WO2014003209A1

WO2014003209A1 - Process for producing olefin oxide

Info

Publication number: WO2014003209A1
Application number: PCT/JP2013/068455
Authority: WO
Inventors: Yoshihiko Ohishi; Anusorn Seubsai; Selim Senkan
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2012-06-29
Filing date: 2013-06-28
Publication date: 2014-01-03

Abstract

A process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) a copper oxide, (b) a ruthenium oxide, (c) an alkaline metal component or alkaline earth metal component, (d) a tellurium component and (e) one and more metal auxiliary component(s) having an efficacy on production of the olefin oxide, said metal auxiliary component(s) being except the components (a), (b), (c) and (d), wherein the metal(s) of said metal auxiliary component(s) / copper molar ratio in the catalyst is 0.001/1 to 50/1.

Description

DESCRIPTION

Title of the invention

PROCESS FOR PRODUCING OLEFIN OXIDE

Technical Field

[0001] The present invention relates to a process for producing an olefin oxide.

Background Art

[0002] As to a process for producing olefin oxides , olefin epoxidation in the presence of a metal -based catalyst has been proposed. For example, US2003/0191328 mentions a process for the epoxidation of hydrocarbon with oxygen in the presence of a mixture containing at least two metals from the specific metal group on a support having a specific BET surface area. JP2002-371074 mentions a process for producing an oxirane compound which process uses a metal oxide catalyst containing at least one metal selected from the metals belonging to the Groups III to XVI of the periodic table.

Summary of Invention

[0003] 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) a copper oxide , (b) a ruthenium oxide ,

(c) an alkaline metal component or alkaline earth metal component, (d) a tellurium component and (e) one and more metal auxiliary component (s) having an efficacy on production of the olefin oxide, said metal auxiliary component (s) being except the components (a) , (b) , (c) and (d) , wherein the metal (s) of said metal auxiliary component (s) / copper molar ratio in the catalyst is 0.001/1 to 50/1.

[2] The process according to [1] , wherein the catalyst comprises (f) a halogen component.

[3] The process according to [1] , wherein the components

(d) and (e) are metal oxides.

[4] The process according to [1] , wherein the component

(e) is derived from one or more selected from the group consisting of Sc, Y, Ti, Zr, Hf , V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Os, Co, Rh, Ir, Ni , Pd, Pt, Ag, Au, Zn, Cd, Hg, B, Al , Ga, In, Tl, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, actinides and lanthanides .

[5] The process according to [1] , wherein the component (e) is derived from one or more selected from the group consisting of Y, Cr, Mn, Re, Co, Pd, Pt , Ge and Se .

[6] The process according to [1] , wherein the components (a), (b) , (c) , (d) and (e) are supported on a support.

[7] The process according to [6] , wherein a total content of the components (a) , (b) , (c) , (d) and (e) falls within a range from 0.01 weight parts to 80 weight parts relative to 100 weight parts of the support.

[8] The process according to [6] , wherein the support is a porous support .

[9] The process according to [6] , wherein the support comprises Al₂0₃, Si0₂, Ti0₂ or Zr0₂.

[10] The process according to [6] , wherein the support comprises Si0₂.

[11] The process according to [1] , wherein the molar ratio of ruthenium of the component (b) / copper of the component (a) in the catalyst is 0.01/1 to 50/1.

[12] The process according to [1] , wherein the molar ratio of tellurium of the component (d) / copper of the component (a) in the catalyst is 0.001/1 to 50/1.

[13] The process according to [1], wherein the molar ratio of alkaline or alkaline earth metal of the component (c) / copper of the component (a) in the catalyst is 0.001/1 to 50/1.

[14] The process according to [1] , wherein the component

(a) is CuO.

[15] The process according to [1] , wherein the component

(b) is Ru0₂.

[16] The process according to [1] , wherein the component

(c) is an alkaline metal-containing compound.

[17] The process according to [1] , wherein the component (d) comprises tellurium and an oxygen atom. [18] The process according to [1] , wherein the component (e) comprises manganese and an oxygen atom.

[19] The process according to [1] , wherein the component (e) comprises yttrium and an oxygen atom.

[20] The process according to [1] , wherein the component (e) comprises selenium and an oxygen atom.

[21] The process according to [1] , wherein the component (e) comprises chromium and an oxygen atom.

[22] The process according to [1] , wherein the component (e) comprises rhenium and an oxygen atom.

[23] The process according to [1] , wherein the component (e) comprises scandium and an oxygen atom.

[24] The process according to [1] , wherein the component (e) comprises cobalt and an oxygen atom.

[25] The process according to [1] , wherein the component (e) comprises platinum and an oxygen atom.

[26] The process according to [1] , wherein the component (e) comprises palladium and an oxygen atom.

[27] The process according to [1] , wherein the component (e) comprises germanium and an oxygen atom.

[28] The process according to [15] , wherein the component (c) is a sodium-containing compound.

[29] The process according to [1] , wherein the olefin is propylene and the olefin oxide is propylene oxide.

[30] A catalyst for production of an olefin oxide comprising (a) a copper oxide, (b) ruthenium oxide, (c) an alkaline metal component or alkaline earth metal component, (d) a tellurium component and (e) one and more metal auxiliary component (s) having an efficacy on production of the olefin oxide, said metal auxiliary component (s) being except the components (a) , (b) , (c) and (d) , wherein the metal (s) of said metal auxiliary component (s) / copper molar ratio in the catalyst is 0.001/1 to 50/1.

[31] The catalyst according to [30] , which comprises (f) a halogen component.

[32] The catalyst according to [30] , wherein the components (a) , (b) , (c) , (d) and (e) are supported on a support .

[33] The catalyst according to [32] , wherein a total content of the components (a) , (b) , (c) , (d) and (e) falls within a range from 0.01 weight parts to 80 weight parts relative to 100 weight parts of the support.

[34] The catalyst according to [32] , wherein the support is a porous support.

Description of Embodiment

[0004] The process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) a copper oxide , (b) a ruthenium oxide , (c) an alkaline metal component or alkaline earth metal component, _.(d) a tellurium component and (e) one and more metal auxiliary component (s) having an efficacy on production of the olefin oxide.

[0005] The catalyst is valuable for production of olefin oxides with good selectivity.

