WO2012094120A1 - Process for producing olefin oxide - Google Patents

Process for producing olefin oxide Download PDF

Info

Publication number
WO2012094120A1
WO2012094120A1 PCT/US2011/065159 US2011065159W WO2012094120A1 WO 2012094120 A1 WO2012094120 A1 WO 2012094120A1 US 2011065159 W US2011065159 W US 2011065159W WO 2012094120 A1 WO2012094120 A1 WO 2012094120A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
oxide
alkaline
catalyst
alkaline earth
Prior art date
Application number
PCT/US2011/065159
Other languages
French (fr)
Inventor
Yoshihiko Ohishi
Anusorn Seubsai
Selim Senkan
Original Assignee
Sumitomo Chemical Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Publication of WO2012094120A1 publication Critical patent/WO2012094120A1/en

Links

Classifications

    • 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
    • B01J21/08—Silica
    • 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
    • B01J23/70—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
    • B01J23/8966—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 germanium, tin or lead
    • 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
    • B01J23/8986—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
    • 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
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0573—Selenium; Compounds 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
    • 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
    • B01J35/615—
    • 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

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, an alkaline metal or alkaline earth metal component and a metal component deriving from one selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
  • a catalyst for production of an olefin oxide which comprises a copper oxide, a ruthenium oxide, an alkaline metal or alkaline earth metal component and a metal component deriving from one element selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
  • 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, a metal component and an alkaline metal or alkaline earth metal component.
  • the copper oxide, the ruthenium oxide and the metal copmonent 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, the metal component and an alkaline metal or alkaline earth metal component.
  • the porous support comprises preferably AI2O3, S1O2, T1O2, or ZrC>2, more preferably S1O 2 .
  • Examples of the porous support comprising S1O 2 include mesoporous silica.
  • Such a porous support 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 stucture.
  • olefin oxides can be prepared with good yield and good selectivity.
  • the catalyst comprises one or more kinds of the copper oxide .
  • 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 R.U2O4, R.U2O5, R.U3O5, R.U3O6, RuC>4, and RuC>2.
  • 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 metal selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Snand b.
  • the metal oxide include a metal oxide composed of oxygen and the metal selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
  • the metal oxide composed of an oxygen atom and bismuth includes bismuth oxides such as BiO, BiC> 2 , Bi 2 0 and ⁇ 2 ⁇ 3 .
  • the metal oxide composed of an oxygen atom and rhenium includes rheniun oxides such as ReC> 2 , ReC>3 and Re 2 0 7 , preferably Re0 2 or Re0 3 .
  • the metal oxide composed of an oxygen atom and chromium includes chromiun oxides such as CrC>3, and Cr 2 C>3, preferably Cr 2 0 3 .
  • the metal oxide composed of an oxygen atom and iron includes iron oxides such as FeO, Fe 2 C>3 and Fe 3 C> , preferably Fe 2 0 3 .
  • the metal oxide composed of an oxygen atom and molybdenum includes molybdenum oxide such as M0O 2 or M0O 3 .
  • the metal oxide composed of an oxygen atom and tungsten includes tungsten oxide such as W 3 0, Wi 7 0 47 , W5O14, W0 2 and W0 3 , preferably WO 2 and WO 3 .
  • the metal oxide composed of an oxygen atom and selenium includes selenium oxide such as Se0 3 and Se0 3 , preferably Se0 3 .
