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. 61/430,068 filed January 5, 2011, incorporated by reference herein in its entirety.

FIELD OF THE INVENTION

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

BACKGROUND ART

As to a process for producing 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 and a metal component deriving from one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce .

[2] The process according to [1], wherein the catalyst comprises an alkaline metal or alkaline earth metal component.

[3] The process according to [1] or [2] , wherein the catalyst comprises a halogen component.

[4] The process according to any one of [1] to [3], wherein the copper oxide, the ruthenium oxide and the metal component are supported on a porous support.

[5] The process according to any one of [2] to [4], 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.

[6] The process according to any one of [3] to [5], 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.

[7] The process according to any one of [4] to [6], wherein the porous support comprises AI2O3, S1O2, T1O2 or ZrC>2.

[8] The process according to any one of [1] to [7], wherein the ruthenium/copper molar ratio in the catalyst is 0.01/1 to 50/1.

[9] The process according to any one of [1] to [8], wherein the molar ratio of the one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce /copper in the catalyst is 0.001/1 to 50/1.

[10] The process according to any one of [2] to [9], wherein the molar ratio of alkaline metal or alkaline earth metal/copper in the catalyst is 0.001/1 to 50/1.

[11] The process according to any one of [1] to [10], wherein the copper oxide is CuO.

[12] The process according to any one of [1] to [11], wherein the ruthenium oxide is RuC>2.

[13] The process according to any one of [1] to [12], wherein the metal component derives from Mn, Ge or La.

[14] The process according to any one of [2] to [13], wherein the alkaline metal or alkaline earth metal component is an alkaline metal-containing compound.

[15] The process according to [14], wherein the alkaline metal-containing compound is a sodium-containing compound.

[16] The process according to any one of [4] to [7], 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.

[17] The process according to any one of [4] to [7], wherein the catalyst is obtained by impregnating a porous support with a solution or a suspension containing a copper ion, a ruthenium 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 Mn, Ge, Tl, In, Ir, La and Ce .

[18] The process according to any one of [1] to [17], wherein the olefin is propylene and the olefin oxide is propylene oxide.

[19] The process according to any one of [1] to [18], which comprises reacting an olefin with oxygen at a temperature of 100 to 350°C.

[20] A catalyst for production of an olefin oxide which comprises a copper oxide, a ruthenium oxide and a metal component deriving from one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce .

[21] The catalyst according to [20], which comprises an alkaline metal or alkaline earth metal component.

[22] The catalyst according to [20] or [21], which comprises a halogen component.

[23] The catalyst according to any one of [20] to [22] , wherein the copper oxide, the ruthenium oxide and the metal component are supported on a porous support.

[24] The catalyst according to any one of [21] to [23] , 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.

[25] The catalyst according to [23] or [24], wherein the copper oxide, the ruthenium oxide and the metal component are supported on a porous support.

[26] The catalyst according to any one of [23] to [25] which is obtained by impregnating a porous support with a solution or a suspension containing a copper ion, a ruthenium 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 Mn, Ge, Tl, In, Ir, La and Ce .

[27] The catalyst according to any one of [20] to [26] , wherein the copper oxide is CuO.

[28] The catalyst according to any one of [20] to [27] , wherein the ruthenium oxide is Ru0 ₂ .

[29] The catalyst according to any one of [20] to [28] , wherein the metal component derives from Mn, Ge or La.

[30] The catalyst according to any one of [21], wherein the alkaline metal or alkaline earth metal component is an alkaline metal-containing compound.

[31] The catalyst according to any one of [23] to [25] , wherein the porous support comprises AI2O3, S1O2, T1O2 or ZrC>2.

[32] The catalyst according to any one of [20] to [31] , 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 and a metal component.

In the catalyst, the copper oxide, the ruthenium oxide and the metal component are preferably supported on a support, and more preferably on a porous support. This catalyst is valuable for production of olefin oxides, which is one aspect of the present invention.

The support may be a porous support, and may be a non-porous support.

The porous support has pores capable of supporting the copper oxide, the ruthenium oxide and the metal component.

The porous support preferably comprises AI ₂ O ₃ , Si0 ₂ , Ti0 ₂ , or Zr02, more preferably Si0 ₂ . Examples of the porous support comprising S1O ₂ include mesoporous silica. Such porous supports may also comprise zeolites.