[0006] In the catalyst , the components (a), (b) , (c) , (d) and (e) 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) . This catalyst is valuable for production of olefin oxides, which is one aspect of the present invention.

[0007] The porous support has pores capable of supporting the components (a) , (b) , (c) , (d) and (e) . The porous support comprises preferably A1₂0₃ , Si0₂, Ti0₂, orZr0₂, more preferably Si0₂.

[0008] Examples of the porous support comprising Si0₂ include mesoporous silica. Such a porous support may also comprise zeolites.

[0009] The support may be in form of powder, or shaped to a desired stucture as necessary.

[0010] If the catalyst comprises Si0₂ as a support, olefin oxides can be produced with good yield and selectivity.

[0011] The catalyst may comprise one or more kinds of (a) copper oxide. [0012] The component (a) is usually composed of copper and oxygen. Examples of the copper oxide include Cu₂0 and CuO. The copper oxide is preferably CuO.

[0013] The catalyst may comprise one or more kinds of (b) ruthenium oxide. The component (b) is usually composed of ruthenium and oxygen.

[0014] Examples of the ruthenium oxide include Ru₂0 , Ru₂0₅,

Ru₃0₅, Ru₃0₆, Ru0 , and Ru0₂. The component (b) is preferably Ru0₂.

[0015] The catalyst may comprise one or more kinds of (c) alkaline metal component or alkaline earth metal component. In the catalyst, the component (c) may be supported on the above-mentioned porous support, or the components (a) and (b) .

[0016] The component (c) may be an alkaline metal-containing compound, an alkaline earth metal-containing compound, an alkaline metal ion or an alkaline earth metal ion.

[0017] 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 Mg, Ca, 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 Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺.

[0018] The alkaline metal component may be an alkaline metal oxide. Examples of the alkaline metal oxide include Na₂0, Na₂0₂, K₂0, K₂0₂₎ Rb₂0, Rb₂0₂, Cs₂0, and Cs₂0₂. The alkaline earth metal component may be alkaline earth metal oxide. Examples of the alkaline earth metal oxide include CaO, Ca0₂, gO, Mg0₂, SrO, Sr0₂, BaO and Ba0₂.

[0019] The component (c) is preferably an alkaline metal-containing compound, more preferably a sodium-containing compound or a potassium-containing compound, still more preferably a sodium-containing compound.

[0020] 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 CI^", Br^", I^", F^", OH^", N0₃ ^", S0₄ ^2", S0₃ ^2", P0₄ ^3", P0₃ ^3", B0₃ ^3", B0₂ ^3", BO^3", B0₃ ^", B₂0^4" 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 .

[0021] The catalyst may comprise one or more kinds of (d) tellurium component. The component (d) may be tellurium-containing compound or tellurium ion.

[0022] Examples of the tellurium-containing compound include tellurium oxide such as TeO, Te0₂, Te0₃ or Te₂0₅, and tellurium salt with anion such as CI^", Br^", I^", F^", OH^", N0₃ ^" orC0₃ ^2". Examples of the tellurium ion include Te²⁺, Te⁴⁺, Te⁶⁺, Te^2". The component (d) is preferably tellurium oxide, more preferably those comprising tellurium and an oxygen atom, still more preferably Te0₂.

[0023] The catalyst comprises one or more kinds of (e) one and more metal auxiliary component (s) having an efficacy on production of the olefin oxide, said metal auxiliary component (s) being except the components (a) , (b) , (c) and (d) . Here, the component (e) includes a metal element or ion and a metal oxide, each of which derives from one or more selected from the group consisting of Sc, Y, Ti, Zr, Hf , V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Os, Co, Rh, Ir, Ni , Pd, Pt, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, actinides and lanthanides, preferably Y, Cr, Mn, Re, Co, Pd, Pt , Ge, and Se, more preferably Cr and Mn, most preferably Mn.

[0024] Examples of the metal oxide include a metal oxide composed of oxygen and the metal selected from the group consisting of Sc, Y, Ti, Zr, Hf , V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Os, Co, Rh, Ir, Ni, Pd, Pt, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, actinides and lanthanides, preferably Y, Cr, Mn, Re, Co, Pd, Pt , Ge, and Se, more preferably Cr and Mn, most preferably Mn.

[0025] The metal oxide composed of an oxygen atom and scandium includes scandium oxide such as Sc₂0₃.

[0026] The metal oxide composed of an oxygen atom and yttrium includes yttrium oxide such as Y₂0₃.

[0027] The metal oxide composed of an oxygen atom and titanium includes titanium oxide such as Ti0₂.

[0028] The metal oxide composed of an oxygen atom and zirconium includes zirconium oxide such as Zr0₂ - [0029] The metal oxide composed of an oxygen atom and hafnium includes zirconium oxide such as Hf0₂.

[0030] The metal oxide composed of an oxygen atom and vanadium includes vanadium oxide such as VO, V0₂, V₂0₃, V₆0i₃ and V₂0₅, preferably V₂0₅.

[0031] The metal oxide composed of an oxygen atom and niobium includes niobium oxide such as NbO, Nb0₂ and Nb₂0₅.

[0032] The metal oxide composed of an oxygen atom and tantalum includes tantalum oxide such as Ta₂0₅.

[0033] The metal oxide composed of an oxygen atom and chromium includes chromiun oxides such as Cr0₃, and Cr₂0₃ , preferably Cr₂0₃.

[0034] The metal oxide composed of an oxygen atom and molybdenum includes molybdenum oxide such as Mo0₂ or Mo0₃.

[0035] The metal oxide composed of an oxygen atom and tungsten includes tungsten oxide such as W₃0, W17O47, W₅0i₄, W0₂ and W0₃, preferably W0₂ and W0₃.

[0036] The metal oxide comosed of an oxygen atom and manganese includes manganese oxide such as MnO, Mn0₂, Mn₂0₃ and Mn₃0₄, preferably Mn₂0₃ and Mn₃0₄.

[0037] The metal oxide composed of an oxygen atom and rhenium includes rhenium oxides such as Re0₂, Re0₃ and Re₂0₇, preferably Re0₂ or Re0₃.

[0038] The metal oxide composed of an oxygen atom and iron includes iron oxides such as FeO, Fe₂0₃ and Fe₃0 , preferably Fe₂0₃.

