WO2013100173A1 - Process for producing olefin oxide using a catalyst comprising a ruthenium oxide and a tellurium component - Google Patents

Process for producing olefin oxide using a catalyst comprising a ruthenium oxide and a tellurium component Download PDF

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Publication number
WO2013100173A1
WO2013100173A1 PCT/JP2012/084274 JP2012084274W WO2013100173A1 WO 2013100173 A1 WO2013100173 A1 WO 2013100173A1 JP 2012084274 W JP2012084274 W JP 2012084274W WO 2013100173 A1 WO2013100173 A1 WO 2013100173A1
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Prior art keywords
oxide
catalyst
tellurium
olefin
ruthenium
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PCT/JP2012/084274
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French (fr)
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WO2013100173A9 (en
Inventor
Yoshihiko Ohishi
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Sumitomo Chemical Company, Limited
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Publication of WO2013100173A1 publication Critical patent/WO2013100173A1/en
Publication of WO2013100173A9 publication Critical patent/WO2013100173A9/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0576—Tellurium; Compounds thereof
    • B01J35/615—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation

Definitions

  • the present invention relates to a process for producing an olefin oxide.
  • olefin epoxidation in the presence of a metal-based catalyst has been proposed.
  • 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.
  • Patent Document 003
  • Patent Document 1 US 2003/0191328
  • Patent Document 2 JP 2002-371074 Summary of Invention
  • An object to be achieved by the present invention is to provide a novel process for producing an olefin oxide and a novel catalyst used for the same that result in providing a further improved olefin oxide yield and selectivity.
  • the present invention provides:
  • a process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising a ruthenium oxide and a tellurium component and no copper oxide;
  • the process of the present invention comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) ruthenium oxide and (b) tellurium component and no copper oxide .
  • the catalyst preferably contains a support, such as a porous support and a non-porous support .
  • a ruthenium oxide and a tellurium component are preferably supported on a support, more preferably supported on a porous support.
  • the non-porous support include a non-poroUs support comprising Si0 2 such as CAB-O-SIL (registered trademark) .
  • the catalyst containing a support is valuable for production of olefin oxides, which is one aspect of the present invention.
  • the porous support has pores capable of supporting one or both of the components (a) and (b) .
  • the porous support preferably comprises A1 2 0 3 , Si0 2 , Ti0 2 , or Zr0 2 , more preferably Si0 2 .
  • Examples of the porous support comprising Si0 2 include mesoporous silica.
  • Such porous supports may also comprise zeolites.
  • the support may be in form of powder, or may be shaped to a desired stucture.
  • the catalyst may comprise one or more kinds of the component (a) .
  • the component (a) is usually composed of ruthenium and oxygen.
  • Examples of the ruthenium oxide include Ru 2 0 4 , Ru 2 0 5 , Ru 3 0 5 , Ru 3 0 6 , Ru0 4 , and Ru0 2 .
  • the component (a) is preferably Ru0 2 .
  • the catalyst may comprise one or more kinds of the component (b) .
  • the component (b) may be tellurium- containing compound or tellurium ion.
  • the tellurium-containing compound include tellurium oxide such as TeO, Te0 2 , Te0 3 or Te 2 0 5 , and tellurium salt with anion such as CI “ , Br “ , I “ , F “ , OH “ , NO 3” or C0 3 2” .
  • Examples of the tellurium ion include Te 2+ , Te 4+ , Te 6+ , Te 2" .
  • the component (b) is preferably tellurium oxide, ,more preferably those comprising tellurium and an oxygen atom, still more preferably Te0 2 .
  • the catalyst may comprise one or more kinds of (c) alkaline metal component or alkaline earth metal component.
  • the component (c) may be supported on the above-mentioned support.
  • 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.
  • Examples of the alkaline metal-containing compound include compounds containing an alkaline metal such as Na, , 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 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.
  • 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 “ , 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 NaCl, as the (c) component, it can show excellent olefin oxide selectivity.
  • the tellurium/ruthenium molar ratio in the catalyst is preferably 0.001/1 to 50/1 based on their atoms. When the molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved.
  • the lower limit of the molar ratio is more preferably 0.005/1, still more preferably 0.008/1.
  • the upper limit of the molar ratio is more preferably 1/1, still more preferably 0.5/1.
  • the (c) component/ruthenium molar ratio in the catalyst is preferably 0.001/1 to 50/1 based on their atoms When the molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved.
