FeBr 3 , FeCl 2 , FeCl 3 , Fe(C10 4 ) 2 , Fe(C10 4 ) 3 , Fe(OC 2 H 5 ) 3 and C 4 H s Fe0 4 .
  • iron metal salt such as FeO(OH) , Fe(N0 3 ) 3 , FeS0 4 , Fe 2 (S0 4 ) 3 , FeC 2 0 4 , Fel 2 , FeBr 2 , FeBr 3 , FeCl 2 , FeCl 3 , Fe(C10 4 ) 2 , Fe(C10 4 ) 3 , Fe(OC 2 H 5 ) 3 and C 4 H s Fe0 4 .
  • molybdenum metal salt such as MoCl 3 , MoCl 5 , MoF 6 , Mo ( CO) s and ( H 4 ) 2 Mo0 4 .
  • tungsten metal salt such as tungsten chloride, tungsten dichloride, tungsten dioxide, and tungsten ethoxide.
  • selenium metal salt such as SeOCl 2 , HeSe0 3 , Se 2 Cl 2 and SeCl 4 .
  • antimony metal salt such as antimony bromide, antimony chloride , antimony iodide, antimony ethoxide, and antimony acetate.
  • vanadium metal salt such as VC1 3 , VF 3 , VF 4 , VBr 3 , VOS0 4 , V0C1 3 , VOC 2 0 4 and V (CH 3 COCHCOCH 3 ) 3 .
  • nickel metal salt such as nickel sulfate, nickel nitrate, nickel bromide, nickel chloride, nickel iodide, nickel perchlorate, nickel carbonate, nickel oxalate, and nickel hydroxide.
  • cobalt metal salt such as cobalt sulfate, cobalt nitrate, cobalt bromide, cobalt chloride, cobalt iodide, cobalt perchlorate, cobalt acetylacetonate , cobalt acetate, cobalt carbonate, cobalt carbonyl, and cobalt hydroxide.
  • tin metal salt such as tin sulfate, tin bromide, tin chloride, tin iodide, tin acetylacetonate, tin acetate, tin methoxide , tin butoxide, tin ethoxide, tin oxalate and tin tartrate.
  • niobium metal salt examples include NbCl 5 , F 5 Nb, Nbl 5 and Nb(OC 2 H 5 ) 5 .
  • 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.
  • Examples of the indium metal salt include halides such as InBr, InBr 3 , InCl , InCl 3 , Inl, Inl 3 , InF 3 , In(0H) 3 , In(OCH(CH 3 ) 2 )3, In(N0 3 ) 3 , In(Cl0 4 ) 3 , In 2 (S0 4 ) 3 , and In (OOCCH 3 ) 3 .
  • halides such as InBr, InBr 3 , InCl , InCl 3 , Inl, Inl 3 , InF 3 , In(0H) 3 , In(OCH(CH 3 ) 2 )3, In(N0 3 ) 3 , In(Cl0 4 ) 3 , In 2 (S0 4 ) 3 , and In (OOCCH 3 ) 3 .
  • Examples of the iridium metal salt includes IrBr 3 , IrBr 4 , IrCl 3 , IrCl 4 and Irl 4 .
  • Examples of the lanthanum metal salt include La(N0 3 ) 3 , La (OH) 3 , La 2 (C0 3 ) 3 , La 2 (S0 4 ) 3 , LaBr 3 , LaCl 3 , LaF 3 , Lal 3 , La(C10 4 ) 3 , La 2 (C20 4 ) 3 , La(OC 3 H 7 ) 3 and La(C 2 H 5 0) 3 ,
  • cerium metal salt examples 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(Cl0 4 ) 3 , (CH 3 COO) 3 Ce and Ce 3 (C 2 0 4 ) 3 .
  • osmium metal salts examples include osmium halides such as osmium chloride.
  • the solvent contains an alkaline metal or alkaline earth metal ion, it can be prepared by adding an alkaline metal or alkaline earth metal salt to a solvent.
  • the alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the alkaline metal component or the 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
  • Such a halogen ion may form the alkaline metal or alkaline earth metal component such as NaCl and the haolgen component such as halides and oxyhalides of Cu or Ru.
  • the solution may contain acidic or basic compounds in order to control its pH.
  • Examples of the solvent for the solution include water and alcohols such as methanol or ethanol .
  • the composition as prepared by the impregnation is usually dried, and the drying method thereof is not limited.
  • the composition as prepared by the impregnation is preferably dried at a temperature of 40°C to 200°C before calcining the composition. Drying may be performed under an atmosphere of oxygen containing gas such as 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.
  • the method of calcining the composition is not limited, and calcining the composition is preferably performed under a gas atmosphere containing oxygen.
  • a gas atmosphere containing oxygen examples 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 gases and the compositions, however, a too high temperature may cause agglomeration of ruthenium oxide and copper oxide. Accordingly, the calcination temperature is typically 200°C to 800°C, preferably 400°C 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, tableting.
  • the calcination is normally performed after shaping into the desired structures, but it can also be performed before shaping them.
  • the catalyst is contacted with water.
  • the catalyst is preferably contacted with water and an an alkaline metal compound or an alkaline earth metal compound.
  • the catalyst is also preferably contacted with water and an inorganic acid.
  • alkaline metal compound examples include compounds containing an alkaline metal such as Na, K, Rb and Cs .
  • alkaline earth metal compound examples include compounds containing an alkaline earth metal such as Ca, Mg, Sr and Ba.
  • the alkaline metal compound or alkaline earth metal compound is preferably an alkaline metal compound, more preferably a sodium-containing compound or a potassium-containing compound, still more preferably a sodium-containing compound.
  • alkaline metal compound and the alkaline earth metal compound examples 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 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 metal hydroxides, alkaline earth metal hydroxides, alkaline metal hypochlorites, alkaline earth metal hypochlorites, alkaline metal halates, alkaline earth metal halates
  • Examples of the inorganic acid include hydrogen chloride, hydrogen bromide , hydrogen fluoride, hydrogen iodide , sulfurous acid, sulfuric acid, phosphorous acid, phosphoric acid, borous acid, boric acid, nitrous acid and nitric acid.
  • preferred are hydrogen chloride , sulfuric acid, phosphoric acid, boric acid and nitric acid, and more preferred is hydrogen chloride.
  • the amount of water used is not limited, and it is preferably 0.01 to 10000 parts by weight relative to 1 part of catalyst, more preferably 0.1 to 2000 parts by weight, and still more preferably 0.5 to 100 parts by weight relative to 1 part of catalyst.
  • the alkaline metal or alkaline earth metal/copper molar ratio in the catalyst is preferably 0.001/1 to 50/1 based on their atoms. When the alkaline metal or alkaline earth metal/copper molar ratio falls within such a range, the selectivity of the olefin oxide can be further improved.