[0039] The metal oxide composed of an oxygen atom and osmium includes osmium oxides such as Os0₄.

[0040] The metal oxide composed of an oxygen atom and cobalt includes cobalt oxide such as CoO, Co₃0₄ and Co₂0₃ , preferably Co₃0₄.

[0041] The metal oxide composed of an oxygen atom and rhodium includes rhodium oxide such as Rh₂0₃.

[0042] The metal oxide composed of an oxygen atom and iridium includes iridium oxide such as Ir0₂.

[0043] The metal oxide composed of an oxygen atom and nickel includes nickel oxide such as NiO.

[0044] The metal oxide composed of an oxygen atom and palladium includes palladium oxide such as PdO.

[0045] The metal oxide composed of an oxygen atom and platinum includes platinum oxide such as PtO and Pt0₂. [0046] The metal oxide composed of an oxygen atom and silver includes silver oxide such as Ag₂0.

[0047] The metal oxide composed of an oxygen atom and gold includes gold oxide such as Au₂0.

[0048] The metal oxide composed of an oxygen atom and zinc includes zinc oxide such as ZnO.

[0049] The metal oxide composed of an oxygen atom and cadmium includes cadmium oxide such as CdO .

[0050] The metal oxide composed of an oxygen atom and mercury includes mercury oxide such as HgO.

[0051] The metal oxide composed of an oxygen atom and aluminium includes aluminium oxide such as A1₂0₃.

[0052] The metal oxide composed of an oxygen atom and gallium includes gallium oxide such as Ga₂0₃.

[0053] The metal oxide composed of an oxygen atom and indium includes indium oxide such as ln₂0₃.

[0054] The metal oxide composed of an oxygen atom and thallium includes thallium oxide such as Tl₂0, T1₂0₃ and T1₄0₃, preferably T1₄0₃.

[0055] The metal oxide composed of an oxygen atom and germanium includes germanium oxide such as GeO and Ge0₂, preferably Ge0₂.

[0056] The metal oxide composed of an oxygen atom and tin includes tin oxide such as Sn0₂, SnO, Sn₂0₃ and Sn₃0_4/ preferably Sn0₂, SnO. [0057] The metal oxide composed of an oxygen atom and lead includes lead oxide such as PbO and Pb0₂.

[0058] The metal oxide composed of an oxygen atom and arsenic includes diarsenic oxide such as As₂0₃ and As₂0₅.

[0059] The metal oxide composed of an oxygen atom and antimony includes antimony oxides such as Sb0₂, Sb₂0₃, Sb₂0₄ and Sb₂0₅, preferably Sb0₂ or Sb₂0₃.

[0060] The metal oxide composed of an oxygen atom and bismuth includes bismuth oxides such as BiO, Bi0₂, Bi₂0 and Bi₂0₃.

[0061] The metal oxide composed of an oxygen atom and selenium includes selenium oxide such as Se0₃ and Se0₃, preferably Se0₃.

[0062] The metal oxide composed of an oxygen atom and actinides such as Ac, Th, Pa, and U includes actinium oxide such as Ac₂0₃, thorium oxide such as Th0₂, protactinium oxide such as Pa0₂ and Pa₂0₅ and uranium oxide such as U0₂ and U₃0₈.

[0063] The metal oxide composed of an oxygen atom and lanthanoids such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,^' Yb and Lu includes lanthanum oxide such as LaO and

La₂0₃, cerium oxide as Ce0₂ and Ce₂0₃ , praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide as Sm₂0₃, europium oxide, gadolinium oxide as Gd₂0₃ , terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide and lutetium oxide, preferably lanthanum oxide, cerium oxide, samarium oxide and gadolinium oxide, more preferably LaO, La₂0₃, Ce₂0₃ , Ce0₂, Sm₂0₃ and Gd₂0₃ , still more preferably Ce0₂.

[0064] The component (e) preferably includes a metal oxide, specifically yttrium oxide, chromium oxide, manganese oxide, rhenium oxide, cobalt oxide, palladium oxide, platinum oxide, germanium oxide and selenium oxide, more preferably chromium oxide and manganese oxide, most preferably manganese oxide .

[0065] The metal ion may form a metal -containing salt comprising the metal ion and a halogen ion.

[0066] The component (e) derives from preferably any one selected from the group consisting of Sc, Y, Ti, Zr, Hf , V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Os, Co, Rh, Ir, Ni, Pd, Pt, Ag, Au, Zn, Cd, Hg, B, Al , Ga, In, Tl, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, actinides and lanthanides, preferably Y, Cr, Mn, Re, Co, Pd, Pt, GeandSe, more preferably Cr and Mn, most preferably Mn.

[0067] The catalyst comprises preferably CuO, Ru0₂ , an alkaline metal-containing compound, Te component and a metal auxiliary component having an efficacy on production of the olefin oxide, more preferably CuO, Ru0₂, a sodium metal-containing compound, Te component and a metal component derived from Cr and Mn,_still more preferably CuO, Ru0₂, a sodium-containing compound, Te component, and a metal component derived from Mn, 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 alkalilne metal or alkaline earth metal component, it can show excellent olefin oxide selectivity.

[0068] The component (e) may also comprise one or more selected from B, P and S. The components are oxide, ion or compound. Examples of the oxides include H₃B0₄, H₃B0₃, H₃P0₄, P₂0₅, H₃P0₃, H₃B0₃ and B₂0₃. Examples of the ions include S0₃ ^2_, S0₄ ^2~, P0₄ ^3~, P0₃ ^3~, B0₃ ^3~, B0₂ ^3~, B0₃ ^", B0₃ ^" and B₂0₄ ^4~. Examples of the compounds are salt composed of the component one or more component selected from B, P and S, and one or more component selected from a group consisting of the component (a) , the component (b) , the component (c) , the component (d) and a component that functions as the component (e) and contains neither B, P nor S.

[0069] The components (d) and (e) are preferably metal oxides .

[0070] The molar ratio of ruthenium of the component (b)

/ copper of the component (a) 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 0.05/1, still more preferably 0.1/1, preferably 0.2/1. The upper limit of the molar ratio is more preferably 5/1, still more preferably 2/1, most preferably 1/1.