  • the metal oxide composed of an oxygen atom and antimony includes antimony oxides such as Sb0 2 , Sb 2 0 3 , Sb 2 0 4 and Sb 2 0 5 , preferably Sb0 2 or Sb 2 0 3 .
  • the metal oxide composed of an oxygen atom and vanadium includes vanadium oxide such as VO, V0 2 , V 2 0 3 , V 6 0i 3 and V 2 Os, preferably V 2 Os.
  • the metal oxide composed of an oxygen atom and nickel includes nickel oxide such as NiO.
  • the metal oxide composed of an oxygen atom and cobalt includes tin oxide such as CoO, Co 3 0 4 and Co 2 0 3 , preferably Co 3 0 4 .
  • the metal oxide composed of an oxygen atom and tin includes tin oxide such as Sn0 2 , SnO, Sn 2 0 3 and Sn 3 0 4 , preferably Sn0 2 , SnO.
  • the metal oxide composed of an oxygen atom and cerium includes cerium oxide such as NbO, Nb0 2 and Nb 2 Os.
  • the metal component preferably includes a metal oxide, specifically bismuth oxide, rhenium oxide, chromium oxide, iron oxide, tungsten oxide, selenium oxide, antimony oxide, vanadium oxide, nickel oxide, cobalt oxide and tin oxide, more preferably bismuth oxide, rhenium oxide, antimony oxide, nickel oxide and tin oxide, and still more preferably bismuth oxide, antimony oxide and tin oxide.
  • a metal oxide specifically bismuth oxide, rhenium oxide, chromium oxide, iron oxide, tungsten oxide, selenium oxide, antimony oxide, vanadium oxide, nickel oxide, cobalt oxide and tin oxide, more preferably bismuth oxide, rhenium oxide, antimony oxide, nickel oxide and tin oxide, and still more preferably bismuth oxide, antimony oxide and tin oxide.
  • the metal ion may form a metal-containing salt comprising the metal ion and a halogen ion.
  • the metal component derives from preferably any one selected from the group consisting of Bi, Re, Cr, Fe, W, Se, Sb, V, Co, Ni and Sn, more preferably any one selected from the group consisting of Bi, Re, Sb, Co, Ni and Sn, still more preferably any one selected from the group consisting of Bi, Sb and Sn.
  • the catalyst comprises 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 .
  • the alkaline metal oxide include a 2 0, Na 2 C> 2 , K 2 0, K2O2, Rb20, Rb2C>2, CS2O, andCs2C>2.
  • the alkaline earth metal component may be alkaline earth metal oxide. Examples of the alkaline earth metal oxide include CaO, CaC>2, MgO, MgC>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 comprises the alkaline metal ion as mentioned above with an anion.
  • the alkaline earth metal salt comprises the alkaline earth metal ion as mentioned above with an anion. Examples of anions in such salts include Cl ⁇ , Br " , I ⁇ , F ⁇ , OH ⁇ , 03 ⁇ , S0 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, R.UO 2 and a metal component deriving from Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb and an alkaline metal-containing compound; more preferably CuO, RuC> 2 , a metal component deriving from Bi, Re, Sb, Co, Ni and Sn and an alkaline metal-containing compound; still more preferably CuO, RUO 2 , a metal component deriving from Bi, Sb and Sn 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 total content of those is preferably 0.01 to 80 weight parts relative to 100 weight parts of a porous support.
  • 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 other components or on the porous support as mentioned above .
  • halogen-containing compound examples include copper halides such as CuCl and CUCI 2 , ruthenium halides such as R.UCI3 and copper oxyhalides such as CUOCI 2 , CUCIO 4 ,
  • 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 copper, ruthenium, sodium and any one selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
  • the component may be supported on the porous support or any of the other components as mentioned above.
  • 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 or suspension containing a copper ion, a ruthenium ion and a metal compound or ion, and an alkaline metal or alkaline earth metal-containing ion to prepare a composition, followed by calcining the composition, said metal compound or ion deriving from one metal selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