  • the lower limit of the molar ratio is more preferably 0.01/1, still more preferably 0.1/1.
  • the upper limit of the molar ratio is more preferably 10/1, still more preferably 5/1.
  • the total content of these components is preferably 0.01 to 80 weight parts relative to 100 weight parts of a porous support.
  • the lower limit of the total content is more preferably 0.05 weight parts, still more preferably 0.1 weight parts relative to 100 weight parts of a porous support.
  • the upper limit of the total content is more preferably 50 weight parts, still more preferably 30 weight parts relative to 100 weight parts of a porous support .
  • the catalyst may comprise (d) halogen component besides the components (a) , (b) , (c) and (d) .
  • the component (d) is generally a halogen-containing compound. Examples of the halogen include chlorine, fluorine, iodine and bromine:.
  • halogen-containing compound examples include copper halides such as CuCl and CuCl 2 , tellurium halides such as TeCl 2 and TeCl 4 ruthenium halides such as RuCl 3 and ruthenium oxyhalides such . as Ru 2 OCl 4 , Ru 2 OCl 5 and Ru 2 OCl 6 , and tellurium oxyhalides such as Te 6 0nCli 2 .
  • the catalyst comprises the component (d)
  • the component may be supported on any of the components (a) , (b) and (c) or the support .
  • the catalyst may further comprise (e) composite oxides including those composed of tellurium, sodium and oxygen, such as Na 2 Te0 3 , Na 2 Te0 4 , Na 2 Te 4 0 9 , and Na 4 Te0 5 , and those composed of sodium, ruthenium and oxygen, and ruthenium, tellurium and oxygen.
  • composite oxides including those composed of tellurium, sodium and oxygen, such as Na 2 Te0 3 , Na 2 Te0 4 , Na 2 Te 4 0 9 , and Na 4 Te0 5 , and those composed of sodium, ruthenium and oxygen, and ruthenium, tellurium and oxygen.
  • the component may be supported on the support or any of the components (a), (b) , (c) and (d) as mentioned above.
  • the catalyst comprises no copper oxide.
  • Production of the catalyst is not restricted to a specific process, ' and examples of which include the conventional methods such as impregnation method, precipitation method, deposition precipitation method, chemical vapour deposition method, mechnano-chemical method, and solid state reaction method, and impregnation method is preferable.
  • the catalyst can be obtained by impregnating a support with a solution or a suspension containing a ruthenium ion, a tellurium ion or compound, and optionally an alkaline metal or alkaline earth metal- containing ion and/or a halogen ion to prepare a composition, followed by calcining the composition obtained.
  • the solution or suspepension containing above- mentioned ions can be prepared by mixing a ruthenium metal salt and a tellurium metal salt,' and optionally an alkaline metal or alkaline earth metal-containing salt and/or a halogen-containing compound in a solvent.
  • tellurium compound or salt examples include a halide such as TeF 6 , TeBr 4 , TeCl 4 and Tel 4 , an oxyhalide, oxide such as TeO, Te0 2 and Te0 3 , an alkoxide such as Te(OC 2 H 5 ) 4i a tellurate such as H 2 Te0 3f H 6 Te0 6 , Na 2 Te0 3 and Na 2 Te0 4 , preferably halide and oxide, more preferably oxide, still more preferably Te0 2 .
  • a halide such as TeF 6 , TeBr 4 , TeCl 4 and Tel 4
  • an oxyhalide, oxide such as TeO, Te0 2 and Te0 3
  • an alkoxide such as Te(OC 2 H 5 ) 4i
  • a tellurate such as H 2 Te0 3f H 6 Te0 6 , Na 2 Te0 3 and Na 2 Te0 4
  • halide and oxide more preferably oxide, still more preferably Te0 2 .
  • the ruthenium metal salt examples include a halide such as ruthenium bromide, ruthenium chloride, ruthenium iodide, an oxyhalide such as Ru 2 OCl , Ru 2 OCl 5 and Ru 2 OCl 6 , a halogeno complex such as [RuCl 2 (H 2 0) ] CI, an ammine complex such as [Ru(NH 3 ')5H 2 0] Cl 2 , [Ru (NH 3 ) 5 C1] Cl 2 , [Ru (NH 3 ) 6 ] Cl 2 and [Ru(NH 3 ) 6 ] cl 3 , a carbonyl complex such as Ru(CO) 5 and Ru 3 (CO)i 2 , a carboxylate complex such as
  • the alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the (c) component.