[0071] The molar ratio of alkaline or alkaline earth metal of the component (c) / copper of the component (a) 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.

[0072] The molar ratio of tellurium of the component (d)

/ copper of the component (a) 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 1/1, still more preferably 0.5/1.

[0073] The molar ratio of the metal of the component (e)

/ copper of the component (a) in the catalyst is 0.001/1 to 50/1 based on their atoms. The lower limit of the molar ratio is preferably 0.01/1, more preferably 0.05/1. The upper limit of the molar ratio is preferably 10/1, more preferably 5/1.

[0074] When the components (a) , (b) , (c) , (d) and (e) are supported on a support in the catalyst, the total content of these components is preferably 0.01 to 80 weight parts relative to 100 weight parts of the 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 the 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 the support.

[0075] The catalyst may comprise (f) halogen component besides the components (a) , (b) , (c) , (d) and (e) . The component (f) is generally a halogen-containing compound. Examples of the halogen include chlorine, fluorine, iodine and bromine.

[0076] Examples of such a halogen-containing compound include copper halides such as CuCl and CuCl₂, tellurium halides such as TeCl₂ and TeCl₄, ruthenium halides such as RuCl₃ and copper oxyhalides such as CuOCl₂, CuC10₄, Cl0₂Cu (C10₄ ) ₃ and Cu₂0(Cl0₄)₂, tellurium oxyhalides such as Te₆0nCli₂, ruthenium oxyhalides such as Ru₂OCl₄, Ru₂OCl₅ and Ru₂OCl₆. In addition, one or more metal, which is selected from Sc, Y, Ti, Zr, Hf , V, Nb, Ta, Cr, W, n, Re, Fe, Os, Co, Rh, Ir, Ni, Pd, Pt, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, actinides and lanthanides, halides and oxyhalides may be included.

[0077] If the catalyst comprises the component (f) , the component may be supported on any of the components (a) , (b) , (c) , (d) , and (e) or the support.

[0078] The catalyst may further comprise (g) composite oxides. Examples of the composite oxides include those composed of copper, tellurium and oxygen, such as CuTe0 , CuTe0₃ and Cu₃Te0₆, those composed of tellurium, sodium and oxygen, such as Na₂Te0₃, Na₂Te0₄, Na₂Te₄0₉, and NaTe0₅, and those composed of sodium, copper and oxygen, such as NaCu0₂, Na₂Cu0₂, NaCuO and Na₆Cu₂0₆, those composed of ruthenium, tellurium and oxygen, those composed of ruthenium, copper and oxygen such as RuCu₂0₂, RuCuC10₃, Ru₂Cu0₆, Ru₂Cu₂0₂ , and those composed of ruthenium, sodium and oxygen. In addition, the composite oxides include those composed of one or more metal selected from Sc, Y, Ti, Zr, Hf , V, Nb, Ta, Cr, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al , Ga, In, Tl, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, actinides, lanthanides, alkaline metal, alkaline earth metal and oxygen.

[0079] If the catalyst comprises the component (g) , the component may be supported on the support or any of the components (a) , (b) , (c) , (d) , (e) and (f) as mentioned above.

[0080] Production of the catalyst is not restricted to a specific process, examples of which include the conventional methods, for example, ^'impregnation method, precipitation method, deposition precipitation, chemical vapour deposition, mechnano-chemical method, solid state reaction method, hydrothermal synthesis and the like, preferably impregnation method .

[0081] When the components (a) , (b) , (c) , (d) , and (e) , optionally in addition with the component (f) and (g) are supported on a support in the catalyst, the catalyst can be obtained by impregnating the support with a solution containing a copper ion, ruthenium ion, a tellurium compound or ion, and an alkaline metal or alkaline earth metal-containing ion, a tellurium compound or ion, and metal auxiliary component (s) [having an efficacy on production of the olefin oxide] or its (their) ion and/or an anion such as a halogen ion to prepare a composition, followed by calcining the composition. The support can be in form of powder, or shaped to a desired stucture as necessary.

[0082] Here, in the case of no catalytic support in the catalyst, the catalyst can be prepared in the same manner described above except no using catalytic support.

[0083] The solution containing above-mentioned ions can be prepared by dissolving a copper metal salt or compound, a ruthenium salt or compound, an alkaline metal or alkaline earth metal salt or compound, a tellurium metal salt or compound, and (e) one and more metal auxiliary component (s) salt or compound and/or an anion-containing compound such as a halogen-containing compound in a solvent.

[0084] Examples of the copper salt include, for example, 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, preferably copper nitrates and copper chlorides.

[0085] Examples of the ruthenium metal salt or compound include, for example, a halide such as ruthenium bromide, ruthenium chloride, ruthenium iodide, an oxyhalide such as Ru₂OCl₄, Ru₂OCl₅ and Ru₂OCl₆, a halogeno complex such as

[RuCl₂ (H₂0) ₄] CI , an ammine complex such as [Ru (NH₃) ₅H₂0] Cl₂ ,

[Ru (NH₃) ₅C1] Cl₂, [Ru(NH₃) _e] 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) ₆ (H20) ₃] , ruthenium nitrosylchloride , and

[Ru₂ (OCOR) ] Cl (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, preferably ruthenium metal salt containing Cl .

[0086] The alkaline metal or alkaline earth metal salt or compound for the solution may be the same as or different from the (d) component. Examples of the alkaline metal and the alkaline earth metal salt or compound include alkaline metal oxide, alkaline earth metal oxide, 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 .

[0087] Examples of the tellurium salt or compound include, for example, a halide such as TeF₆, TeBr , 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, H₆Te0₆, Na₂Te0₃ and Na₂Te0₄, preferably halide and oxide, more preferably oxide, still more preferably Te0₂ and H₆Te0₆.

[0088] Examples of the (e) one and more metal auxiliary component (s) salt or compound, for example, the metal oxide, the metal nitrate , the metal halides such as fluoride , chloride, bromide, and iodide, preferably the metal halides.

[0089] At least one of the metal salts for the solvent contains preferably a halogen ion, more preferably a chloride ion .