  • Such metal ion includes Bi cations, Re cations, Cr cations, Fe cations, Mo cations, W cations, Se cations, Sb cations, V cations, Ni cations, Co cations, Sn cations and Nb cations.
  • the 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 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 ion, an alkaline metal or alkaline earth metal-containing compound or ion and a halogen ion.
  • metal-containing ion and the above-mentioned metal compound or ion can be prepared by mixing a copper metal salt, a ruthenium metal salt, a metal conatining salt as mentioned below and an alkaline metal or alkaline earth metal-containing 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 oxide, copper nitrates, and copper chlorides, and copper nitrates and copper chlorides are preferable .
  • Examples of the metal-containing salt include the following ones.
  • Bismuth metal salt such as 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 (S04) 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 6 Fe0 4 .
  • Molybdenum metal salt such as MoCl 3 , MoCl 5 , MoF 6 , Mo (CO) 6 and (NH 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 , H 2 Se0 3 , Se 2 Cl 2 and
  • 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 include NbCls, FsNb, Nbls and
  • 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 for the solution examples include water and 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.
  • 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, 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 stucture 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 ruthenium component and copper component. 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, 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 a monoolefin or a diolefin .
  • the monoolefin include ethylene, propylene, butene, pentene, hexane, 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. 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.
  • 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.
  • the 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 .
  • Examples of the olefin oxides 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 (SiC> 2 , Japan Aerosil, 380 m 2 /g) was added to an aqueous solution mixture containing 0.54 g of (NH ) 2 RuCl6 (Aldrich) , 0.30 g of Cu(N0 3 ) 2 (Wako) , 0.12 g of BiCl 3 (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, 16.5mL/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 0.05 g of ReCls (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
  • Example 3
  • Catalysts were prepared in the same manner as Example 1 except that 0.4 g of CrCl 3 (Wako) was used instead of BiCl 3 .
  • 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 0.38 g of FeCl3 (Wako) was used instead of BiCl3. 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 0.17 g of M0CI 3 (Wako) was used instead of BiCl 3 .
  • 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 WCI 4 (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
  • Example 7
  • Catalysts were prepared in the same manner as Example 1 except that 0.23 g of SeCl (Wako) was used instead of BiCl 3 .
  • 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 0.02 g of SbCl3 (Wako) was used instead of BiCl3. 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 0.02 g of VCI 3 (Wako) was used instead of BiCl 3 .
  • 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 0.02 g of iCl 2 (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
  • Example 11
  • Catalysts were prepared in the same manner as Example 1 except that 0.02 g of SnCl 2 (Wako) was used instead of BiCl 3 .
  • 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 0.06 g of NbCls (Wako) was used instead of BiCl3. 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 0.02 g of C0CI 2 (Wako) was used instead of BiCl 3 .
  • 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 (SiC> 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) 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.