  • the alkaline metal or 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 earth metal benzoates, alkaline metal alkoxides, alkaline earth metal alkoxides, alkaline metal carbonates, alkaline earth metal carbonates, alkaline metal citrates, alkaline earth metal citrates, alkaline metal formates, alkaline earth metal formates, alkaline metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, alkaline metal hydroxides, alkaline earth metal hydro
  • the catalyst comprising the components (a) , (b) , (c) and (d) can be produced from a solution obtained by mixing the ruthenium metal salt, the tellurium compound or salt, and the alkaline metal salt or alkaline earth metal salt in a solvent.
  • Atr-least one selected from the group consisting of the above-mentioned ' metal salts preferably contains a halogen ion, more preferably a chloride ion.
  • Such a halogen ion may form the (c) component such as NaCl and the (d) component such as halides and oxyhalides of Ru or Te .
  • the solution may contain acidic or basic compounds in order to control its pH.
  • the acid compounds include hydrochloric acid, nitric acid, nitrous acid perchloric acid.
  • Examples of basic compounds include alkaline metal hydroxides, amine compounds, imine compounds, hydrazine or hydrazine compounds, ammonia, hydroxylamine , hydroxyamine and ammonium hydroxides .
  • the solvent examples include water, alcohols such as methanol or ethanol , and ethers .
  • the amount of the solvent is preferably 0.01 to 2000 parts by weight per 1 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 1 part by weight of the support, and more preferably 0.1 to 100 parts by weight.
  • the molar ratio of V, Mo or W to ruthenium metal in the cattalyst is preferably less than 0.25, and more preferably less than 0.1, and it is still more peferable that the catalyst substantially contains no V, Mo or W.
  • 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 usually dried, and the drying method thereof is not limited.
  • the composition as prepared by the impregnation is preferably dried at a temperature of 10°C to c 250°C, and more preferably 40°C to 200°C before calcining the composition. Drying may be performed under an atmosphere of oxygen containing gas such as air or also under an inert gas atmosphere (for example, Ar, N 2 , He) at standard pressure or reduced pressure.
  • a drying time is preferably in the range from 0.5 to 24 hours.
  • the method of calcining the composition is not limited, and calcining the composition is preferably performed under a gas atmosphere containing oxygen and/or inert gas such as nitrogen, helium and argon.
  • a gas examples include air, an oxygen gas, nitrous oxide, and other oxidizing gases.
  • the gas may be used after being mixed at an appropriate ratio with a diluting gas such as nitrogen, helium, argon, and water vapor.
  • a diluting gas such as nitrogen, helium, argon, and water vapor.
  • An optimal temperature for calcination varies depending on the kind of the gases and the compositions, however, a too high temperature may cause agglomeration of ruthenium oxide. Accordingly, the calcination temperature is typically 200°C to 800°C, preferably 400°C to 600°C.
  • the calcining time is preferably in the range from 0.5 hour to 24 hours .
  • the catalyst can be used as powder, but it is usual to shape it into desired structures such as spheres, pellets, cylinders, rings, hollow cylinders or stars.
  • the catalyst can be shaped by a known procedure such as extrusion, ram extrusion, tableting.
  • the calcination is normally performed after shaping into the desired structures, but it can also be performed before shaping them.
  • the olefin may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms.
  • the olefin may be a monoolefin or a diolefin.
  • the monoolefin include ethylene, propylene, butene, pentene, hexane, heptene, octene, nonene, and decene.
  • the diene include butadiene such as 1, 3 -butadiene or 1, 2 -butadiene.
  • olefin examples include preferably monoolefin, more preferably ethylene, propylene, butene, pentene, hexene, heptene and octene, still more preferably ethylene, propylene and butene, most preferably propylene.
  • the reaction is generally performed in the gas phase.
  • the olefin and oxygen may be fed respectively in the form of a gas.
  • Olefin and oxygen gases can be fed in the form of .their mixed gas.
  • Olefin and oxygen gases may be fed with diluent gases. Examples of diluent gases include nitrogen methane, ethane, propane, carbon dioxide, or rare gases, such as argon and helium.
  • oxygen source pure oxygen may be used, or a mixed gas containing a gas inactive to the reaction, such as air, may be used.
  • the amount of oxygen used varies depending on the reaction type, the catalyst, the reaction temperature or the like.