  • the lower limit of the alkaline metal or alkaline earth metal/copper molar ratio is more preferably 0.01/1, and still more preferably 0.1/1.
  • the upper limit of the alkaline metal or alkaline earth metal/copper molar ratio is more preferably 10/1, and still more preferably 5/1.
  • the inorganic acid/copper molar ratio is usually 0.01 to 100, more preferably 0.05 to 90, and still more preferably 0.1 to 80.
  • the contacting is usually carried out at a temperature from 0°C to 120°C, and preferably from 5°C to 100°C.
  • the contacting time is not limited, and is usually 1 minute to 48 hours, and preferably 5 minutes to 24 hours.
  • the catalyst obtained by contacting is preferably dried to remove water .
  • the mixture obtained by contacting may be dried as it is or may be dried after filtration.
  • the mixture obtained after the filtration can be washed with water, or both of water and inorganic acid.
  • the drying method is not limited.
  • the mixture obtained by contacting is preferably dried at a temperature of 15°C to 200°C before calcining the composition. Drying may be performed under an atmosphere of oxygen containing gas such as 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.
  • the catalyst obtained can be calcined at a temperature from 200°C to 800°C, and preferably from 400°C to 600°C after contacting.
  • the calcining time is usually 10 minutes to 48 hours, preferably 20 minutes to 24 hours, more preferably 30 minutes to 20 hours.
  • the method of calcining the catalyst is not limited, and the calcination of the catalyst is preferably performed under a gas atmosphere containing oxygen.
  • a gas atmosphere containing oxygen examples 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.
  • the second step is a step of reacting an olefin with oxygen in the presence of the catalyst obtained in the first step.
  • the olefin may have a linear or branched structure.
  • the olefin usually contains 2 to 10 carbon atoms, and preferably contains 2 to 8 carbon atoms.
  • Examples of the olefin include ethylene, propylene, butene, pentene, hexene, heptene, octene, and butadiene, ethylene, propylene and butane are preferable, and propylene is more preferable.
  • the reaction is generally performed in the gas phase.
  • the olefin and oxygen may be fed in the form of a gas, respectively.
  • Olefin and oxygen gases can be fed in the form of their mixed gas.
  • Olefin and oxygen gases may be fed with diluent gases .
  • diluent gases include nitrogen, rare gases such as argon and helium, carbon dioxide, water vapor, methane, ethane and propane.
  • Preferable diluent gases are nitrogen, carbon dioxide and the both thereof.
  • oxygen source pure oxygen may be used, or a mixed gas containing pure oxygen and a gas inactive to the reaction, such as air, may be used.
  • gas inactive to the reaction include nitrogen, rare gases such as argon and helium, carbon dioxide, water vapor, methane, ethane and propane.
  • gases inactive to the reaction are nitrogen, carbon dioxide and the both thereof.
  • the amount of oxygen used varies depending on the reaction type, the kind of catalyst, the reaction temperature or the like.
  • the amount of oxygen is typically 0.01 mole to 100 mole, and preferably 0.03 mole to 30 mole, and more preferably 0.05 mole to 10 mole, and especially preferably 0.25 mole to 10 mole, with respect to 1 mol of the olefin .
  • the reaction is usually performed at a temperature of 100°C to 350°C, preferably of 120°C to 330°C, and more preferably of 170°C 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 reaction may be carried out as a batch reaction or a continuous reaction, preferably as a continuous 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. More than one reactor can be used. If the number of reactors is large, small reactors as for example microreactors , can be used, which can have multiple channels. Adiabatic type or heat exchange type may also be used.
  • the olefin oxide can be produced.
  • the olefin oxide may have a linear or branched structure .
  • the olefin oxide usually contains 2 to 10 carbon atoms, and preferably contains 2 to 8 carbon atoms .
  • Examples of the olefin oxides include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, and 3 , 4-epoxy-l-butene, and ethylene oxide, propylene oxide and butene oxide are preferable, and propylene oxide is more preferable .
  • the olefin oxide as obtained can be collected by 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
  • Each metal weight was determined from the amounts of the metal salts used for preparation of catalyst.
  • Amorphous silica powder (3.9 g; Si0 2 , Japan Aerosil , 380 m 2 /g) was added to an aqueous solution mixture containing 0.43 g of (NH 4 ) 2 R Cl s (Alfa) , 0.60 g of Cu(N0 3 ) 2 (Wako) , 0.20 gof NaCl (Wako) , 0.05 gof Te0 2 (Wako) and40gof H 2 0. The obtained mixture was stirred for 24 hours in air, at room temperature. The resulting material was then heated at 100°C until dried, and calcined at 500°C for 12 hours in air to obtain the metal oxide composition having the following composition.
  • the molar ratio of Ru/Cu/Na/Te 0.5/1/1.4/0.1
  • the total amount of Ru, Cu ; Na and Te 10.4 parts by weight relative to 100 parts by weight of Si0 2 .
  • the catalyst was evaluated by using a fixed-bed reactor. Filling a 0.6 inch OD reaction tube made of quartz glass with 1 mL of the prepared catalyst, the reaction tube was supplied with 7.5 mL/min. of propylene, 15 mL/min. of the air, and 16.5 mL/min. of a nitrogen gas to carry out the reaction, at the reaction temperature of 250°C under atmospheric pressure.
  • the feed ratio of propylene to oxygen was 2.4 (molar ratio, propylene/oxygen) .
  • Gas hourly space velocity (GHSV) 2340 ( If 1 ) .
  • Table 1 The result of Example 1 is shown in Table 1.
  • Amorphous silica powder (3.9 g; Si0 2 , Japan Aerosil , 380 m 2 /g) was added to an aqueous solution mixture containing 0.43 g of (NH 4 ) 2 RuCl 6 (Alfa), 0.60 g of Cu(N0 3 ) 2 ( Wako ) , 0.20 gof NaCl (Wako) , 0.05gof Te0 2 (Wako) and40gofH 2 0.
  • the obtained mixture was stirred for 24 hours in air, at room temperature.
  • the resulting material was then heated at 100°C until dried, and calcined at 500°C for 12 hours in air to obtain the metal oxide composition having the following composition.
  • the total amount of Ru, Cu, Na and Te 10.4 parts by weight relative to 100 parts by weight of Si0 2 .
  • Amorphous silica powder (1.9 g; Si0 2 , Japan Aerosil, 380 m 2 /g) was added to an aqueous solution mixture containing 0.55 g of (NH 4 ) 2 RuCl 6 (Alfa), 0.30 g of Cu(N0 3 ) 2 (Wako) and 40 g of H 2 0. The obtained mixture was stirred for 24 hours in air at 25°C.