Abstract

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, an alkaline metal or alkaline earth metal component and a metal component deriving from one selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb.

Description

DESCRIPTION
PROCESS FOR PRODUCING OLEFIN OXIDE
CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of
U.S. Provisional Application No. 61/430,002, filed January 5, 2011, incorporated by reference herein in its entirely.
FIELD OF THE INVENTION
The present invention relates to a process for producing an olefin oxide.
BACKGROUND ART
As to a process for producicng olefin oxides, olefin epoxidation in the presence of a metal-based catalyst has been proposed .
SUMMARY OF THE INVENTION
The present invention provides:
[1] 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, an alkaline metal or alkaline earth metal component and a metal component deriving from one selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
[2] The process according to [1], wherein the catalyst comprises a halogen component.
[3] The process according to [1] or [2], wherein the copper oxide, the ruthenium oxide, the metal component and the alkaline metal or alkaline earth metal component are supported on a porous support.
[4] The process according to [2], wherein the copper oxide, the ruthenium oxide, the metal component, the alkaline metal or alkaline earth metal component and the halogen component are supported on a porous support.
[5] The process according to [3] or [4], wherein the porous support comprises AI2O3, S1O2, T1O2 or ZrC>2.
[6] The process according to any one of [1] to [5], wherein the ruthenium/copper molar ratio in the catalyst is 0.01/1 to 50/1.
[7] The process according to any one of [1] to [6], wherein the molar ratio of the one selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb/copper in the catalyst is 0.001/1 to 50/1.
[8] The process according to any one of [1] to [7], wherein the molar ratio of alkaline metal or alkaline earth metal/copper in the catalyst is 0.001/1 to 50/1.
[9] The process according to any one of [1] to [8], wherein the copper oxide is CuO.
[10] The process according to any one of [1] to [9], wherein the ruthenium oxide is RuC>2.
[11] The process according to any one of [1] to [10], wherein the metal component derives from Bi, Re, Sb, Ni, Co, or Sn.
[12] The process according to any one of [1] to [11], wherein the alkaline metal or alkaline earth metal component is an alkaline metal-containing compound.
[13] The process according to [12], wherein the alkaline metal-containing compound is a sodium-containing compound.
[14] The process according to any one of [3] to [5], wherein the total amount of the copper oxide, the ruthenium oxide and the metal component is 0.01 to 80 weight parts relative to 100 weight parts of a porous support.
[15] The process according to any one of [3] to [5], wherein the catalyst is obtained by impregnating a porous support with a solution or a suspension containing a copper ion, a ruthenium ion, an alkaline metal or alkaline earth metal ion and a metal compound or ion to prepare a composition, followed by calcining the composition, said metal compound or ion deriving from one selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
[16] The process according to any one of [1] to [15], wherein the olefin is propylene and the olefin oxide is propylene oxide.
[17] The process according to any one of [1] to [16], which comprises reacting an olefin with oxygen at a temperature of 100 to 350°C.
[18] A catalyst for production of an olefin oxide which comprises a copper oxide, a ruthenium oxide, an alkaline metal or alkaline earth metal component and a metal component deriving from one element selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
[19] The catalyst according to [18] , which comprises a halogen component .
[20] The catalyst according to [18] or [19], wherein the copper oxide, the ruthenium oxide, the metal component and the alkaline metal or alkaline earth metal component are supported on a porous support.
[21] The catalyst according to [19] , wherein the copper oxide, the ruthenium oxide, the metal component, the alkaline metal or alkaline earth metal component and the halogen component are supported on a porous support.
[22] The catalyst according to [20] or [21] which is obtained by impregnating a porous support with a solution or a suspension containing a copper ion, a ruthenium ion, an alkaline metal or alkaline earth metal ion and a metal compound or ion to prepare a composition, followed by calcining the composition, said metal compound or ion deriving from one selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb. [23] The catalyst according to any one of [18] to [22] , wherein the copper oxide is CuO.
[24] The catalyst according to any one of [18] to [23] , wherein the ruthenium oxide is Ru02.
[25] The catalyst according to any one of [18] to [24] , wherein the metal component derives from Bi, Re, Sb, Ni, Co or Sn.
[26] The catalyst according to any one of [18] to [25] , wherein the alkaline metal or alkaline earth metal component is an alkaline metal-containing compound.
[27] The catalyst according to [20] or [21], wherein the porous support comprises A1203, Si02, Ti02 or Zr02.