  • the amount of oxygen is typically 0.01 mol to 100 mol, and preferably 0.03 to 30 mol, more preferably 0.05 to 10 mol, and especially preferably 0.25 mol 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.
  • reaction 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 l/(l.h) to 100000 Nl/(l.h), preferably
  • 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.
  • the reaction may be carried out as a batch reaction or a continuous flow reaction, preferably as a continuous flow reaction for industrial application.
  • the reaction of the present invention may be carried out by mixing an olefin and oxygen and then contacting the mixture with the catalyst under reduced pressure to the increased pressure.
  • the reactor type is not limited. Examples of the reactor type are fluid bed reactor, fixed bed reactor, moving bed reactor, and the like, preferably fixed bed reactor. In the case of using fixed bed reactor, single tube reactor or multi tube reactor can be employed. More than one reactor can be used. If the number of reactors is large, small reactors as for example microreactors, can be used, which can have multiple channels.
  • the catalyst can be packed into the reactor or coated on the surface of the reactor wall.
  • the coated type reactor is suitable for microreactors and the packed bed reactor is suitable for a large reactor.
  • reaction mixture can be passed through the packed bed reactor in up-flow mode or in downflow mode.
  • Adiabatic type reactor or heat exchange type reactor may also be used.
  • adiabatic type reactor a part of the reaction mixture from the reactor can be recycled into the reactor after heat-exchanging to control the reaction temperature.
  • the reactors can be arranged in series and/or in parallel.
  • a heat exchanger can be used between the reactors for controling reaction temperature .
  • the olefin oxide may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms.
  • the olefin oxide may have one carbon-carbon double bond when the diolefin is applied for the reaction.
  • Examples of the olefin oxide having one carbon-carbon double bond include 3 , 4 -epoxy- 1-butene .
  • Examples of the olefin oxides include preferably ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide and octene oxide, more preferably ethylene oxide, propylene oxide and butene oxide, still more preferably propylene oxide .
  • the olefin oxide as obtained can be collected by absorption with a suitable solvent such as water and acetonitrile followed by conducting a method known in the art such as separation by distillation.
  • a reaction gas was mixed with ethane (10 Nml/min) as an external standard, and then directly introduced in the TCD-GC equipped with a column of Gaskuropack 54 (2 m) . All products in the reaction gas were collected for 1 hour with double methanol traps connected in series and cooled with an ice bath. The two methanol solutions were mixed together and added to anisole as an external standard, and then analyzed with two FID-GCs equipped with different columns, PoraBOND U (25 m) and PoraBOND Q (25 m) .
  • the detected products were propylene oxide (PO) , acetone (AT) , acetaldehyde (AD) , CO x (C0 2 and CO) , and propanal (PaL) and acrolein (AC).
  • Each metal weight was determined from the amounts of the metal salts used for preparation of catalyst.
  • a catalyst was prepared by an impregnation method. A " predetermined weights 2.0 g of Ru0 2 (Furuya Metal) and 0..022 g of Te0 2 (Wako) was crushed and mixed by a mortar. The resulting material ' was then calcined at 500°C for 12 hours in the air to give a catalyst. Te/Ru molar ratio is 0.01.
  • the catalyst was evaluated by using a fixed-bed reactor. Filling a 22mmcp reaction tube made of grass 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 220°C under the atmospheric pressure.
  • 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 m 2 /g) was added to an aqueous solution mixture containing 0.55 g of (NH ) 2 R Cl 6 (Aldrich) , and 0.04 g of TeCl 4 (Wako) , followed by stirring it 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 total amount of Ru and Te was 9.2 weight parts relative to 100 weight parts of Si0 2 , and Te/Ru molar ratio is 0.1.
  • 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 condition of the increased pressure (equicalent to 0.3 MPa in the absolute pressure).
  • 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 m 2 /g) was added to an aqueous solution mixture containing 0.55 g of (NH ) 2 RuCl 6 (Aldrich) , 0.1 g of NaCl (Wako) and 0.04 g of TeCl 4 (Wako) , followed by stirring it 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 total amount of Ru, Te and Na was 11.2 weight parts relative to 100 weight parts of Si0 2 , and Te/Ru/Na molar ratio is 0.1/1/1.1.
  • the present invention by using a . catalyst comprising a ruthenium oxide and a tellurium component and no copper oxide, it is possible to provide a novel process for producing an olefin oxide. Furthermore, the present invention provides a novel catalyst used for the same .