  • the resulting material was then heated at 100°C until dried, and calcined at 500°C for 12 hours in air to obtain the metal oxide composition.
  • the total amount of Ru, Cu, Na 14.3 parts by weight relative to 100 parts by weight of Si0 2 .
  • Amorphous silica powder (1.9 g; Si0 2 , Japan Aerosil , 380 m 2 /g) was added to an aqueous solution mixture containing 0.55 g of (NH 4 ) 2 RuCl 6 (Alfa), 0.30 g of Cu (N0 3 ) 2 (Wako), 0.10 gof NaCl (Wako) and 40g of H 2 0.
  • the obtained mixture was stirred for 24 hours in air, at 25°C.
  • the resulting material was then heated at 100°C until dried, and calcined at 500°C for 12 hours in air to obtain the catalyst having the following composition.
  • the total amount of Ru, Cu and Na 14.3 parts by weight relative to 100 parts by weight of Si0 2 .
  • the catalyst was evaluated in the same manners as Example 1 except the reaction temperature of 270°C and the result is shown in Table 2.
  • Amorphous silica powder (44mg; Si0 2 , Alfa, 85-115 m 2 /g) was added to an aqueous solution mixture containing 3.6 mg of (NH 4 ) 2 RuCl 6 (Aldrich) , 1.8 mg of Cu(N0 3 ) 2 (Alfa), 0.90mg of NaCl (Alfa) and 950 mg of H 2 0. The obtained mixture was stirred for 1 hour in air, at room temperature.
  • the resulting material was then heated at 165°C until dried, and calcined at 480°C for 6 hours in air to obtain the metal oxide composition having the following composition.
  • the total amount of Ru, Cu and Na 14.3 parts by weight relative to 100 parts by weight of Si0 2 .
  • the mixture gas consisting of 1 vol% propylene (C 3 H 6 ) , 4 vol% 0 2 , and 95 vol% He was fed to the well at a gas hourly space velocity (GSHV) of 20,000 h "1 with a mass flow controller (MKS , Andover, MA) , at a reactor temperature of 250°C.
  • GSHV gas hourly space velocity
  • MKS mass flow controller
  • MA mass flow controller
  • TCD thermal conductivity detector
  • PoraPLOT U 10M
  • Molecular sieve 13X 10M
  • the detected products were propylene oxide (PO) , acetone
  • Each metal weight was determined from the amounts of the metal salts used for preparation of catalyst.
  • Amorphous silica powder (44 mg; Si0 2 , Alfa, 85-115 m 2 /g) was added to an aqueous solution mixture containing 3.6 mg of (NH 4 ) 2 RuCl 6 (Aldrich) , 1.8 mg of Cu(N0 3 ) 2 (Alfa) , 0.90 mg of NaCl (Alfa) and 950 mg of H 2 0. The obtained mixture was stirred for
  • the resulting material was then heated at 100°C until dried, and calcined at 480°C for 6 hours in air to obtain the metal oxide composition having the following composition.
  • the molar ratio of Ru/Cu/Na 1.3/1/1.4.
  • the total amount of Ru, Cu and Na 14.3 parts by weight relative to 100 parts by weight of Si0 2 .
  • the catalyst was evaluated in the same manner as Example 3, and the result is shown in Table 3.
  • the catalyst was evaluated in the same manner as Example 3, and the result is shown in Table 4.

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Abstract

A process for producing an olefin oxide comprising: a first step of contacting a catalyst comprising a copper oxide, and one or both of ruthenium oxide and one metal oxide other than a copper oxide and a ruthenium oxide, with water and a second step of reacting an olefin with oxygen in the presence of the catalyst obtained in the first step.

Description

DESCRIPTION
PROCESS FOR PRODUCING OLEFIN OXIDE
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit U.S. Provisional Application No. 61/550,850 filed on October 24, 2011, the contents of which are hereby incorporated by reference in their entirety into the present disclosure.
FIELD OF THE INVENTION
The present invention relates to a process for producing an olefin oxide.
BACKGROUND ART
Olefin oxides, such as propylene oxide, are important and versatile intermediates used in the production of a large variety of valuable consumer products such as polyurethane foams, polymers, alkylene glycol, cosmetics, food emulsifiers and as fumigants and insecticides. SUMMARY OF THE INVENTION
The present invention provides:
[1] A process for producing an olefin oxide comprising: a first step of contacting a catalyst comprising a copper oxide, and one or both of a ruthenium oxide and one metal oxide other than a copper oxide and a ruthenium oxide, with water and a second step of reacting an olefin with oxygen in the presence of the catalyst obtained in the first step;
[2] The process according to [1] , wherein the catalyst is contacted with water and an alkaline metal compound or an alkaline earth metal compound;
[3] The process according to [1] , wherein the catalyst is contacted with water and an inorganic acid;
[4] The process according to any one of [1] to [3] , wherein the first step further comprises calcining the catalyst at a temperature from 350°C to 650°C after contacting;
[5] The process according to any one of [1] to [4] , wherein the catalyst comprises a copper oxide and a ruthenium oxide;
[6] The process according to any one of [1] to [5] , wherein the catalyst further comprises an alkaline metal component or an alkaline earth metal component;
[7] The process according to any one of [1] to [6] , wherein the catalyst further comprises a halogen component.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a process for producing an olefin oxide comprising:
a first step of contacting a catalyst comprising a copper oxide, and one or both of a ruthenium oxide and one metal oxide other than a copper oxide and a ruthenium oxide, with water and a second step of reacting an olefin with oxygen in the presence of the catalyst obtained in the first step.
The catalyst comprises a copper oxide, and one or both of a ruthenium oxide and one metal oxide other than a copper oxide and a ruthenium oxide. The catalyst preferably comprises a copper oxide and one metal oxide other than copper oxide, and more preferably comprises a copper oxide and a ruthenium oxide and one metal oxide other than copper oxide and ruthenium oxide .
The copper oxide is generally composed of an oxygen atom and copper, and examples thereof include Cu20 and CuO, and CuO is preferable. The ruthenium oxide is generally composed of an oxygen atom and ruthenium, and examples thereof include Ru04 and Ru02, and Ru02 is preferable. Examples of the metal oxides other than copper oxide and ruthenium oxide include manganese oxides, tellurium oxides, bismuth oxides, antimony oxides, chromium oxides, rhenium oxides, cobalt oxides, nickel oxides, osmium oxides, cerium oxides, germanium oxides , tin oxides, tungsten oxides , thallium oxides, indium oxides, iridium oxides, lanthanum oxides, iron oxides, molybdenum oxides , selenium oxides , vanadium oxides and niobium oxides.