Examples of the non-porous support include a non-porous support comprising S1O ₂ such as CAB-O-SIL (registered trademark) .

The support may be in form of powder or may be shaped to a desired structure.

If the catalyst comprises Si0 ₂ as a support, olefin oxides can be prepared with good yield and good selectivity.

The catalyst comprises one or more kinds of copper oxides .

The copper oxide is usually composed of copper and oxygen.

Examples of the copper oxide include CU2O and CuO. The copper oxide is preferably CuO.

The catalyst comprises one or more kinds of the ruthenium oxide. The ruthenium oxide is usually composed of ruthenium and oxygen. Examples of the ruthenium oxide include RU2O4 , RU2O5 , RU3O5 , RU3O6 , RUC , and RUO2. The ruthenium oxide is preferably Ru0 ₂ .

The catalyst comprises one or more kinds of the metal components. Here, the metal component includes a metal element or ion and a metal oxide, each of which derives from one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce . Examples of the metal oxide include a metal oxide composed of oxygen and the metal selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce .

The metal oxide composed of an oxygen atom and manganese includes manganese oxides such as MnO, Μηθ ₂ , Μη ₂ θ ₃ and Μη ₃ θ ₄ , preferably Mn ₂ 0 ₃ .

The metal oxide composed of an oxygen atom and germanium includes germanium oxide such as GeO and Ge0 ₂ , preferably Ge0 ₂ .

The metal oxide composed of an oxygen atom and thallium includes thallium oxide such as T1 ₂ 0, TI ₂ O ₃ and TI ₄ O ₃ , preferably TI4O3.

The metal oxide composed of an oxygen atom and indium includes indium oxide such as In ₂ 0 ₃ .

The metal oxide composed of an oxygen atom and iridium includes iridium oxide such as I r0 ₂ .

The metal oxide composed of an oxygen atom and lanthanum includes lanthanum oxide such as La ₂ <0 ₃ .

The metal oxide composed of an oxygen atom and cerium includes cerium oxide such as Ce0 ₂ .

The metal component preferably includes a metal oxide, specifically manganese oxide, germanium oxide and lanthanum, more preferably manganese oxide and germanium oxide, still more preferably manganese oxide. The metal ion may form a metal-containing salt comprising the metal ion and a halogen ion.

The metal component derives from preferably one selected from the group consisting of Mn, Ge, Tl, La and Ce, more preferably one selected from the group consisting of Mn, Ge and La, still more preferably a metal selected from the group consisting of Mn and Ge .

The catalyst may comprise one or more kinds of the alkaline metal or alkaline earth metal component.

The alkaline metal or alkaline earth metal component may be an alkaline metal-containing compound, an alkaline earth metal-containing compound, an alkaline metal ion or an alkaline earth metal ion.

Examples of the alkaline metal-containing compound include compounds containing an alkaline metal such as Na, K, Rb and Cs . Examples of the alkaline earth metal-containing compound include compounds containing an alkaline earth metal such as Ca, Mg, Sr and Ba. Examples of the alkaline metal ion include Na ⁺ , K ⁺ , Rb ⁺ and Cs ⁺ . Examples of the alkaline earth metal ion include such as Ca ²⁺ , Mg ²⁺ , Sr ²⁺ and Ba ²⁺ .

The alkaline metal component may be an alkaline metal oxide . Examples of the alkaline metal oxide include Na ₂ 0, Na ₂ 0 ₂ , K ₂ 0, K ₂ 0 ₂ , Rb ₂ 0, Rb ₂ 0 ₂ , Cs ₂ 0, and Cs ₂ 0 ₂ . The alkaline earth metal component may be alkaline earth metal oxide. Examples of the alkaline earth metal oxide include CaO, Ca0 ₂ , MgO, Mg0 ₂ , SrO, Sr0 ₂ , BaO and Ba0 ₂ .

The alkaline metal or alkaline earth metal component is preferably an alkaline metal-containing compound, more preferably a sodium-containing compound.

The alkaline metal-containing compound and alkaline earth metal-containing compound are preferably an alkaline metal salt and an alkaline earth metal salt. The alkaline metal salt may comprise the alkaline metal ion as mentioned above with an anion The alkaline earth metal salt may comprise the alkaline earth metal ion as mentioned above with an anion. Examples of anions in such salts include CI ^" , Br ^" or I ^" , F ^" , OH ^" , N0 ₃ ^" , S0 ₄ ^2" and C0 ₃ ^2" . Such salts are preferably an alkaline metal salt with a halogen, such as an alkaline metal halide, or an alkaline earth metal-containing salt with a halogen, such as an alkaline earth metal halide, more preferably an alkaline metal salt with a halogen, still more preferably an alkaline metal chloride.