Abstract

The invention relates to a process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising a ruthenium oxide and a tellurium component. Herein, the catalyst contains no copper oxide.

Description

DESCRIPTION
Title of 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 producicng 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.
Citation List
Patent Document 003]
Patent Document 1: US 2003/0191328
Patent Document 2: JP 2002-371074 Summary of Invention
Technical Problem
[0004]
An object to be achieved by the present invention is to provide a novel process for producing an olefin oxide and a novel catalyst used for the same that result in providing a further improved olefin oxide yield and selectivity.
Solution to Problem
[0005]
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 ruthenium oxide and a tellurium component and no copper oxide;
[2] The process according to [1], wherein the ruthenium oxide and the tellurium component are supported on a support ;
[3] The process according to [2] , wherein the support comprises A1203/ Si02, Ti02 or Zr02; [4] The process according to [2] or [3] , wherein the support comprises Si02;
[5] The process according to any .one of [1] to [4] , wherein the tellurium/ruthenium molar ratio in the catalyst is 0.001/1 to 50/1;
[6] The process according to any one of [1] to [5], wherein the ruthenium oxide is Ru02;
[7] The process according to any one of [1] to [6] , wherein the tellurium component comprises tellurium and an oxygen atom;
[8] The process according to any one of [2] to [7], wherein the total amount of the ruthenium oxide and the tellurium component is 0.01 to 80 weight parts relative to 100 weight parts of a support;
[9] The process according to any one of [2] to [8] , wherein the catalyst is obtained by impregnating a support with a solution or a suspension containing a ruthenium ion and a tellurium ion or compound, followed by calcining the composition obtained;
[10] The process according to any one of [1] to [9] , wherein the olefin is propylene and the olefin oxide is propylene oxide;
[11] The process according to any one of [1] to [10] , which comprises reacting an olefin with oxygen at a temperature of 100 to 350°C; [12] A catalyst for production of an olefin oxide which comprises a ruthenium oxide and a tellurium component and no copper oxide;
[13] The catalyst according to [12] , wherein the ruthenium oxide is Ru02;
[14] The catalyst according to [12] or [13], wherein the tellurium component comprises tellurium and an oxygen atom;
[15] The catalyst according to any one of [12] to [14] , wherein the ruthenium oxide and the tellurium component are supported on a support.
Advantageous Effects of Invention
[0006]
According to the present invention, it is possible to provide a process for producing an olefin oxide that results in providing a further improved olefin oxide yield and selectivity by using a catalyst comprising a ruthenium oxide and a tellurium component and no copper oxide.
Furthermore, it is possible to provide a novel catalyst that provides a further improved olefin oxide yield and selectivity.
Description of Embodiments
[0007]
The process of the present invention comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) ruthenium oxide and (b) tellurium component and no copper oxide .
[0008]
The catalyst preferably contains a support, such as a porous support and a non-porous support . A ruthenium oxide and a tellurium component are preferably supported on a support, more preferably supported on a porous support. Examples of the non-porous support include a non-poroUs support comprising Si02 such as CAB-O-SIL (registered trademark) . The catalyst containing a support is valuable for production of olefin oxides, which is one aspect of the present invention.
[0009]
The porous support has pores capable of supporting one or both of the components (a) and (b) . The porous support preferably comprises A1203, Si02, Ti02, or Zr02, more preferably Si02. Examples of the porous support comprising Si02 include mesoporous silica. Such porous supports may also comprise zeolites.
[0010]
The support may be in form of powder, or may be shaped to a desired stucture.
[0011]
The catalyst may comprise one or more kinds of the component (a) .
[0012]
The component (a) is usually composed of ruthenium and oxygen.
[0013]
Examples of the ruthenium oxide include Ru204, Ru205, Ru305, Ru306, Ru04, and Ru02. The component (a) is preferably Ru02.
[0014]
The catalyst may comprise one or more kinds of the component (b) . The component (b) may be tellurium- containing compound or tellurium ion. 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", NO3" or C03 2" . Examples of the tellurium ion include Te2+, Te4+, Te6+, Te2". The component (b) is preferably tellurium oxide, ,more preferably those comprising tellurium and an oxygen atom, still more preferably Te02.
[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 support.
[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, , Rb and Cs . · Examples of the alkaline earth metal- containing compound include compounds containing an alkaline earth metal such as Ca, Mg, Sr and Ba. Examples of the alkaline metal ion include Na+, K+, Rb+ and Cs+. Examples of the alkaline earth metal ion include such as Ca2+, Mg2+, Sr2+ and Ba2+.