[0090] The catalyst comprising the components (a) , (b) ,

(c) , (d) and (e) can be produced from a solution obtained by dissolving the copper metal salt, the ruthenium metal salt, the alkaline metal salt or alkaline earth metal salt, the tellurium metal salt or compound and the (e) one and more metal auxiliary component (s) salt or compound, in a solvent. 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 component (c) such as NaCl and the component (f) such as halides and oxyhalides of Cu, Ru or Te . The solution may contain acidic or basic compounds in order to control its pH. The acidic or basic compounds are not limited to the specific one if the catalyst is prepared. Examples of the acid compounds include hydrochloric acid, nitric acid, nitrous acid and perchloric acid. Examples of basic compounds include alkaline metal hydroxides, amine compounds, imine compounds, hydrazine or hydrazine compounds, ammonia, hydroxylamine , hydroxyamine and ammonium hydroxides.

[0091] Examples of the solvent for the solution include water, -alcohols such as methanol or ethanol, and ethers. As a source of water, ion-exchanged water is usually used. The amount of water, alcohols or ethers as the solvent is not limited, preferably 0.01 to 2000 parts by weight per 1 part by weight of copper in the mixture. If the catalyst contains support, the amount of water, alcohols or ethers as the solvent is preferably 0.01 to 500 parts by weight per 1 part by weight of support in the mixture, more preferably 0.1 to 100 parts by weight per 1 part by weight of support in the mixture.

[0092] The mixture solution composed of metal salts described above or support is preferably aged with stirring at a temperature of 5°C to 100°C, more preferably 10°C to 50°C. The mixture solution can be used as is, but is preferably aged for some time. Aging time is preferably in the range from 0.5 to 48 hours, more preferably 1 to 25 hours.

[0093] The composition as prepared by the impregnation is usually dried, and the drying method thereof is not limited. For example, evaporation to dryness, spray drying, drum drying, flash drying and the like. The composition as prepared by the impregnation is preferably dried at a temperature of 10 ^°C to 250 ^°C, more preferably 40^°C to 200^°C, before calcining the composition. Drying may be conducted under an atmosphere maintained at a relative humidity of 10 to 90%, preferably 20 to 60%. Furthermore, drying may be performed under an atmosphere of 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.

[0094] 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, chlorine-containing compound and water vapor.

[0095] In the case of gas flow, the gaseous hourly space velocity (Milliliters of gas at standard temperature and pressure passing over the one gram of packed catalyst per hour) is generally in the range from 10 to 5000 ml/ (g-h) , preferably 100 to 3000 ml/ (g-h), more preferably 200 to 1500 ml/ (g-h) .

[0096] 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, tellurium and copper components. Accordingly, the calcination temperature is typically 250 to 800 ^°C, preferably 400 to 600 ^°C. The calcining time is preferably in the range from 0.5 hour to 24 hours. Temperature programmed rate from

0.1 to 100 °C/min., preferably 0.1 to 30 °C/min. The metal oxides as the components (a) , (b) , (c) , (d) and (e) can be made by the calcination.

[0097] 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.

[0098] Next, the following explains a reaction of an olefin with oxygen in the presence of the catalyst as described above .

[0099] 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, hexene , 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 .

[0100] 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 maybe fed with diluent gases. Examples of diluent gases include nitrogen, methane, ethane, propane, carbon dioxide, or rare gases, such as argon and helium.

[0101] 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 0.05 to 10 mol, with respect to 1 mol of the olefin.

[0102] Halogen compound additives increase olefin oxide selectivities or prevent their decrease with time-on-stream. The halogen compound additive is preferably a saturated or unsaturated organohalogen compound capable of existing as a gas under the conditions of temperature and pressure in the reaction system of olefin epoxidation. More specifically, examples of the saturated or unsaturated halogen compound include, for example, an organic fluorine compound such as fluorinated hydrocarbon; an organic chlorine compound such as chlorinated hydrocarbon; an organic bromine compound such as bromo hydrocarbon; and an organic iodine compound such as iodo hydrocarbon. Each of the hydrocabons is preferably an alkane or alkene, more preferably a C1-C4 alkane or alkene . More preferavly, an organic chlorine compound is used, and the compound includes , for example, chlorinated hydrocarbon . The chlorinated hydrocarbon includes alkyl chlorides or allyl chlorides, e.g. chloromethane , . chloroethane ,

1 , 2 -dichloroethane , vinyl chloride, tetrachloroethylene , trichloroethylene, 1 -chloropropane , 1 , 2-dichloropropane, 1 , 3 -dichloropropane , 1 , 2 , 3 -trichloropropane and allyl chloride. The optimum amount of the halogen compound to be supplied varies depending on factors such as a concentration of olefin, a concentration of oxygen, an amount of the catalysts described above, but is usually from 0.1 ppm to 1000 ppm, and preferably from 1 ppm to 500 ppm, of the entire reaction gas.

[0103] 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.

[0104] 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.

[0105] 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/ ( 1. 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 m/s to 50 m/s.

[0106] 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.

[0107] 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.

[0108] In the case of using fixed bed reactor, the catalyst can be packed into a 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 large reactor.

[0109] Generally, the reaction mixture can be passed through the packed bed reactor in up-flow mode or in downflow mode .

[0110] Adiabatic type reactor or heat exchange type reactor may also be used. In the case of using adiabatic type reactor, part of reaction mixture from reactor can be recycled into the reactor after heat-exchanging to control the reaction temperature .

[0111] In the case of using at least two reactors, the reactors can be arranged in series and/or in parallel. In the case of using at least two reactors arranged in series, a heat exchanger can be used between the reactors for controling reaction temperature.

[0112] 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.

[0113] The olefin oxide as obtained can be collected by absorption with a suitable solvent as water, acetonitrile and the like, and subsequent a method known in the art such as separation by distillation.

EXAMPLES

[0114] In Examples 1 to 10 , 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) .

[0115] The detected products were propylene oxide (PO) , acetone (AT) , acetaldehyde (AD) , CO_x (C0₂ and CO) , and propanal (PaL) and acrolein (AC) .

[0116] Propylene conversions (X_PR) were determined from the following:

Xp_R = { [PO+AC+AT+PaL+C0₂/3]_out/ [C₃H₅] _in} ^χ 100%; and PO selectivities (S_P0) were then calculated using the following expression:

Spo = { [PO] / [PO+AC+AT+PaL+C0₂/3] } ^χ 100% Each metal weight was determined from the amounts of the metal salts used for preparation of catalyst.