[28] The catalyst according to any one of [18] to [27] , wherein the olefin oxide is propylene oxide. DETAILED DESCRIPTION OF THE INVENTION
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, a metal component and an alkaline metal or alkaline earth metal component.
In the catalyst, the copper oxide, the ruthenium oxide and the metal copmonent 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, the metal component and an alkaline metal or alkaline earth metal component. The porous support comprises preferably AI2O3, S1O2, T1O2, or ZrC>2, more preferably S1O2. Examples of the porous support comprising S1O2 include mesoporous silica. Such a porous support may also comprise zeolites.
Examples of the non-porous support include a non-porous support comprising S1O2 such as CAB-O-SIL (registered trademark) .
The support may be in form of powder or may be shaped to a desired stucture.
If the catalyst comprises S1O2 as a support, olefin oxides can be prepared with good yield and good selectivity.
The catalyst comprises one or more kinds of the copper oxide .
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 R.U2O4, R.U2O5, R.U3O5, R.U3O6, RuC>4, and RuC>2. The ruthenium oxide is preferably Ru02. The catalyst comprises one or more kinds of the metal components. Here, the metal component includes a metal element or ion and a metal oxide, each of which derives from one metal selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Snand b. Examples of the metal oxide include a metal oxide composed of oxygen and the metal selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
The metal oxide composed of an oxygen atom and bismuth includes bismuth oxides such as BiO, BiC>2, Bi20 and Βΐ2θ3.
The metal oxide composed of an oxygen atom and rhenium includes rheniun oxides such as ReC>2, ReC>3 and Re207, preferably Re02 or Re03.
The metal oxide composed of an oxygen atom and chromium includes chromiun oxides such as CrC>3, and Cr2C>3, preferably Cr203.
The metal oxide composed of an oxygen atom and iron includes iron oxides such as FeO, Fe2C>3 and Fe3C> , preferably Fe203.
The metal oxide composed of an oxygen atom and molybdenum includes molybdenum oxide such as M0O2 or M0O3.
The metal oxide composed of an oxygen atom and tungsten includes tungsten oxide such as W30, Wi7047, W5O14, W02 and W03, preferably WO2 and WO3.
The metal oxide composed of an oxygen atom and selenium includes selenium oxide such as Se03 and Se03, preferably Se03.
The metal oxide composed of an oxygen atom and antimony includes antimony oxides such as Sb02, Sb203, Sb204 and Sb205, preferably Sb02 or Sb203.
The metal oxide composed of an oxygen atom and vanadium includes vanadium oxide such as VO, V02, V203, V60i3 and V2Os, preferably V2Os.
The metal oxide composed of an oxygen atom and nickel includes nickel oxide such as NiO.
The metal oxide composed of an oxygen atom and cobalt includes tin oxide such as CoO, Co304 and Co203, preferably Co304.
The metal oxide composed of an oxygen atom and tin includes tin oxide such as Sn02, SnO, Sn203 and Sn304, preferably Sn02, SnO.
The metal oxide composed of an oxygen atom and cerium includes cerium oxide such as NbO, Nb02 and Nb2Os.
The metal component preferably includes a metal oxide, specifically bismuth oxide, rhenium oxide, chromium oxide, iron oxide, tungsten oxide, selenium oxide, antimony oxide, vanadium oxide, nickel oxide, cobalt oxide and tin oxide, more preferably bismuth oxide, rhenium oxide, antimony oxide, nickel oxide and tin oxide, and still more preferably bismuth oxide, antimony oxide and tin oxide.
The metal ion may form a metal-containing salt comprising the metal ion and a halogen ion. The metal component derives from preferably any one selected from the group consisting of Bi, Re, Cr, Fe, W, Se, Sb, V, Co, Ni and Sn, more preferably any one selected from the group consisting of Bi, Re, Sb, Co, Ni and Sn, still more preferably any one selected from the group consisting of Bi, Sb and Sn.
The catalyst comprises 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 Ca2+, Mg2+, Sr2+ and Ba2+.
The alkaline metal component may be an alkaline metal oxide . Examples of the alkaline metal oxide include a20, Na2C>2, K20, K2O2, Rb20, Rb2C>2, CS2O, andCs2C>2. The alkaline earth metal component may be alkaline earth metal oxide. Examples of the alkaline earth metal oxide include CaO, CaC>2, MgO, MgC>2, SrO, Sr02, BaO and Ba02. 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 comprises the alkaline metal ion as mentioned above with an anion. The alkaline earth metal salt comprises the alkaline earth metal ion as mentioned above with an anion. Examples of anions in such salts include Cl~, Br", I~, F~, OH~, 03~, S02~ and C03 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, R.UO2 and a metal component deriving from Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb and an alkaline metal-containing compound; more preferably CuO, RuC>2, a metal component deriving from Bi, Re, Sb, Co, Ni and Sn and an alkaline metal-containing compound; still more preferably CuO, RUO2, a metal component deriving from Bi, Sb and Sn 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.
Particularly if 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 molar ratio of [the metal of the metal