The tellurium oxide is generally composed of an oxygen atom and tellurium, and examples thereof include TeO, Te02 and Te03, and Te02 is preferable.
The manganese oxide is generally composed of an oxygen atom and manganese, and examples thereof include MnO, Mn02, Mn203 and Mn304, and Mn203 is preferable.
The bismuth oxide is generally composed of an oxygen atom and bismuth, and examples thereof include BiO, Bi02, Bi20 and Bi203.
The antimony oxide is generally composed of an oxygen atom and antimony, and examples thereof include Sb02, Sb203 , Sb204 and Sb205, and Sb02 and Sb203 are preferable.
The chromium oxide is generally composed of an oxygen atom and chromium, and examples thereof include Cr03 and Cr203 , and Cr03 is preferable.
The rhenium oxide is generally composed of an oxygen atom and rhenium, and examples thereof include Re02, Re03 and Re207, and Re02 and Re03 are preferable.
The cobalt oxide is generally composed of an oxygen atom and cobalt, and examples thereof include CoO, Co30 and Co203 , and C03O4 is preferable.
The nickel oxide is generally composed of an oxygen atom and nickel, and examples thereof include NiO .
The osmium oxide is generally composed of an oxygen atom and osmium, and examples thereof include 0s02 and 0s0 , and 0s02 is preferable.
The cerium' oxide is generally composed of an oxygen atom and cerium, and examples thereof include Ce203 and Ce02, and Ce02 is preferable.
The germanium oxide is generally composed of an oxygen atom and germanium, and examples thereof include GeO and Ge02, and Ge02 is preferable.
The tin oxide is generally composed of an oxygen atom and tin, and examples thereof include Sn02, SnO, Sn203 and Sn30 , and Sn02 and SnO are preferable.
The tungsten oxide is generally composed of an oxygen atom and tungsten, and examples thereof include 30, W17O47, W50i4, W02 and 03 , and W02 and W03 are preferable.
The thallium oxide is generally composed of an oxygen atom and thallium, and examples thereof include Tl20, Tl203 and T1403 , and T1403 is preferable.
The indium oxide is generally composed of an oxygen atom and indium, and examples thereof include ln203.
The iridium oxide is generally composed of an oxygen atom and iridium, and examples thereof include Ir02.
The lanthanum oxide is generally composed of an oxygen atom and lanthanum, and examples thereof include La203.
The iron oxide is generally composed of an oxygen atom and lanthanum, and examples thereof include FeO, Fe203 and Fe304 , and Fe203 is preferable.
The molybdenum oxide is generally composed of an oxygen atom and molybdenum, and examples thereof include Mo02 or Mo03. The selenium oxide is generally composed of an oxygen atom and selenium, and examples thereof include Se02 and Se03, and Se02 is preferable.
The vanadium oxide is generally composed of an oxygen atom and vanadium, and examples thereof include VO, V02, V203 , Ve013 and V205, and V205 is preferable.
The niobium oxide is generally composed of an oxygen atom and niobium, and examples thereof include NbO, Nb02 and Nb205. The catalyst preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide, manganese oxide, tellurium oxide, bismuth oxide, antimony oxide, chromium oxide, rhenium oxide, cobalt oxide, nickel oxide, osmium oxide, cerium oxide, germanium oxide , tin oxide, tungsten oxide , thallium oxide , indium oxide, iridium oxide, lanthanum oxide, iron oxide, molybdenum oxide, selenium oxide, vanadium oxide and niobium oxide. The catalyst more preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide, tellurium oxide, manganese oxide, bismuth oxide, antimony oxide, cerium oxide, germanium oxide and tin oxide. The catalyst still more preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide , tellurium oxide, manganese oxide and tin oxide. The catalyst especially preferably consists of copper oxide and one or both of ruthenium oxide and tellurium oxide.
The catalyst may comprise a composite metal oxide. Examples of the composite metal oxide include those composed of copper, ruthenium and oxygen; those composed of copper, sodium and oxygen; those composed of sodium, ruthenium and oxygen; those composed of copper, ruthenium, sodium and any other metals and oxygen; those composed of copper, any other metals and oxygen; and those composed of ruthenium, any other metals and oxygen; those composed of sodium and any other metals and oxygen. If the catalyst comprises the composite metal oxide, it may be supported on the support or any of the other components .
The catalyst preferably contains a support, such as a porous support and a non-porous support . One or both of a copper oxide and a ruthenium oxide are preferably supported on a support, more preferably supported on a porous support. Examples of the non-porous support include a non-porous support comprising Si02 such as CAB-O-SIL (registered trademark) . The catalyst containing a support is valuable for production of olefin oxides , which is one aspect of the present invention.
The porous support has pores capable of supporting one or both of a copper oxide and a ruthenium oxide . The porous support preferably comprises Al203, Si02, Ti02, or Zr02, more preferably Si02. Examples of the porous support comprising Si02 include mesoporous silica. Such porous supports may also comprise zeolites.
The support may be in form of powder, or shaped to a desired structure as necessary.
The catalyst preferably comprises one or more selected from the group consisting of an alkaline metal component and an alkaline earth metal component.
The alkaline metal component may be an alkaline metal-containing compound, and may be an alkaline metal ion. The alkaline earth metal component may be an alkaline earth metal-containing compound, and may be 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 . The alkaline metal component may be an alkaline metal oxide. Example of the alkaline metal oxide include Na20, Na202, K20, K02, K202, Rb20, Rb202, Cs20, Cs202, Cs02, Cs03 , Cs203, Csu03, Cs0 and Cs70. Examples of the alkaline metal ion include 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. The alkaline earth metal component may be an alkaline metal earth oxide. Examples of the alkaline earth metal oxide include CaO, Ca02, MgO, Mg02, SrO, Sr02, BaO and Ba02. Examples of the alkaline earth metal ion include Ca2+, Mg2+, Sr2+ and Ba2+.
The alkaline metal-containing compound is preferable, and a sodium- containing compound is more preferable.
The alkaline metal-containing compound is preferably an alkaline metal salt. The alkaline earth metal-containing compound is preferably an alkaline earth metal salt. The alkaline metal salt comprises the alkaline metal ion as mentioned above and an anion. The alkaline earth metal salt comprises the alkaline earth metal ion as mentioned above and an anion. Examples of anions in such salts include F" , CI", Br~ , I", OH", N03 ~, S04 2~, C03 2", HC03 " and S03 2" . Such salt is preferably an alkaline metal salt containing a halogen such as an alkaline metal halide, or an alkaline earth metal-containing salt containing a halogen such as an alkaline earth metal halide, and an alkaline metal salt containing a halogen is more preferable, and an alkaline metal chloride is still more preferable.