Example 1

[0117] A catalyst was prepared by a co-impregnation method. A predetermined weights (1.9 g) of an amorphous silica powder (Si0₂, Japan Aerosil, 380 m²/g) was added to an aqueous solution mixture containing 0.22 g of (NH₄) ₂RuCl_s (Alfa) , 0.30 g of Cu (N0₃) 2 (Wako) , 0.03 g of MnCl₂ (Wako) , 0.03 g of Te0₂ (Wako) , 0.10 g of NaCl (Wako) and 40 g of ion-exchanged water, followed by stirring it for 24 hours at room temperature 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.

[0118] The catalyst was evaluated by using a fixed-bed reactor. Filling a 1/2-inch reaction tube made of stainless steel with lmL of thus obtained catalyst, the reaction tube was supplied with 450 NmL/h of propylene, 900 NmL/h of the air, 990 NmL/h of a nitrogen gas to carry out the reaction at the reaction temperature of 270 °C under the atmospheric pressure.

[0119] In the catalyst, the total amount of Ru, Cu, Na, Te and Mn was 10.8 weight parts relative to 100 weight parts of Si0₂.

The results are shown in Table 1.

Table 1

Example 2

[0120] A catalyst was prepared by a co-impregnation method. A predetermined weights (1.9 g) of an amorphous silica powder (Si0₂, Japan Aerosil , 380 m²/g) was added to an aqueous solution mixture containing 0.22 g of (NH₄) ₂RuCl₆ (Alfa) , 0.30 g of Cu (N0₃) 2 (Wako) , 0.02 g of YC1₃ (Wako) , 0.03 g of Te0₂ (Wako) , 0.10 g of NaCl (Wako) and 40 g of ion-exchanged water, followed by stirring it for 24 hours at room temperature 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.

[0121] In the catalyst, the total amount of Ru, Cu, Na,

Te and Y was 10.9 weight parts relative to 100 weight parts of Si0₂- [0122] The catalyst was evaluated in the same manners as

Example 2. The results are shown in Table 2. Table 2

Example 3

[0123] A catalyst was prepared by a co- impregnation method. A predetermined weights (1.9 g) of an amorphous silica powder (Si0₂, Japan Aerosil, 380 m²/g) was added to an aqueous solution mixture containing 0.22 g of (NH₄) ₂RuCl_s (Alfa) , 0.30 g of Cu (N0₃) 2 ( ako) , 0.03 g of SeCl₄ (Wako) , 0.03 g of Te0₂ (Wako) , 0.10 g of NaCl (Wako) and 40 g of ion-exchanged water, followed by stirring it for 24 hours at room temperature 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.

[0124] In the catalyst, the total amount of Ru, Cu, Na, Te and Se was 10.9 weight parts relative to 100 weight parts of Si0₂.

[0125] The catalyst was evaluated in the same manners as

Example 2. The results are shown in Table 3. Table 3 Total metal loading (wt parts) 10.9

Ru/Cu/Na/Te/Se (molar ratio of metal) 0.5/1/1.4/0.1/0.1

Propylene oxide selectivity (%) 41

Example 4

[0126] A catalyst was prepared by a co-impregnation method. A predetermined weights (1.9 g) of an amorphous silica powder (Si0₂, Japan Aerosil, 380 m²/g) was added to an aqueous solution mixture containing 0.22 g of (NH₄ ) ₂RuCl₆ (Alfa) , 0.30 g of Cu (N0₃) 2 (Wako) , 0.03 g of CrCl₃ (Wako) , 0.03 g of Te0₂ (Wako) , 0.10 g of NaCl (Wako) and 40 g of ion-exchanged water, followed by stirring it for 24 hours at room temperature 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.

[0127] In the catalyst, the total amount of Ru, Cu, Na,

Te and Cr was 10.7 weight parts relative to 100 weight parts of Si0₂.

[0128] The catalyst was evaluated in the same manners as

Example 1 except the reaction temperature of 250 °C. The results are shown in Table 4. Table 4 Total metal loading (wt parts) 10.7

Ru/Cu/Na/Te/Cr (molar ratio of metal) 0.5/1/1.4/0.1/0.1

Propylene oxide selectivity (%) 34

Example 5

[0129] A catalyst was prepared by a co- impregnation method. A predetermined weights (1.9 g) of an amorphous silica powder (Si0₂, Japan Aerosil, 380 m²/g) was added to an aqueous solution mixture containing 0.22 g of (NH₄)₂RuCl₆ (Alfa) , 0.30 g of Cu(N0₃)₂ (Wako) , 0.045 g of ReCl₅ (Wako) , 0.03 g of Te0₂ (Wako) , 0.10 g of NaCl (Wako) and 40 g of ion-exchanged water, followed by stirring it for 24 hours at room temperature 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.

[0130] In the catalyst, the total amount of Ru, Cu, Na,

Te and Re was 11.6 weight parts relative to 100 weight parts of Si0₂.

[0131] The catalyst was evaluated in the same manners as

Example 1. The results are shown in Table 5.

Table 5 Total metal loading (wt parts) 11.6

Ru/Cu/Na/Te/Re (molar ratio of metal) 0.5/1/1.4/0.1/0.1

Propylene oxide selectivity (¾) 40

Example 6

[0132] A catalyst was prepared by a co-impregnation method. A predetermined weights (1.9 g) of an amorphous silica powder (Si0_2/ Japan Aerosil, 380 m²/g) was added to an aqueous solution mixture containing 0.22 g of (NH )₂RuCl₆ (Alfa) , 0.30 g of Cu (N0₃) 2 (Wako) , 0.02 g of ScCl₃ (Wako) , 0.03 g of Te0₂ (Wako) , 0.10 g of NaCl (Wako) and 40 g of ion-exchanged water, followed by stirring it for 24 hours at room temperature 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.

[0133] In the catalyst, the total amount of Ru, Cu, Na,

Te and Sc was 10.9 weight parts relative to 100 weight parts of Si0₂.

[0134] The catalyst was evaluated in the same manners as

Example 1. The results are shown in Table 6.