[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, MgO, 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" 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]
Particularly if the catalyst comprises NaCl, as the (c) component, it can show excellent olefin oxide selectivity.
[0022]
The tellurium/ruthenium molar ratio in the catalyst is preferably 0.001/1 to 50/1 based on their atoms. When the molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved. The lower limit of the molar ratio is more preferably 0.005/1, still more preferably 0.008/1. The upper limit of the molar ratio is more preferably 1/1, still more preferably 0.5/1. [0023]
The (c) component/ruthenium molar ratio in the catalyst is preferably 0.001/1 to 50/1 based on their atoms When the molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved. The lower limit of the molar ratio is more preferably 0.01/1, still more preferably 0.1/1. The upper limit of the molar ratio is more preferably 10/1, still more preferably 5/1.
[0024]
When the components (a) and (b) , and optionally any of the components (c) 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 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 .
[0025]
The catalyst may comprise (d) halogen component besides the components (a) , (b) , (c) and (d) . The component (d) is generally a halogen-containing compound. Examples of the halogen include chlorine, fluorine, iodine and bromine:.
[0026]
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 ruthenium oxyhalides such . as Ru2OCl4, Ru2OCl5 and Ru2OCl6, and tellurium oxyhalides such as Te60nCli2. If the catalyst comprises the component (d) , the component may be supported on any of the components (a) , (b) and (c) or the support .
[0027]
The catalyst may further comprise (e) composite oxides including those composed of tellurium, sodium and oxygen, such as Na2Te03, Na2Te04, Na2Te409, and Na4Te05, and those composed of sodium, ruthenium and oxygen, and ruthenium, tellurium and oxygen.
[0028]
If the catalyst comprises the component (e) , the component may be supported on the support or any of the components (a), (b) , (c) and (d) as mentioned above.
[0029]
The catalyst comprises no copper oxide.
[0030] Production of the catalyst is not restricted to a specific process,' and examples of which include the conventional methods such as impregnation method, precipitation method, deposition precipitation method, chemical vapour deposition method, mechnano-chemical method, and solid state reaction method, and impregnation method is preferable.
[0031]
When the components (a) and (b) , optionally in addition with the component (c) , (d) or (e) are supported on a support in the catalyst, the catalyst can be obtained by impregnating a support with a solution or a suspension containing a ruthenium ion, a tellurium ion or compound, and optionally an alkaline metal or alkaline earth metal- containing ion and/or a halogen ion to prepare a composition, followed by calcining the composition obtained.
[0032]
The solution or suspepension containing above- mentioned ions can be prepared by mixing a ruthenium metal salt and a tellurium metal salt,' and optionally an alkaline metal or alkaline earth metal-containing salt and/or a halogen-containing compound in a solvent.
[0033]
Examples of the tellurium compound or salt include a halide such as TeF6, TeBr4, TeCl4 and Tel4, an oxyhalide, oxide such as TeO, Te02 and Te03, an alkoxide such as Te(OC2H5)4i a tellurate such as H2Te03f H6Te06, Na2Te03 and Na2Te04, preferably halide and oxide, more preferably oxide, still more preferably Te02.
[0034]
Examples of the ruthenium metal salt include a halide such as ruthenium bromide, ruthenium chloride, ruthenium iodide, an oxyhalide such as Ru2OCl , Ru2OCl5 and Ru2OCl6, a halogeno complex such as [RuCl2 (H20) ] CI, an ammine complex such as [Ru(NH3')5H20] Cl2, [Ru (NH3) 5C1] Cl2 , [Ru (NH3) 6] Cl2 and [Ru(NH3) 6] cl3, a carbonyl complex such as Ru(CO)5 and Ru3(CO)i2, a carboxylate complex such as
[Ru30 (OCOCH3) 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 (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 (NH )2RuCl6, and ruthenium salt containing CI is preferable.
[0035]
The alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the (c) component. Examples of the alkaline metal or 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 NaN03 and NaCl are more preferable.