component/copper] in the catalyst is preferably 0.001/1 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 0.01/1, still more preferably 0.05/1. The upper limit of the molar ratio is more preferably 20/1, still more preferably 5/1.
The molar ratio of alkaline or alkaline earth
metal/copper 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 0.05/1, still more preferably 0.1/1. The upper limit of the molar ratio is more preferably 20/1, still more preferably 10/1.
When the copper oxide, the ruthenium oxide, the metal component and the alkaline or alkaline earth metal component is supported on a porous support in the catalyst, the total content of those is preferably 0.01 to 80 weight parts relative to 100 weight parts of a porous 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 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.
Examples of the halogen include chlorine, fluorine, iodine and bromine .
Examples of such a halogen-containing compound 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 other components or on the porous support as mentioned above .
Examples of such a halogen-containing compound include copper halides such as CuCl and CUCI2, ruthenium halides such as R.UCI3 and copper oxyhalides such as CUOCI2, CUCIO4,
CIO2CU (CIO4) 3 and CU2O (010 )2, ruthenium oxyhalides such as Ru2OCl4, Ru2OCl5 and Ru2OCl6.
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 copper, ruthenium, sodium and any one selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
If the catalyst comprises the composite oxide, the component may be supported on the porous support or any of the other components as mentioned above.
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.
When the copper oxide, the ruthenium oxide and the metal component are supported on a porous support in the catalyst, the catalyst can be obtained by impregnating a porous support with a solution or suspension containing a copper ion, a ruthenium ion and a metal compound or ion, and an alkaline metal or alkaline earth metal-containing ion to prepare a composition, followed by calcining the composition, said metal compound or ion deriving from one metal selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb . Such metal ion includes Bi cations, Re cations, Cr cations, Fe cations, Mo cations, W cations, Se cations, Sb cations, V cations, Ni cations, Co cations, Sn cations and Nb cations. The 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.
If the alkaline metal or alkaline earth metal component is an alkaline metal salt with a halogen or alkaline earth metal salt with a halogen, 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 ion, an alkaline metal or alkaline earth metal-containing compound or ion and a halogen ion.
The solution or suspension containing a copper ion, a ruthenium ion, an alkaline metal or alkaline earth
metal-containing ion and the above-mentioned metal compound or ion can be prepared by mixing a copper metal salt, a ruthenium metal salt, a metal conatining salt as mentioned below and an alkaline metal or alkaline earth metal-containing 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 oxide, copper nitrates, and copper chlorides, and copper nitrates and copper chlorides are preferable .
Examples of the ruthenium metal salt include, for example, a halide such as ruthenium bromide, ruthenium chloride, ruthenium iodide, an oxyhalide such as R.U2OCI4, R.U2OCI5 and R.U2OC16, a halogeno complex such as [RuCl2 (H20) 4 ] CI , an ammine complex such as [Ru (NH3) 5H20] Cl2, [Ru (NH3) 5C1 ] Cl2, [Ru (NH3) 6] Cl2 and [Ru (NH3) β] CI3, a carbonyl complex such as Ru(CO)s and Ru3(CO)i2, a carboxylate complex such as [Ru30 (OCOCH3) 6 (H20) 3] , ruthenium nitrosylchloride, and [Ru2 (OCOR) ] 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, an oxide such as Ru02, and ammonium salt such as (NH4)2RuCl6, and ruthenium salt containing CI is preferable.
Examples of the metal-containing salt include the following ones.
Bismuth metal salt such as 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 (N03) 3, FeS04, Fe2 (S04) 3, FeC204, Fel2, FeBr2, FeBr3, FeCl2, FeCl3, Fe(C104)2, Fe(C104)3, Fe(OC2H5)3 and C4H6Fe04.
Molybdenum metal salt such as MoCl3, MoCl5, MoF6, Mo (CO) 6 and (NH4)2Mo04.
Tungsten metal salt such as tungsten chloride, tungsten dichloride, tungsten dioxide, and tungsten ethoxide.
Selenium metal salt such as SeOCl2, H2Se03, Se2Cl2 and
SeCl4.
Antimony metal salt such as antimony bromide, antimony chloride, antimony iodide, antimony ethoxide, and antimony acetate .
Vanadium metal salt such as VC13, VF3, VF4, VBr3, VOS04, V0C13, VOC204 and V (CH3COCHCOCH3) 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 include NbCls, FsNb, Nbls and
Nb(OC2H5)5.
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. 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, and alkaline metal halides and alkaline metal nitrates are preferable, and a 03 and NaCl are more preferable.
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. Such 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.
Examples of the solvent for the solution include water and 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, 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 stucture 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. 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 gas and the composition, however, a too high temperature may cause agglomeration of ruthenium component and copper component. 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, tableting. The calcination is normally performed after shaping into the desired structures, but it can also be performed before shaping them.