The catalyst comprises preferably CuO, Ru0 ₂ and a metal component deriving from Mn, Ge, Tl, In, Ir, La or Ce; more preferably CuO, Ru0 ₂ , a metal component deriving from Mn, Ge, Tl, La or Ce and an alkaline metal-containing compound; still more preferably CuO, Ru0 ₂ , a metal component deriving from Mn, and Ge and a sodium-containing compound, because the olefin oxide yield and selectivity can be improved by adopting such combination to the production of an olefin oxide. 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 and the metal component, and optionally the alkaline or alkaline earth metal component are 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 porous support as mentioned above.

Examples of such a halogen-containing compound include copper halides such as CuCl and CuC± ₂ , ruthenium halides such as RuC± ₃ and copper oxyhalides such as CuOC± ₂ , CUCIO ₄ ,

CIO ₂ CU (CIO ₄ ) ₃ and CU ₂ O (010 ₄ ) _2/ ruthenium oxyhalides such as RU ₂ OCI ₄ , RU ₂ OCI ₅ and RU ₂ OCI ₆ . If the catalyst comprises the halogen component, the component may be supported on the porous support as mentioned above.

The catalyst may further comprise a composite oxide including those composed of copper, ruthenium and oxygen; those composed of copper, sodium and oxygen; those composed of sodium, ruthenium and oxygen; those composed of sodium, oxygen and any one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce; those composed of oxygen, any of copper and ruthenium, and any one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce .

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.

The molar ratio of V, Mo or W to ruthenium metal in the catalyst is preferably less than 0.25, and more preferably less than 0.1, and it is still more preferable that the catalyst substantially contains no V, Mo or W.

Production of the catalyst is not restricted to a specific process, and examples of which include the conventional methods such as an impregnation method, a precipitation method, a deposition precipitation method, a chemical vapour deposition method, a mechnano-chemical method, and a solid state reaction method, and an impregnation method is preferable.

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 containing a copper ion, a ruthenium ion and a metal ion to prepare a composition, followed by calcining the composition, said metal ion deriving from one selected from the group consisting of Mn, Ge, Tl, In, Ir, La and Ce . The porous support can be in form of powder, or shaped to a desired stucture as necessary.

The composition obtained by impregnating the porous support with the solution or the suspension is preferably aged with stirring at a temperature of 5°C to 100°C, and more preferably 10°C to 50°C. The composition can be used as it is, and is preferably aged for some time. Aging time is preferably in the range from 0.5 to 48 hours, and more preferably 1 to 25 hours .

The porous support can be in form of powder, or shaped to a desired structure as necessary.

If the catalyst comprises the alkaline metal or alkaline earth metal component, it can be obtained in the same procedure as mentioned above except that solution or a suspension contains copper ion, a ruthenium ion, a metal compound or ion, an alkaline metal or alkaline earth metal ion.

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 compound or ion, an alkaline metal or alkaline earth metal ion and a halogen ion.

The solution or a suspension containing a copper ion, a ruthenium ion and the above-mentioned metal compound or ion can be prepared by mixing a copper metal salt, a ruthenium metal salt and a metal-containing salt as mentioned below in a solvent .

Examples of the copper metal salt include copper acetate, copper ammonium chloride, copper bromide, copper carbonate, copper ethoxide, copper hydroxide, copper iodide, copper isobutyrate, copper isopropoxide, copper oxalate, copper oxychroride, copper oxide, copper nitrates, and copper chlorides, and copper nitrates and copper chlorides are preferable.