[0036]
If an alkaline metal salt with a halogen or alkaline earth metal salt with a halogen is used for production of the catalyst, the catalyst comprising the components (a) , (b) , (c) and (d) can be produced from a solution obtained by mixing the ruthenium metal salt, the tellurium compound or salt, and the alkaline metal salt or alkaline earth metal salt in a solvent. Atr-least one selected from the group consisting of the above-mentioned' metal salts preferably contains a halogen ion, more preferably a chloride ion. Such a halogen ion may form the (c) component such as NaCl and the (d) component such as halides and oxyhalides of Ru or Te . The solution may contain acidic or basic compounds in order to control its pH. Examples of the acid compounds include hydrochloric acid, nitric acid, nitrous acid perchloric acid. Examples of basic compounds include alkaline metal hydroxides, amine compounds, imine compounds, hydrazine or hydrazine compounds, ammonia, hydroxylamine , hydroxyamine and ammonium hydroxides .
[0037]
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 1 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 1 part by weight of the support, and more preferably 0.1 to 100 parts by weight.
[0038]
The molar ratio of V, Mo or W to ruthenium metal in the cattalyst is preferably less than 0.25, and more preferably less than 0.1, and it is still more peferable that the catalyst substantially contains no V, Mo or W.
[0039]
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.
[0040]
The composition as prepared by the impregnation is usually dried, and the drying method thereof is not limited. The composition as prepared by the impregnation is preferably dried at a temperature of 10°C toc 250°C, and more preferably 40°C to 200°C before calcining the composition. Drying may be performed under an atmosphere of oxygen containing gas such as air or also under an inert gas atmosphere (for example, Ar, N2, He) at standard pressure or reduced pressure. A drying time is preferably in the range from 0.5 to 24 hours. The method of calcining the composition is not limited, and calcining the composition is preferably performed under a gas atmosphere containing oxygen and/or inert gas such as nitrogen, helium and argon. Examples of such a gas include air, an oxygen gas, nitrous oxide, and other oxidizing gases. The gas may be used after being mixed at an appropriate ratio with a diluting gas such as nitrogen, helium, argon, and water vapor. An optimal temperature for calcination varies depending on the kind of the gases and the compositions, however, a too high temperature may cause agglomeration of ruthenium oxide. Accordingly, the calcination temperature is typically 200°C to 800°C, preferably 400°C to 600°C. The calcining time is preferably in the range from 0.5 hour to 24 hours .
[0041]
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.
[0042]
-Next, the following explains a reaction of an olefin with oxygen in the presence of the catalyst as described above .
[0043]
In the present invention, the olefin may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms. The olefin may be a monoolefin or a diolefin. Examples of the monoolefin include ethylene, propylene, butene, pentene, hexane, heptene, octene, nonene, and decene. Examples of the diene include butadiene such as 1, 3 -butadiene or 1, 2 -butadiene. Examples of the olefin include preferably monoolefin, more preferably ethylene, propylene, butene, pentene, hexene, heptene and octene, still more preferably ethylene, propylene and butene, most preferably propylene.
[0044]
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.
[0045]
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 mol to 100 mol, and preferably 0.03 to 30 mol, more preferably 0.05 to 10 mol, and especially preferably 0.25 mol to 10 mol with respect to 1 mol of the olefin.
[0046]
■ 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.
[0047]
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.
[0048]
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 l/(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 m/s to 50 m/s.
[0049]
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.
[0050]
• 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.
[0051]
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.
[0052]
Generally, the reaction mixture can be passed through the packed bed reactor in up-flow mode or in downflow mode.
[0053]
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.
[0054]
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 .
[0055]
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- 1-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 .
[0056]
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
[0057]
In Examples 1 to 3 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) .
[0058]
The detected products were propylene oxide (PO) , acetone (AT) , acetaldehyde (AD) , COx (C02 and CO) , and propanal (PaL) and acrolein (AC).
[0059]
Propylene conversions (XPR) were determined from the following:
XPR = { [PO+AC+AT+PaL+C02/3]out/ [C3H6] in} x 100%; and PO selectivities (SP0) were then calculated using the following expression:
Spo = { [PO] / [PO+AC+AT+PaL+C02/3] } x 100%
Each metal weight was determined from the amounts of the metal salts used for preparation of catalyst.
[0060]
Example 1
A catalyst was prepared by an impregnation method. A "predetermined weights 2.0 g of Ru02 (Furuya Metal) and 0..022 g of Te02 (Wako) was crushed and mixed by a mortar. The resulting material ' was then calcined at 500°C for 12 hours in the air to give a catalyst. Te/Ru molar ratio is 0.01.
[0061]
The catalyst was evaluated by using a fixed-bed reactor. Filling a 22mmcp reaction tube made of grass 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 220°C under the atmospheric pressure.