Next, the following explains a reaction of an olefin with oxygen in the presence of the catalyst as described above.
In the present invention, 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 a monoolefin or a diolefin . Examples of the monoolefin include ethylene, propylene, butene, pentene, hexane, heptene, octene, nonene, and decene. Examples of the diene include butadiene such as 1 , 3-butadiene or 1 , 2-butadiene . Examples of the olefin 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. In the reaction, 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.
As the 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 . 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 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. 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.
When a fixed bed reactor is used, 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.
Generally, the 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. When adiabatic type reactor is used, a part of the reaction mixture from the reactor can be recycled into the reactor after heat-exchanging to control the reaction temperature.
When two or more reactors are used, the reactors can be arranged in series and/or in parallel. When two or more reactors arranged in series are used, a heat exchanger can be used between the reactors for controling reaction temperature.
In the present invention, 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 . Examples of the olefin oxides 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. EXAMPLES
In Examples 1 to 13 and Comparative Example 1, 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) , acetaldehyde (AD) , COx (C02 and CO) , and propanal (PaL) and acrolein (AC) .
Propylene conversions (XPR) were determined from the following :
XPR = { [PO+AC+AT+PaL+C02/3] out / [C3H6] ml x 100%; and PO selectivities (SPo) were then calculated using the following expression:
SPO = { [PO] / [PO+AC+AT+PaL+C02/3] } 100% Each metal weight was determined from the amounts of the metal salts used for preparation of catalyst. Example 1
The metal compostion was prepared by a co-impregnation method. A predetermined weight (1.9 g) of an amorphous silica powder (SiC>2, Japan Aerosil, 380 m2/g) was added to an aqueous solution mixture containing 0.54 g of (NH )2RuCl6 (Aldrich) , 0.30 g of Cu(N03)2 (Wako) , 0.12 g of BiCl3 (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, 16.5mL/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. Example 2
Catalysts were prepared in the same manner as Example 1 except that 0.05 g of ReCls (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1. Example 3
Catalysts were prepared in the same manner as Example 1 except that 0.4 g of CrCl3 (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
Example 4
Catalysts were prepared in the same manner as Example 1 except that 0.38 g of FeCl3 (Wako) was used instead of BiCl3. 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 0.17 g of M0CI3 (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
Example 6
Catalysts were prepared in the same manner as Example 1 except that 0.03 g of WCI4 (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1. Example 7
Catalysts were prepared in the same manner as Example 1 except that 0.23 g of SeCl (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
Example 8
Catalysts were prepared in the same manner as Example 1 except that 0.02 g of SbCl3 (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
Example 9
Catalysts were prepared in the same manner as Example 1 except that 0.02 g of VCI3 (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
Example 10
Catalysts were prepared in the same manner as Example 1 except that 0.02 g of iCl2 (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1. Example 11
Catalysts were prepared in the same manner as Example 1 except that 0.02 g of SnCl2 (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
Example 12
Catalysts were prepared in the same manner as Example 1 except that 0.06 g of NbCls (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
Example 13
Catalysts were prepared in the same manner as Example 1 except that 0.02 g of C0CI2 (Wako) was used instead of BiCl3. The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.
Comparative Example 1
The metal compostion was prepared by a co-impregnation method. A predetermined weight (1.9 g) of an amorphous silica powder (SiC>2, Japan Aerosil, 380 m2/g) was added to an aqueous solution mixture containing 0.54 g of (NH4)2RuCl6 (Aldrich) , 0.30 g of Cu(N03)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.
The results of Examples 1 to 13 and Comparative Example 1 are shown in Table 1.
[Table 1]
Figure imgf000031_0001
Note: (1) The total metal loading of Ru, Cu, Na and M is weight parts relative to 100 weight parts of Si02.
Example 14
The preparation and the reaction are conducted in the same manner as Example 1, except that 1 , 3-butadiene is used instead of propylene to give 3, 4-epoxy-l-butene .