The alkaline metal component or the alkaline earth metal component may be supported on the support as mentioned above. The catalyst may contain a halogen component . The halogen component is generally a halogen- containing compound . Examples of the halogen include chlorine, fluorine, iodine and bromine.
Examples of the halogen-containing compound include halides of copper, ruthenium or any other metals of metal oxides and oxyhalides of copper, ruthenium or any other metals of metal oxides. If the catalyst comprises the halogen component, the component may be supported on the porous support as mentioned above .
When a copper oxide, and one or both of a ruthenium oxide and one metal oxide other than a copper oxide and a ruthenium oxide, and optionally any of the components are supported on a porous support in the catalyst, the total content of these components is preferably 0.01 to 80 parts by weight relative to 100 parts of support. When the total content falls within such a range, the olefin oxide yield and selectivity can be further improved. The lower limit of the total content is more preferably 0.05 part by weight, still more preferably 0.1 part by weight relative to 100 parts by weight of a support . The upper limit of the total content is more preferably 50 parts by weight, still more preferably 30 parts by weight relative to 100 parts by weight of a support .
When both of a copper oxide and a ruthenium oxide are included, the ruthenium/copper molar ratio in the catalyst is preferably 0.01/1 to 50/1 based on their atoms. When the 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 0.1/1, still more preferably 0.2/1 The upper limit of the molar ratio is more preferably 5/1, still more preferably 1/1. When a copper oxide and alkaline metal or alkaline earth metal are included, alkaline metal or alkaline earth metal/copper molar ratio in the catalyst is preferably 0.001/1 to 50/1 based on their atoms. When the 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 0.1/1. The upper limit of the molar ratio is more preferably 10/1, still more preferably 5/1.
When a copper oxide and other oxide except ruthenium oxide are included, the other component/copper molar ratio in the catalyst is preferably 0.001/1 to 50/1 based on their atoms. When the 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 10/1, still more preferably 5/1.
The catalyst can be produced according to the conventional methods.
When each of the metal oxides is supported on a support, the catalyst can be obtained by impregnating a support with a solution containing a copper ion and one or both of a ruthenium ion and other metal ion other than a copper ion and a ruthenium ion to prepare a composition, followed by calcining the composition .
If the catalyst comprises an alkaline metal or alkaline earth metal component or any other components as mentioned above, the catalyst can be obtained in the same procedure as mentioned above except that solution further contains an alkaline metal or alkaline earth metal-containing ion, a halogen ion or an metal ion of any other metal which forms any of the metal oxides as mentioned above .
The solution containing a copper ion and one of both of a ruthenium ion and one metal ion other than a copper ion and a ruthenium ion can be prepared by dissolving a copper metal salt and one or both of a ruthenium metal salt and one metal salt other than a copper metal salt and a ruthenium metal salt 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 nitrates, and copper chlorides. Examples of the ruthenium metal salt include, for example, a halide such as ruthenium bromide, ruthenium chloride , ruthenium iodide, an oxyhalide such as Ru2OCl4, Ru2OCl5 and Ru2OCi6, a halogeno complex such as [RuCl2 (H20) 4] CI , an ammine complex such as [Ru(NH3)5H20] Cl2, [Ru(NH3)5Cl] Cl2, [Ru (NH3 ) 6] Cl2 and [Ru (NH3 ) 6] Cl3 , a carbonyl complex such as Ru(CO)5 and Ru3(CO)i2, a carboxylate complex such as [Ru30 (OCOCH3 ) s (H20) 3] , ruthenium nitrosylchloride , and [Ru2 (OCOR) 4] CI (R=alkyl group having 1 to 3 carbon atoms), a nitrosyl complex such as [Ru (NH3 ) 5 (NO) ] Cl3 , [Ru(OH) (NH3)4(NO)] (N03)2 and [Ru(NO)] (N03)3, an amine complex, an acetylacetonate complex, and ammonium salt such as (NH4)2RuCl6.
Examples of the tellurium salt or compound include, for example, a halide such as TeFs, TeBr4, TeCl4 and Tel4 , an oxyhalide, oxide such as TeO, Te02 and Te03, an alkoxide such as Te(OC2H5)4, ammonium tellurate, a tellurate such as H2Te03, HsTe06, Na2Te03 and Na2Te0 , preferably halide and oxide, more preferably oxide, still more preferably Te02.
Examples of the manganese metal salt include manganese carbonate, manganese nitrate, manganese sulfate, manganese bromide, manganese chloride, manganese iodide, manganese perchlorate, manganese acetate, and manganese acetylacetonate .
Examples of the bismuth metal salt include bismuth carbonate, bismuth nitrate, bismuth sulfate, bismuth bromide, bismuth chloride, bismuth iodide, bismuth oxychloride and bismuth acetate.
Examples of the rhenium metal salt such as rhenium carbonyl, rhenium chloride, rhenium pentacarbonyl bromide, and rhenium pentacarbonyl chloride .
Examples of the chromium metal salt such as chromium nitrate, chromium bromide, chromium chloride, chromium perchlorate, chromium sulfate, chromium acetate, and chromium acetylacetonate .
Examples of the iron metal salt such as FeO(OH) , Fe(N03)3, FeS04, Fe2(S04)3, FeC204, Fel2, FeBr2, FeBr3 , FeCl2, FeCl3 , Fe(C104)2, Fe(C104)3, Fe(OC2H5)3 and C4HsFe04.
Examples of the molybdenum metal salt such as MoCl3, MoCl5, MoF6 , Mo ( CO) s and ( H4) 2Mo04.
Examples of the tungsten metal salt such as tungsten chloride, tungsten dichloride, tungsten dioxide, and tungsten ethoxide.
Examples of the selenium metal salt such as SeOCl2, HeSe03, Se2Cl2 and SeCl4.
Examples of the antimony metal salt such as antimony bromide, antimony chloride , antimony iodide, antimony ethoxide, and antimony acetate.
Examples of the vanadium metal salt such as VC13, VF3 , VF4, VBr3, VOS04, V0C13, VOC204 and V (CH3COCHCOCH3 ) 3.
Examples of the nickel metal salt such as nickel sulfate, nickel nitrate, nickel bromide, nickel chloride, nickel iodide, nickel perchlorate, nickel carbonate, nickel oxalate, and nickel hydroxide. Examples of the cobalt metal salt such as cobalt sulfate, cobalt nitrate, cobalt bromide, cobalt chloride, cobalt iodide, cobalt perchlorate, cobalt acetylacetonate , cobalt acetate, cobalt carbonate, cobalt carbonyl, and cobalt hydroxide.
Examples of the tin metal salt such as tin sulfate, tin bromide, tin chloride, tin iodide, tin acetylacetonate, tin acetate, tin methoxide , tin butoxide, tin ethoxide, tin oxalate and tin tartrate.