The results are shown in Table 1.
[0062]
Comparative Example 1
Procuction of propylene oxide is carried out in the same manner as Example 1 except that the catalyst of Ru02 (Furuya Metal) is used. The result is shown in Table 1.
[0063]
Table 1
Figure imgf000024_0001
[0064]
Example 2
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 0.55 g of (NH )2R Cl6 (Aldrich) , and 0.04 g of TeCl4 (Wako) , followed by stirring it 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. In the catalyst, the total amount of Ru and Te was 9.2 weight parts relative to 100 weight parts of Si02, and Te/Ru molar ratio is 0.1.
[0065]
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 condition of the increased pressure (equicalent to 0.3 MPa in the absolute pressure).
The results are shown in Table 2.
[0066]
Example 3
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 0.55 g of (NH )2RuCl6 (Aldrich) , 0.1 g of NaCl (Wako) and 0.04 g of TeCl4 (Wako) , followed by stirring it 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. In the catalyst, the total amount of Ru, Te and Na was 11.2 weight parts relative to 100 weight parts of Si02, and Te/Ru/Na molar ratio is 0.1/1/1.1.
[0067]
Table 2
Figure imgf000025_0001
Industrial Applicability
[0068]
According to the present invention, by using a. catalyst comprising a ruthenium oxide and a tellurium component and no copper oxide, it is possible to provide a novel process for producing an olefin oxide. Furthermore, the present invention provides a novel catalyst used for the same .

Claims

1. A process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising a ruthenium oxide and a tellurium component and no copper oxide .
2. The process according to claim 1, wherein the ruthenium oxide and the tellurium component are supported on a support .
3. The process according to claim 2 wherein the support comprises Al203, Si02, Ti02 or Zr02.
4. The process according to claim 2 or 3 , wherein the support comprises Si02.
5. The process according to claim 1, wherein the tellurium/ruthenium molar ratio in the catalyst is 0.001/1 to 50/1.
6. The process according to claim 1, wherein the ruthenium oxide is Ru02.
7. The process according to claim 1, wherein the tellurium component comprises tellurium and an oxygen atom.
8. The process according to claim 2, wherein the total amount of the ruthenium oxide and the tellurium component is 0.01 to 80 weight parts relative to 100 weight parts of a support.
9. The process according to claim 2, wherein the catalyst is obtained by impregnating a support with a solution or a suspension containing a ruthenium ion and a tellurium ion or compound, followed by calcining the composition obtained.
10. The process according to claim 1 or 2, wherein the olefin is propylene and the olefin oxide is propylene oxide .
11. The process according to claim 1 or 2, which comprises reacting an olefin with oxygen at a temperature of 100 to 350°C.
12. A catalyst for production of an olefin oxide which comprises a ruthenium oxide and a tellurium component and no copper oxide .
13. The catalyst according to claim 12, wherein the ruthenium oxide is Ru02.
14. The catalyst according to claim 12, wherein the tellurium component comprises tellurium and an oxygen atom.
15. The catalyst according to claim 12, wherein the ruthenium oxide and the tellurium component are supported on a support .
PCT/JP2012/084274 2011-12-27 2012-12-26 Process for producing olefin oxide using a catalyst comprising a ruthenium oxide and a tellurium component WO2013100173A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002371074A (en) 2001-04-13 2002-12-26 Mitsubishi Chemicals Corp Method for producing oxysilane compound
US20030191328A1 (en) 2000-05-18 2003-10-09 Ursula Jansen Method for expoxidation of hydrocarbons
US20050239643A1 (en) * 2004-04-22 2005-10-27 Abraham Benderly Structured oxidation catalysts

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Publication number Priority date Publication date Assignee Title
US20030191328A1 (en) 2000-05-18 2003-10-09 Ursula Jansen Method for expoxidation of hydrocarbons
JP2002371074A (en) 2001-04-13 2002-12-26 Mitsubishi Chemicals Corp Method for producing oxysilane compound
US20050239643A1 (en) * 2004-04-22 2005-10-27 Abraham Benderly Structured oxidation catalysts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALAN J. BAILEY ET AL: "Oxo complexes of ruthenium with N,N?-donors as oxidation catalysts for alkenes, alkanes and alcohols, and their osmium analogues", JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS, no. 21, 1 January 1995 (1995-01-01), pages 3537, XP055053951, ISSN: 0300-9246, DOI: 10.1039/dt9950003537 *

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