Claims

WHAT WE CLAIM ARE:
1. 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, an alkaline metal or alkaline earth metal component and a metal component deriving from one selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
2. The process according to claim 1, wherein the catalyst comprises a halogen component.
3. The process according to claim 1, wherein the copper oxide, the ruthenium oxide, the metal component and the alkaline metal or alkaline earth metal component are supported on a porous support .
4. The process according to claim 2, wherein the copper oxide, the ruthenium oxide, the metal component, the alkaline metal or alkaline earth metal component and the halogen component are supported on a porous support.
5. The process according to claim 3 or 4, wherein the porous support comprises A1203, Si02, Ti02 or Zr02.
6. The process according to claim 1, wherein the ruthenium/copper molar ratio in the catalyst is 0.01/1 to 50/1.
7. The process according to claim 1, wherein the molar ratio of the one selected from the group consisting of Bi, Re, Cr,
Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb/copper in the catalyst is 0.001/1 to 50/1.
8. The process according to claim 1, wherein the molar ratio of alkaline metal or alkaline earth metal/copper in the catalyst is 0.001/1 to 50/1.
9. The process according to claim 1, wherein the copper oxide is CuO.
10. The process according to claim 1, wherein the ruthenium oxide is Ru02.
11. The process according to claim 1, wherein the metal component derives from Bi, Re, Sb, Ni, Co or Sn.
12. The process according to claim 1, wherein the alkaline metal or alkaline earth metal component is an alkaline metal-containing compound.
13. The process according to claim 12, wherein the alkaline metal-containing compound is a sodium-containing compound.
14. The process according to claim 3, 4 or 5, wherein the total amount of the copper oxide, the ruthenium oxide, the alkaline metal or alkaline earth metal component and the metal component is 0.01 to 80 weight parts relative to 100 weight parts of a porous support.
15. A catalyst for production of an olefin oxide which comprises a copper oxide, a ruthenium oxide, an alkaline metal or alkaline earth metal component and a metal component deriving from one element selected from the group consisting of Bi, Re, Cr, Fe, Mo, W, Se, Sb, V, Ni, Co, Sn and Nb .
16. The catalyst according to claim 15, which comprises a halogen component.
17. The catalyst according to claim 15, wherein the copper oxide, the ruthenium oxide, the metal component and the alkaline metal or alkaline earth metal component are supported on a porous support.
18. The catalyst according to claim 16, wherein the copper oxide, the ruthenium oxide, the metal component, the alkaline metal or alkaline earth metal component and the halogen component are supported on a porous support.
PCT/US2011/065159 2011-01-05 2011-12-15 Process for producing olefin oxide WO2012094120A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161430002P 2011-01-05 2011-01-05
US61/430,002 2011-01-05

Publications (1)

Publication Number Publication Date
WO2012094120A1 true WO2012094120A1 (en) 2012-07-12

Family

ID=46457663

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/065159 WO2012094120A1 (en) 2011-01-05 2011-12-15 Process for producing olefin oxide

Country Status (1)

Country Link
WO (1) WO2012094120A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014003209A1 (en) * 2012-06-29 2014-01-03 Sumitomo Chemical Company, Limited Process for producing olefin oxide

Citations (7)

* Cited by examiner, † Cited by third party
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
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
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 (en) * 2012-06-29 2014-01-03 Sumitomo Chemical Company, Limited Process for producing olefin oxide

Similar Documents

Publication Publication Date Title
US9079154B2 (en) Catalyst for the epoxidation of alkenes
US8822372B2 (en) Process for producing olefin oxide
US20140005039A1 (en) Process for preparing catalyst
US8765981B2 (en) Process for producing olefin oxide
WO2014003209A1 (en) Process for producing olefin oxide
US20130296586A1 (en) Direct conversion of olefin to olefin oxide by molecular oxygen
WO2012009056A1 (en) Process for producing olefin oxide
WO2012094120A1 (en) Process for producing olefin oxide
US8889892B2 (en) Process for producing olefin oxide
WO2012094121A1 (en) Process for producing olefin oxide
WO2012094122A1 (en) Process for producing olefin oxide
WO2012009058A2 (en) Process for producing olefin oxide
WO2013025316A1 (en) Process for producing olefin oxide
WO2013100173A1 (en) Process for producing olefin oxide using a catalyst comprising a ruthenium oxide and a tellurium component
WO2012009054A1 (en) Process for producing olefin oxide
WO2013025315A1 (en) Process for producing olefin oxide
WO2013062791A1 (en) Process for producing olefin oxide
WO2012005831A1 (en) Process for producing olefin oxide
WO2012094119A1 (en) Process for producing olefin oxide
WO2012009055A1 (en) Process for producing olefin oxide
WO2012009059A1 (en) Process for producing olefin oxide
WO2012009053A1 (en) Process for producing olefin oxide
WO2012094123A1 (en) Process for producing olefin oxide
WO2012005837A1 (en) Process for producing olefin oxide
WO2012005832A1 (en) Process for producing olefin oxide

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11855004

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11855004

Country of ref document: EP

Kind code of ref document: A1