Examples of the niobium metal salt include NbCl5, F5Nb, Nbl5 and Nb(OC2H5)5.
Examples of the germanium metal salt such as germanium bromide, germanium chloride, germanium iodide, germanium isopropoxide , germanium ethoxide, and germanium methoxide.
Examples of the thallium metal salt such as thallium sulfate, thallium nitrate , thallium bromide , thallium chloride , thallium iodide, thallium acetate, thallium carbonate, and thallium oxalate.
Examples of the indium metal salt include halides such as InBr, InBr3 , InCl , InCl3, Inl, Inl3, InF3 , In(0H)3, In(OCH(CH3)2)3, In(N03)3, In(Cl04)3, In2(S04)3, and In (OOCCH3 ) 3.
Examples of the iridium metal salt includes IrBr3, IrBr4 , IrCl3, IrCl4 and Irl4.
Examples of the lanthanum metal salt include La(N03)3, La (OH) 3, La2(C03)3, La2(S04)3, LaBr3, LaCl3 , LaF3 , Lal3 , La(C104)3, La2(C204) 3, La(OC3H7)3 and La(C2H50)3,
Examples of the cerium metal salt include Ce(N03)3, Ce2(C03)3, Ce(S04)2, Ce2(S04)3, CeBr, CeCl3, CeF3, Cel2, Ce(Cl04)3, (CH3COO)3Ce and Ce3(C204) 3.
Examples of the osmium metal salts include osmium halides such as osmium chloride.
If the solvent contains an alkaline metal or alkaline earth metal ion, it can be prepared by adding an alkaline metal or alkaline earth metal salt to a solvent.
The alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the alkaline metal component or the alkaline earth metal component. Examples of 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 metal hydroxides, alkaline earth metal hydroxides, alkaline metal hypochlorites, alkaline earth metal hypochlorites, alkaline metal halates, alkaline earth metal halates, alkaline metal nitrites, alkaline earth metal nitrites, alkaline metal oxalates, alkaline earth metal oxalates, alkaline metal perhalates, alkaline earth metal perhalates, alkaline metal propionates, alkaline earth metal propionates, alkaline metal tartrates and alkaline earth metal tartrates, preferably alkaline metal halides and alkaline metal nitrates, more preferably NaN03 and NaCl . At least one of the metal salts for the solvent contains preferably a halogen ion, more preferably a chloride ion.
Such a halogen ion may form the alkaline metal or alkaline earth metal component such as NaCl and the haolgen component such as halides and oxyhalides of Cu or Ru. The solution may contain acidic or basic compounds in order to control its pH.
Examples of the solvent for the solution include water and alcohols such as methanol or ethanol .
The composition as prepared by the impregnation is usually dried, and the drying method thereof is not limited. The composition as prepared by the impregnation is preferably dried at a temperature of 40°C to 200°C before calcining the composition. Drying may be performed under an atmosphere of oxygen containing gas such as air or also under an inert gas atmosphere (for example, Ar, N2, 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.
The method of calcining the composition is not limited, and calcining the composition is preferably performed under a gas atmosphere containing oxygen. Examples of such a gas 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 gases and the compositions, however, a too high temperature may cause agglomeration of ruthenium oxide and copper oxide. Accordingly, the calcination temperature is typically 200°C to 800°C, preferably 400°C 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, tableting. The calcination is normally performed after shaping into the desired structures, but it can also be performed before shaping them. In the first step, the catalyst is contacted with water. The catalyst is preferably contacted with water and an an alkaline metal compound or an alkaline earth metal compound. The catalyst is also preferably contacted with water and an inorganic acid.
Examples of the alkaline metal compound include compounds containing an alkaline metal such as Na, K, Rb and Cs . Examples of the alkaline earth metal compound include compounds containing an alkaline earth metal such as Ca, Mg, Sr and Ba.
The alkaline metal compound or alkaline earth metal compound is preferably an alkaline metal compound, more preferably a sodium-containing compound or a potassium-containing compound, still more preferably a sodium-containing compound.
Examples of the alkaline metal compound and the alkaline earth metal compound 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 metal hydroxides, alkaline earth metal hydroxides, alkaline metal hypochlorites, alkaline earth metal hypochlorites, alkaline metal halates, alkaline earth metal halates, alkaline metal nitrites, alkaline earth metal nitrites, alkaline metal oxalates, alkaline earth metal oxalates, alkaline metal perhalates, alkaline earth metal perhalates, alkaline metal propionates, alkaline earth metal propionates, alkaline metal tartrates and alkaline earth metal tartrates . Among them, preferred are alkaline metal halides and alkaline metal nitrates, and more preferred are NaN03 and NaCl .
Examples of the inorganic acid include hydrogen chloride, hydrogen bromide , hydrogen fluoride, hydrogen iodide , sulfurous acid, sulfuric acid, phosphorous acid, phosphoric acid, borous acid, boric acid, nitrous acid and nitric acid. Among them, preferred are hydrogen chloride , sulfuric acid, phosphoric acid, boric acid and nitric acid, and more preferred is hydrogen chloride.
The amount of water used is not limited, and it is preferably 0.01 to 10000 parts by weight relative to 1 part of catalyst, more preferably 0.1 to 2000 parts by weight, and still more preferably 0.5 to 100 parts by weight relative to 1 part of catalyst.
The alkaline metal or alkaline earth metal/copper molar ratio in the catalyst is preferably 0.001/1 to 50/1 based on their atoms. When the alkaline metal or alkaline earth metal/copper molar ratio falls within such a range, the selectivity of the olefin oxide can be further improved. The lower limit of the alkaline metal or alkaline earth metal/copper molar ratio is more preferably 0.01/1, and still more preferably 0.1/1. The upper limit of the alkaline metal or alkaline earth metal/copper molar ratio is more preferably 10/1, and still more preferably 5/1.
The inorganic acid/copper molar ratio is usually 0.01 to 100, more preferably 0.05 to 90, and still more preferably 0.1 to 80. The contacting is usually carried out at a temperature from 0°C to 120°C, and preferably from 5°C to 100°C. The contacting time is not limited, and is usually 1 minute to 48 hours, and preferably 5 minutes to 24 hours.
The catalyst obtained by contacting is preferably dried to remove water . The mixture obtained by contacting may be dried as it is or may be dried after filtration. Herein, when the filtration is carried out, the mixture obtained after the filtration can be washed with water, or both of water and inorganic acid.