Table 6 Total metal loading (wt parts) 10.9

Ru/Cu/Na/Te/Sc (molar ratio of metal) 0.5/1/1.4/0.1/0.1

Propylene oxide selectivity (%) 39

Example 7

[0135] A catalyst was prepared by a co- impregnation method. A predetermined weights (1.9 g) of an amorphous silica powder (Si0₂, Japan Aerosil, 380 m²/g) was added to an aqueous solution mixture containing 0.22 g of (NH₄) ₂RuCl₆ (Alfa) , 0.30 g of Cu (N0₃) 2 (Wako) , 0.02 g of CoCl₂ (Wako) , 0.03 g of Te0₂ (Wako) , 0.10 g of NaCl(Wako) and 40 g of ion-exchanged water, followed by stirring it for 24 hours at room temperature 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.

[0136] In the catalyst, the total amount of Ru, Cu, Na,

Te and Co was 10.8 weight parts relative to 100 weight parts of Si0₂.

[0137] The catalyst was evaluated in the same manners as

Example 1. The results are shown in Table 7.

Table 7 Total metal loading (wt parts) 10.8

Ru/Cu/Na/Te/Co (molar ratio of metal) 0.5/1/1.4/0.1/0.1

Propylene oxide selectivity (%) 38

Example 8

[0138] A catalyst was prepared by a co- impregnation method. A predetermined weights (1.9 g) of an amorphous silica powder (Si0₂, Japan Aerosil, 380 m²/g) was added to an aqueous solution mixture containing 0.22 g of (NH₄)₂RuCl₆ (Alfa) , 0.30 gof Cu(N0₃)₂ (Wako) , 0.03 g of PtCl₂ ( ako) , 0.03 g of Te0₂ (Wako) , 0.10 g of NaCl (Wako) and 40 g of ion-exchanged water, followed by stirring it for 24 hours at room temperature 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.

[0139] In the catalyst, the total amount of Ru, Cu, Na,

Te and Pt was 11.7 weight parts relative to 100 weight parts of Si0₂.

[0140] The catalyst was evaluated in the same manners as

Example 1. The results are shown in Table 8.

Table 8 Total metal loading (wt parts) 11.7

Ru/Cu/Na/Te/Pt (molar ratio of metal) 0.5/1/1.4/0.1/0.1

Propylene oxide selectivity (%) 38

Example 9

[0141] A catalyst was prepared by a co- impregnation method. A predetermined weights (1.9 g) of an amorphous silica powder (Si0₂, Japan Aerosil , 380 m²/g) was added to an aqueous solution mixture containing 0.22 g of (NH₄)₂R Cl₆ Alfa) , 0.30 g of Cu (N0₃) 2 (Wako) , 0.02 g of PdCl₂ (Wako) , 0.03 g of Te0₂ (Wako) , 0.10 g of NaCl (Wako) and 40 g of ion-exchanged water, followed by stirring it for 24 hours at room temperature 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.

[0142] In the catalyst, the total amount of Ru, Cu, Na,

Te and Pd was 11.1 weight parts relative to 100 weight parts of Si0₂.

[0143] The catalyst was evaluated in the same manners as

Example 1. The results are shown in Table 9.

Table 9 Total metal loading (wt parts) 11.1

Ru/Cu/Na/Te/Pd (molar ratio of metal) 0.5/1/1.4/0.1/0.1

Propylene oxide selectivity (%) 37

Example 10

[0144] A catalyst was prepared by a co-impregnation method. A predetermined weights (1.9 g) of an amorphous silica powder (Si0₂, Japan Aerosil , 380 m²/g) was added to an aqueous solution mixture containing 0.22 g of (NH )₂RuCl₆ (Alfa) , 0.30 g of Cu (N0₃) 2 ( ako) , 0.03 g of GeCl₄ ( ako) , 0.03 g of Te0₂ (Wako) , 0.10 g of NaCl (Wako) and 40 g of ion-exchanged water, followed by stirring it for 24 hours at room temperature 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.

[0145] In the catalyst, the total amount of Ru, Cu, Na,

Te and Ge was 10.9 weight parts relative to 100 weight parts of Si0₂.

[0146] The catalyst was evaluated in the same manners as

Example 1. The results are shown in Table 10.

Table 10 Total metal loading (wt parts) 10.9

Ru/Cu/Na/Te/Ge (molar ratio of metal) 0.5/1/1.4/0.1/0.1

Propylene oxide selectivity (%) 35

Example 11

[0147] A catalyst was prepared by a co- impregnation method. A predetermined weights (3.9 g) of a silica (CARiACT Q-30, 1.18-2.36 mm, Fuji Silysia) was added to an aqueous solution mixture containing 0.51 g of RuCl₃ ·ηΗ₂0 (Ru : 40 wt%, Furuya metal) , 0.60 g of Cu (N0₃ ) ₂ (Wako) , 0. lOg of MnCl₂ (Wako) , 0.08 g of Te0₂ (Wako), 0.20 g of NaCl (Wako) and 3.8 g of ion-exchanged water to impregnate the support with the metal salts . The resulting material was then aged at room temperature for 0.5 hour, and dried at 85°C and a relative humidity of 30% for 3 hours. Finally, the product was calcined at 540 °C for 12 hours in the air to give a catalyst.

[0148] In the catalyst, the total amount of Ru, Cu, Na, Te and Mn was 13.7 weight parts relative to 100 weight parts of Si0₂.

[0149] The catalyst was evaluated in the same manners as

Example 1. The results are shown in Table 11. Table 11 Total metal loading (wt parts) 13.7

Ru/Cu/Na/Te/Mn (molar ratio of metal) 0.8/1/1.4/0.2/0.2

Propylene oxide selectivity (%) 51

Example 12

[0150] The catalyst prepared in Example 11 was evaluated by using a fixed-bed reactor . Filling a 3/4 - inch reaction tube made of stainless steel with 0.4 mL of thus obtained catalyst, the reaction tube was supplied with 45 NmL/min of propylene, 90 NmL/min of the air, 25 NmL/min of 1% chloroethane/N₂ mixed gas, 74 NmL/min of a nitrogen gas to carry out the reaction at the reaction temperature of 250 °C under the 0.5 MPa . The results are shown in Table 12.