Examples of the ruthenium metal salt include, for example, a halide such as ruthenium bromide, ruthenium chloride, ruthenium iodide, an oxyhalide such as RU ₂ OCI ₄ , RU ₂ OCI ₅ and RU ₂ OC ₁₆ , a halogeno complex such as [RUCI ₂ (H ₂ O) ₄ ] CI , an ammine complex such as [Ru (NH ₃ ) ₅ H ₂ 0] Cl ₂ , [Ru (NH ₃ ) ₅ C1 ] Cl ₂ , [Ru (NH ₃ ) ₆ ] Cl ₂ and [Ru (NH ₃ ) ₆ ] CI ₃ , a carbonyl complex such as Ru (CO) 5 and Ru ₃ (CO)i2, a carboxylate complex such as [RU ₃ O (OCOCH ₃ ) ₆ (H20) 3] , ruthenium nitrosylchloride, and [RU2 (OCOR) 4 ] CI (R=alkyl group having 1 to 3 carbon atoms) , a nitrosyl complex such as

[Ru(NH ₃ ) ₅ (NO) ]C1 ₃ , [Ru (OH) (NH ₃ ) 4 (NO) ] (N0 ₃ ) 2 and [Ru (NO) ] (N0 ₃ ) 3, an amine complex, an acetylacetonate complex, an oxide such as RUO2, and ammonium salt such as (NIHU^RuCle, and ruthenium salt containing CI is preferable.

Examples of the metal-containing salt include the following ones.

Manganese metal salt such as manganese carbonate, manganese nitrate, manganese sulfate, manganese bromide, manganese chloride, manganese iodide, manganese perchlorate, manganese acetate, and manganese acetylacetonate.

Germanium metal salt such as germanium bromide, germanium chloride, germanium iodide, germanium isopropoxide, germanium ethoxide, and germanium methoxide.

Thallium metal salt such as thallium sulfate, thallium nitrate, thallium bromide, thallium chloride, thallium iodide, thallium acetate, thallium carbonate, and thallium oxalate.

Indium metal salt include halides such as InBr, InBr ₃ , InCl, InCla, Inl, Inl ₃ , InF ₃ , In (OH) 3, In (OCH (CH ₃ ) 2) 3, In(N0 ₃ ) ₃ , In(C10 ₄ ) ₃ , In ₂ (S0 ₄ ) ₃ , and In(OOCCH ₃ ) ₃ .

Iridium metal salt includes IrBr ₃ , IrBr ₄ , IrCl ₃ , IrCl ₄ and IrI4. Lanthanum metal salt include La (NO ₃ ) 3, La (OH) ₃ , La2 (CO ₃ ) 3, La ₂ (S0 ₄ ) ₃ , LaBr ₃ , LaCl ₃ , LaF ₃ , Lal ₃ , La(C10 ₄ ) ₃ , La2(C20 ₄ ) ₃ , La(OC ₃ H7) ₃ and La(C ₂ H ₅ 0) ₃ .

Cerium metal salt include Ce(N0 ₃ ) ₃ , Ce ₂ (C0 ₃ ) ₃ , Ce(S0 ₄ ) ₂ , Ce ₂ (S0 ₄ ) ₃ , CeBr, CeCl ₃ , CeF ₃ , Cel ₂ , Ce(C10 ₄ ) ₃ , (CH ₃ COO) ₃ Ce and Ce ₂ (C ₂ 0 ₄ ) ₃ .

The alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the alkaline metal or alkaline earth metal component. 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 include water, alcohols such as methanol or ethanol, and ethers. The amount of the solvent is preferably 0.01 to 2000 parts by weight per part by weight of copper salt. If the catalyst contains the support, the amount of the solvent is preferably 0.01 to 500 parts by weight per part by weight of the support, and more preferably 0.1 to 100 parts by weight.

The composition as prepared by the impregnation is usually dried, and examples of the drying method include evaporation to dryness, spray drying, drum drying and flash drying. The composition as prepared by the impregnation is preferably dried at a temperature of 10°C to 250°C, and more preferably 40 ^° C to 200 ^° C before calcining the composition. Drying may be performed under an atmosphere of air or also under an inert gas atmosphere (for example, Ar, N ₂ , He) at standard pressure or reduced pressure. A drying time is preferably in the range from 0.5 to 24 hours. After drying, the composition can be shaped to a desired structure as necessary.

Calcining the composition is not limited, but preferably may be performed under a gas atmosphere containing oxygen and/or inert gas such as nitrogen, helium and argon. Examples of such a gas stream include air, an oxygen gas, nitrous oxide, and other oxidizing gases. The gas may be used after being mixed at an appropriate ratio with a diluting gas such as nitrogen, helium, argon, and water vapor. An optimal temperature for calcination varies depending on the kind of the gas and the composition, however, a too high temperature may cause agglomeration of the ruthenium component and copper oxide. Accordingly, the calcination temperature is typically 200 to 800°C, preferably 400 to 600°C. The calcining time is preferably in the range from 0.5 hour to 24 hours.