The drying method is not limited. The mixture obtained by contacting is preferably dried at a temperature of 15°C to 200°C before calcining the composition. Drying may be performed under an atmosphere of oxygen containing gas such as air or also under an inert gas atmosphere (for example, Ar, N2, He) at standard pressure or reduced pressure. A drying time is preferably in the range from 0.5 to 24 hours. The catalyst obtained can be calcined at a temperature from 200°C to 800°C, and preferably from 400°C to 600°C after contacting. The calcining time is usually 10 minutes to 48 hours, preferably 20 minutes to 24 hours, more preferably 30 minutes to 20 hours.
The method of calcining the catalyst is not limited, and the calcination of the catalyst is preferably performed under a gas atmosphere containing oxygen. Examples of such a gas 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. The second step is a step of reacting an olefin with oxygen in the presence of the catalyst obtained in the first step.
The olefin may have a linear or branched structure. The olefin usually contains 2 to 10 carbon atoms, and preferably contains 2 to 8 carbon atoms. Examples of the olefin include ethylene, propylene, butene, pentene, hexene, heptene, octene, and butadiene, ethylene, propylene and butane are preferable, and propylene is more preferable.
The reaction is generally performed in the gas phase. In the reaction, the olefin and oxygen may be fed in the form of a gas, respectively. 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, rare gases such as argon and helium, carbon dioxide, water vapor, methane, ethane and propane. Preferable diluent gases are nitrogen, carbon dioxide and the both thereof.
As the oxygen source, pure oxygen may be used, or a mixed gas containing pure oxygen and a gas inactive to the reaction, such as air, may be used. Examples of the gas inactive to the reaction include nitrogen, rare gases such as argon and helium, carbon dioxide, water vapor, methane, ethane and propane. Preferable gases inactive to the reaction are nitrogen, carbon dioxide and the both thereof. The amount of oxygen used varies depending on the reaction type, the kind of catalyst, the reaction temperature or the like. The amount of oxygen is typically 0.01 mole to 100 mole, and preferably 0.03 mole to 30 mole, and more preferably 0.05 mole to 10 mole, and especially preferably 0.25 mole to 10 mole, with respect to 1 mol of the olefin .
The reaction is usually performed at a temperature of 100°C to 350°C, preferably of 120°C to 330°C, and more preferably of 170°C to 310°C.
The reaction is usually carried out under reaction pressure in the range of reduced pressure to increased pressure . By carrying out the reaction under such a reaction pressure condition, the productivity and selectivity of olefin oxides can be improved. 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 reaction may be carried out as a batch reaction or a continuous reaction, preferably as a continuous 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. More than one reactor can be used. If the number of reactors is large, small reactors as for example microreactors , can be used, which can have multiple channels. Adiabatic type or heat exchange type may also be used.
In the second step, the olefin oxide can be produced. The olefin oxide may have a linear or branched structure . The olefin oxide usually contains 2 to 10 carbon atoms, and preferably contains 2 to 8 carbon atoms . Examples of the olefin oxides include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, and 3 , 4-epoxy-l-butene, and ethylene oxide, propylene oxide and butene oxide are preferable, and propylene oxide is more preferable .
The olefin oxide as obtained can be collected by a method known in the art such as separation by distillation.
The catalyst used in the above-mentioned reaction may be used in the above-mentioned first step. EXAMPLES
In Examples 1 and 2 and Comparative Examples 1 and 2, each measurement was performed according to the following method:
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) , C02, CO, propanal (PaL) and acrolein (AC) .
Propylene selectivities (SP0) were calculated using the following expression:
Spo = { [PO] / [PO+AC+AT+PaL+C02/3] } x 100%
Each metal weight was determined from the amounts of the metal salts used for preparation of catalyst.
Example 1
Amorphous silica powder (3.9 g; Si02, Japan Aerosil , 380 m2/g) was added to an aqueous solution mixture containing 0.43 g of (NH4)2R Cls (Alfa) , 0.60 g of Cu(N03)2 (Wako) , 0.20 gof NaCl (Wako) , 0.05 gof Te02 (Wako) and40gof H20. The obtained mixture was stirred for 24 hours in air, at room temperature. The resulting material was then heated at 100°C until dried, and calcined at 500°C for 12 hours in air to obtain the metal oxide composition having the following composition.
The molar ratio of Ru/Cu/Na/Te: 0.5/1/1.4/0.1 The total amount of Ru, Cu; Na and Te : 10.4 parts by weight relative to 100 parts by weight of Si02.
Then, 1.0 g of the metal oxide composition was contacted with 10 g of H20, and the resultant mixture was filtrated and washed with 2 L of H20. The solid obtained was dried at room temperature for 24h and calcined at 500°C for 2h to obtain the catalyst .
The catalyst was evaluated by using a fixed-bed reactor. Filling a 0.6 inch OD reaction tube made of quartz glass with 1 mL of the prepared catalyst, the reaction tube was supplied with 7.5 mL/min. of propylene, 15 mL/min. of the air, and 16.5 mL/min. of a nitrogen gas to carry out the reaction, at the reaction temperature of 250°C under atmospheric pressure. The feed ratio of propylene to oxygen was 2.4 (molar ratio, propylene/oxygen) . Gas hourly space velocity (GHSV) =2340 ( If 1 ) . The result of Example 1 is shown in Table 1.
Comparative Example 1
Amorphous silica powder (3.9 g; Si02, Japan Aerosil , 380 m2/g) was added to an aqueous solution mixture containing 0.43 g of (NH4)2RuCl6 (Alfa), 0.60 g of Cu(N03)2 ( Wako ) , 0.20 gof NaCl (Wako) , 0.05gof Te02 (Wako) and40gofH20. The obtained mixture was stirred for 24 hours in air, at room temperature. The resulting material was then heated at 100°C until dried, and calcined at 500°C for 12 hours in air to obtain the metal oxide composition having the following composition.
The molar ratio of Ru/Cu/Na/Te: 0.5/1/1.4/0.1
The total amount of Ru, Cu, Na and Te : 10.4 parts by weight relative to 100 parts by weight of Si02.
The catalyst was evaluated in the same manners as Example
1 and the result of Comparative Example 1 is shown in Table 1. Table 1
Figure imgf000023_0001
Example 2
Amorphous silica powder (1.9 g; Si02, Japan Aerosil, 380 m2/g) was added to an aqueous solution mixture containing 0.55 g of (NH4)2RuCl6 (Alfa), 0.30 g of Cu(N03)2 (Wako) and 40 g of H20. The obtained mixture was stirred for 24 hours in air at 25°C.
The resulting material was then heated at 100°C until dried, and calcined at 500°C for 12 hours in air to obtain the metal oxide composition.
Two point two (2.2) g of the metal oxide composition and 0.1 g of NaCl (Wako) was added to 5 g of H20 and mixed them at 25°C for 24 hours . Then, the obtained mixture was heated at 100°C until dried followed by calcining at 500°C for 12 hours in air to obtain the catalyst having the following composition.