Table 12

Example 13

[0151] A catalyst was prepared by a co- impregnation method. A predetermined weights (3.9 g) of a silica (CARiACT Q-30, 1.18-2.36 mm, Fuji Silysia) was added to an aqueous solution mixture containing 0.51 g of RuCl₃ -nH₂0 (Ru : 40 wt%, Furuya metal) , 0.60 g of Cu (N0₃) ₂ (Wako) , 0.07 g of CrCl₃ (Wako) , 0.08 g of Te0₂ (Wako) , 0.20 g of NaCl (Wako) and 3.8 g of ion-exchanged water to impregnate the support with the metal salts . The resulting material was then heated at 40 °C for 20h, and calcined at 500 °C for 12 hours in the air to give a catalyst .

[0152] In the catalyst, the total amount of Ru, Cu, Na,

Te and Cr was 13.4 weight parts relative to 100 weight parts of Si0₂.

[0153] The catalyst was evaluated in the same manners as

Example 12. The results are shown in Table 13.

Table 13

Example 14

[0154] A catalyst was prepared by a co- impregnation method. A predetermined weights (3.9 g) of a silica (CARiACT Q-30, 1.18-2.36 mm, Fuji Silysia) was added to an aqueous solution mixture containing 0.51 g of RuCl₃ ·ηΗ₂0 (Ru : 40 wt%, Furuya metal) , 0.60 g of Cu (N0₃) ₂ (Wako) , 0.07 g of CrCl₃ (Wako) , 0.08 g of Te0₂ (Wako), 0.10g of MnCl₂ (Wako), 0.20 g of NaCl (Wako) and 3.8 g of ion-exchanged water to impregnate the support with the metal salts. The resulting material was then heated at 40 °C for 20h, and calcined at 500 °C for 12 hours in the air to give a catalyst.

[0155] In the catalyst, the total amount of Ru, Cu, Na,

Te, Mn and Cr was 13.9 weight parts relative to 100 weight parts of Si0₂.

[0156] The catalyst was evaluated in the same manners as

Example 12. The results are shown in Table 14.

Table 14

Claims

1. A process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) a copper oxide , (b) a ruthenium oxide , (c) an alkaline metal component or alkaline earth metal component, (d) a tellurium component and (e) one and more metal auxiliary component (s) having an efficacy on production of the olefin oxide, said metal auxiliary component (s) being except the components (a) , (b) , (c) and (d) , wherein the metal (s) of said metal auxiliary component (s) / copper molar ratio in the catalyst is 0.001/1 to 50/1.

.

2. The process according to claim 1 , wherein the catalyst comprises (f) a halogen component.

3. The process according to claim 1, wherein the components (d) and (e) are metal oxides.

4. The process according to claim 1, wherein the component (e) is derived from one or more selected from the group consisting of Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Os, Co, Rh, Ir, Ni , Pd, Pt , Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl , Ge, Sn, Pb, P, As, Sb, Bi, S, Se, actinides and lanthanides .

5. The process according to claim 1, wherein the component (e) is derived from one or more selected from the group consisting of Y, Cr, Mn, Re, Co, Pd, Pt, Ge, and Se .

6. The process according to claim 1, wherein the components (a), (b) , (c) , (d) and (e) are supported on a support .

7. The process according to claim 6, wherein a total content of the components (a) , (b) , (c) , (d) and (e) falls within a range from 0.01 weight parts to 80 weight parts relative to 100 weight parts of the support.

8. The process according to claim 6, wherein the support is a porous support.

9. The process according to claim 6, wherein the support comprises A1₂0₃₍ Si0₂, Ti0₂ or Zr0₂.

10. The process according to claim 6 , wherein the support comprises Si0₂.

11. The process according to claim 1, wherein the molar ratio of ruthenium of the component (b) / copper of the component (a) in the catalyst is 0.01/1 to 50/1.

12. The process according to claim 1, wherein the molar ratio of tellurium of the component (d) / copper of the component (a) in the catalyst is 0.001/1 to 50/1.

13. The process according to claim 1, wherein the molar ratio of alkaline or alkaline earth metal of the component (c) / copper of the component (a) in the catalyst is 0.001/1 to 50/1.

14. The process according to claim 1, wherein the component (a) is CuO.

15. The process according to claim 1, wherein the component (b) is Ru0₂.

16. The process according to claim 1, wherein the component (c) is an alkaline metal-containing compound.

17. The process according to claim 1, wherein the component (d) comprises tellurium and an oxygen at :eom .

18. The process according to claim 1, wherein the component (e) comprises manganese and an oxygen atom.

19. The process according to claim 1, wherein the component (e) comprises yttrium and an oxygen atom.

20. The process according to claim 1, wherein the component (e) comprises selenium and an oxygen atom.

21. The process according to claim 1, wherein the component (e) comprises chromium and an oxygen atom.

22. The process according to claim 1, wherein the component (e) comprises rhenium and an oxygen atom.

23. The process according to claim 1, wherein the component (e) comprises scandium and an oxygen atom.

24. The process according to claim 1, wherein the component (e) comprises cobalt and an oxygen atom.

25. The process according to claim 1, wherein the component (e) comprises platinum and an oxygen atom.

26. The process according to claim 1, wherein the component (e) comprises palladium and an oxygen atom.

27. The process according to claim 1, wherein the component (e) comprises germanium and an oxygen atom.

28. The process according to claim 15, wherein the component (c) is a sodium-containing compound.

29. The process according to claim 1, wherein the olefin is propylene and the olefin oxide is propylene oxide.

30. A catalyst for production of an olefin oxide comprising (a) a copper oxide, (b) ruthenium oxide, (c) an alkaline metal component or alkaline earth metal component, (d) a tellurium component and (e) one and more metal auxiliary component (s) having an efficacy on production of the olefin oxide, said metal auxiliary component (s) being except the components (a) , (b) , (c) and (d) , wherein the metal (s) of said metal auxiliary component (s) / copper molar ratio in the catalyst is 0.001/1 to 50/1.

31. The catalyst according to claim 30, which comprises

(f) a halogen component.

32. The catalyst according to claim 30, wherein the components (a) , (b) , (c) , (d) and (e) are supported on a support.

33. The catalyst according to claim 3'2, wherein a total content of the components (a) , (b) , (c) , (d) and (e) falls within a range from 0.01 weight parts to 80 weight parts relative to 100 weight parts of the support.

34. The catalyst according to claim 32, wherein the support is a porous support.