The catalyst can be used as powder, but it is usual to shape it into desired structures such as spheres, pellets, cylinders, rings, hollow cylinders or stars. The catalyst can be shaped by a known procedure such as extrusion, ram extrusion, and tableting. The calcination is normally performed after shaping into the desired structures, but it can also be performed before shaping them.

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 amonoolefin 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.

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. One or more reactors can be used for the reaction. If the number of reactors is large, small reactors, for example microreactors , can be used. The reactors each can have multiple channels.

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 7 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), CO _x (C0 ₂ and CO), and propanal (PaL) and acrolein (AC) .

Propylene conversions (X _PR ) were determined from the following:

X _PR = { [PO+AC+AT+PaL+C0 ₂ /3] out/ [C ₃ H ₆ ] _in } 100%; and PO selectivities (S _P o) were then calculated using the following expression:

S _P O = { [PO] / [PO+AC+AT+PaL+C0 ₂ /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 (Si0 ₂ , Japan Aerosil, 380 m ² /g) was added to an aqueous solution mixture containing 0.54 g of (NH ₄ ) ₂ RuCl ₆ (Aldrich) , 0.30 g of Cu(N0 ₃ ) ₂ (Wako) , 0.28 g of MnCl ₂ (Wako) and 0.10 g of NaCl (Wako) , followed by stirring for 24 hours in the air to impregnate the support with the metal salts. The resulting material was then heated at 100 °C until dried, and calcined at 500 °C for 12 hours in the air to give a catalyst.

The catalyst was evaluated by using a fixed-bed reactor. Filling a 1/2-inch reaction tube made of stainless steel with 1 mL of the thus obtained catalyst, the following gases were fed to the reaction tube to carry out the reaction : 7.5 mL/minute of propylene, 15 mL/minute of the air, 16.5 mL/minute of a nitrogen gas. Such a reaction was carried out at the reaction temperature of 270°C under the increased pressure (equivalent to 0.3 MPa in the absolute pressure), with GHSV of 2340hr ^_1 .

Example 2

Catalysts were prepared in the same manner as Example 1 except that 0.23 g of GeCl ₄ (Wako) was used instead of MnCl ₂ . The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.

Example 3

Catalysts were prepared in the same manner as Example 1 except that 0.15 g of TICI3 (Wako) was used instead of MnCl ₂ . The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.

Example 4

Catalysts were prepared in the same manner as Example 1 except that 0.15 g of InCl ₃ (Wako) was used instead of MnCl ₂ . The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1. Example 5

Catalysts were prepared in the same manner as Example 1 except that 0.03 g of IrCl ₃ (Wako) was used instead of MnCl ₂ . The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.

Example 6

Catalysts were prepared in the same manner as Example 1 except that 0.03 g of LaCl ₃ (Wako) was used instead of MnCl ₂ . The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.

Example 7

Catalysts were prepared in the same manner as Example 1 except that 0.05 g of CeCl ₃ (Wako) was used instead of MnCl ₂ . The reaction was conducted at the reaction temperature shown in Table 1, in the same manner as Example 1.

Comparative Example 1

The metal compostion was prepared by a co-impregnation method. A predetermined weight (1.9 g) of an amorphous silica powder (Si0 ₂ , Japan Aerosil, 380 m /g) was added to an aqueous solution mixture containing 0.54 g of ( H ₄ ) ₂ RuCl ₆ (Aldrich) , 0.30 g of Cu(N0 ₃ ) ₂ (Wako) and 0.10 g NaCl (Wako) , followed by stirring for 24 hours in the air to impregnate the support with the metal salts. The resulting material was then heated at 100 °C until dried, and calcined at 500 °C for 12 hours in the air to give a catalyst .

The catalyst as obtained was applied to the same reaction as Example 1 except that the catalyst was changed.

The results of Examples 1 to 7 and Comparative Example 1 are shown in Table 1.

670693 Atty. Docket No. 098068-0155

[Table 1]

Note: (1) The total metal loading of Ru, Cu, Na and M is weight parts relative to 100 weight parts of Si02.

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4843-2089-9598.1

Example 8

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 .