The molar ratio of Ru/Cu/Na: 1.3/1/1.4
The total amount of Ru, Cu, Na: 14.3 parts by weight relative to 100 parts by weight of Si02.
The catalyst was evaluated in the same manners as Example
1 except the reaction temperature of 270°C and the result is shown in Table 2.
Comparative Example 2
Amorphous silica powder (1.9 g; Si02, Japan Aerosil , 380 m2/g) was added to an aqueous solution mixture containing 0.55 g of (NH4)2RuCl6 (Alfa), 0.30 g of Cu (N03) 2 (Wako), 0.10 gof NaCl (Wako) and 40g of H20. The obtained mixture was stirred for 24 hours in air, at 25°C. The resulting material was then heated at 100°C until dried, and calcined at 500°C for 12 hours in air to obtain the catalyst having the following composition.
The molar ratio of Ru/Cu/Na: 1.3/1/1.4.
The total amount of Ru, Cu and Na: 14.3 parts by weight relative to 100 parts by weight of Si02.
The catalyst was evaluated in the same manners as Example 1 except the reaction temperature of 270°C and the result is shown in Table 2.
Table 2
Figure imgf000024_0001
Example 3
Amorphous silica powder (44mg; Si02, Alfa, 85-115 m2/g) was added to an aqueous solution mixture containing 3.6 mg of (NH4)2RuCl6 (Aldrich) , 1.8 mg of Cu(N03)2 (Alfa), 0.90mg of NaCl (Alfa) and 950 mg of H20. The obtained mixture was stirred for 1 hour in air, at room temperature.
The resulting material was then heated at 165°C until dried, and calcined at 480°C for 6 hours in air to obtain the metal oxide composition having the following composition.
The molar ratio of Ru/Cu/Na: 1.3/1/1.4.
The total amount of Ru, Cu and Na: 14.3 parts by weight relative to 100 parts by weight of Si02.
Next, 10 mg of the metal oxide composition was added to
400 pL of 1.0 M HC1 (Ru/Cu/Na/HCl=l .3/1/1.4/71 molar ratio), and stirred at room temperature for 1 hour. The slurry was dried at 165°C, and calcined at 480°C for 2hours . The catalyst was evaluated by using a micro-reactor. The catalyst (5.0 mg) was placed in a well of a reactor as mentioned in Angew. Chem. Int. Ed. 38 (1999) 2794, equipped with array microreactors , wells along each reactor channel and a passivated 200 micron ID capillary sampling probe within the reactor channel . The mixture gas consisting of 1 vol% propylene (C3H6) , 4 vol% 02, and 95 vol% He was fed to the well at a gas hourly space velocity (GSHV) of 20,000 h"1 with a mass flow controller (MKS , Andover, MA) , at a reactor temperature of 250°C. Gas sampling was accomplished by withdrawing reactor exit gases using the passivated 200 micron ID capillary sampling probe. The data analysis was conducted by an on-line Micro-Gas Chromatograph (Varian, CP-4900) equipped with a thermal conductivity detector (TCD) , PoraPLOT U (10M) and Molecular sieve 13X (10M) .
The detected products were propylene oxide (PO) , acetone
(AT) , C02, CO, and propanal (PaL) and acrolein (AC) .
PO selectivities (SP0) were then calculated using the following expression:
Spo = { [PO] / [PO+AC+AT+PaL+C02/3] } x 100%
Each metal weight was determined from the amounts of the metal salts used for preparation of catalyst.
The result is shown in Table 3.
Comparative Example 3
Amorphous silica powder (44 mg; Si02, Alfa, 85-115 m2/g) was added to an aqueous solution mixture containing 3.6 mg of (NH4)2RuCl6 (Aldrich) , 1.8 mg of Cu(N03)2 (Alfa) , 0.90 mg of NaCl (Alfa) and 950 mg of H20. The obtained mixture was stirred for
1 hour in air, at room temperature.
The resulting material was then heated at 100°C until dried, and calcined at 480°C for 6 hours in air to obtain the metal oxide composition having the following composition. The molar ratio of Ru/Cu/Na: 1.3/1/1.4.
The total amount of Ru, Cu and Na: 14.3 parts by weight relative to 100 parts by weight of Si02.
The catalyst was evaluated in the same manner as Example 3, and the result is shown in Table 3.
Table 3
Figure imgf000026_0001
Example 4
The catalyst prepared in Comparative Example 3 was evaluated for 12 hours in the same condition as Example 3. Then, 10 mg of the used catalyst in the above-mentioned evaluation was added to 400 L of 1.0 M HCl (Ru/Cu/Na/HCl=l .3/1/1.4/71 molar ratio) , and stirred at room temperature for 1 hour. The slurry was dried at 165°C, and calcined at 480°C for 2 hours.
The catalyst was evaluated in the same manner as Example 3, and the result is shown in Table 4.
Table 4
Figure imgf000026_0002

Claims

WHAT WE CLAIM ARE:
1. A process for producing an olefin oxide comprising: a first step of contacting a catalyst comprising a copper oxide, and one or both of ruthenium oxide and one metal oxide other than a copper oxide and a ruthenium oxide, with water and a second step of reacting an olefin with oxygen in the presence of the catalyst obtained in the first step.
2. The process according to claim 1, wherein the catalyst is contacted with water and an alkaline metal compound or an alkaline earth metal compound.
3. The process according to claim 1, wherein the catalyst is contacted with water and an inorganic acid.
4. The process according to claim 1, wherein the first step further comprises calcining the catalyst at a temperature from 350°C to 650°C after contacting.
5. The process according to claim 1, wherein the catalyst comprises a copper oxide and a ruthenium oxide.
6. The process according to claim 1, wherein the catalyst further comprises an alkaline metal component or an alkaline earth metal component.
7. The process according to claim 1, wherein the catalyst further comprises a halogen component.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7348444B2 (en) * 2003-04-07 2008-03-25 Shell Oil Company Process for the production of an olefin oxide
US7507845B1 (en) * 2007-08-27 2009-03-24 Sd Lizenzverwertungsgesellschaft Mbh & Co Kg Process for production of an olefin oxide
US20110152547A1 (en) * 2009-12-17 2011-06-23 Sumitomo Chemical Company, Limited Process for producing olefin oxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7348444B2 (en) * 2003-04-07 2008-03-25 Shell Oil Company Process for the production of an olefin oxide
US7507845B1 (en) * 2007-08-27 2009-03-24 Sd Lizenzverwertungsgesellschaft Mbh & Co Kg Process for production of an olefin oxide
US20110152547A1 (en) * 2009-12-17 2011-06-23 Sumitomo Chemical Company, Limited Process for producing olefin oxide

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