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WO2012094122A1 - Procédé de préparation d'un oxyde d'oléfine - Google Patents

Procédé de préparation d'un oxyde d'oléfine Download PDF

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Publication number
WO2012094122A1
WO2012094122A1 PCT/US2011/065167 US2011065167W WO2012094122A1 WO 2012094122 A1 WO2012094122 A1 WO 2012094122A1 US 2011065167 W US2011065167 W US 2011065167W WO 2012094122 A1 WO2012094122 A1 WO 2012094122A1
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Prior art keywords
catalyst
oxide
copper
process according
component
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English (en)
Inventor
Yoshihiko Ohishi
Anusorn Seubsai
Selim Senkan
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Publication of WO2012094122A1 publication Critical patent/WO2012094122A1/fr
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    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors

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.
  • USP6765101 mentions a method for synthesizing alkylene oxides from lower alkene which comprises reacting a source of lower alkylene with a source of oxygen in the presence of a phosphate modified catalyst .
  • the present invention provides:
  • a process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising a copper oxide and a sulfur-containing component.
  • a catalyst for production of an olefin oxide which comprises a copper oxide and a sulfur-containing component.
  • the process of the present invention comprises reacting an olefin with oxygen in the presence of a catalyst comprising a copper oxide and a sulfur-containing component.
  • a copper oxide and a sulfur-containing 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 one or both of a copper oxide and a phosphorous-containing component .
  • the porous support preferably comprises AI 2 O 3 , S 1O 2 , T1 O 2 , or Zr0 2 , more preferably Si0 2 .
  • Examples of the porous support comprising S1O 2 include mesoporous silica.
  • Such porous supports may also comprise zeolites.
  • non-porous support examples include a non-porous support comprising S1O 2 such as CAB-O-SIL (registered trademark) .
  • the support may be in form of powder or may be shaped to a desired structure.
  • 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 CU 2 O and CuO.
  • the copper oxide is preferably CuO.
  • the catalyst comprises one or more kinds of
  • the sulfur-containing component is, for example, a sulfur-containing ion.
  • the sulfur-containing ion include sulphate ions such as SC ⁇ 2- , sulfite ions such as HS03 ⁇ , SC>3 2 ⁇ .
  • the sulfur-containing ion is preferably sulphate ion.
  • the sulfur-containing component may form a sulfur-containing salt with the alkaline metal ions or the metal as described below .
  • the sulfur-containing salt may comprise a sulphate ion as mentioned above with a cation.
  • the cation include H , NH 4 , or the alkaline metal or alkaline earth metal ions as described below .
  • the sulfur-containing salt include H 2 S0 4 , NaHS0 4 , Na 2 S0 4 , (NH 4 )HS0 4 or (NH 4 ) 2 S0 4 , preferably H 2 S0 4 or Na 2 S0 4 , more preferably H 2 S0 4 .
  • the catalyst may comprise one or more kinds of ruthenium oxides.
  • the ruthenium oxide is usually composed of ruthenium and oxygen. Examples of the ruthenium oxide include Ru 2 0 4 , Ru 2 Os, RU 3 O 5 , RU 3 O 6 , Ru0 4 , and Ru0 2 .
  • the ruthenium oxide is preferably Ru0 2 .
  • the catalyst may further comprise one or more kinds of alkaline metal or alkaline earth metal component.
  • 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, andCs 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-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.
  • anions in such salts include halogen ions such as Cl ⁇ , Br " or I " , F “ ; OH “ ; N0 3 “ ; S0 4 2” ; C0 3 2” ; and a sulfur-containing ion as described above.
  • Such salts are preferably an alkaline metal salt with a halogen, such as an alkaline metal halide, more preferably an alkaline metal chloride.
  • the alkaline metal or alkaline earth metal component is preferably a sodium-containing compound.
  • the catalyst may comprise one or more kinds of tellurium components.
  • the tellurium component may be any tellurium component.
  • tellurium-containing compound or tellurium ion examples include tellurium oxide such as TeO, Te0 2 , Te03 or Te 2 0s, and tellurium salt with anion such as CI “ , Br “ , I “ , F “ , OH-, N0 3 " or C0 3 2" .
  • tellurium ion examples include Te , Te , Te , Te .
  • the tellurium component is preferably tellurium oxide, more preferably one comprising tellurium and an oxygen atom, still more preferably Te0 2 .
  • the catalyst comprises preferably copper oxides, any of ruthenium oxides and tellurium oxides, and a sulfate ion; more preferably copper oxides, ruthenium oxides, sodium salt and a sulfate ion; and still more preferably CuO, RuC>2, NaCl and H 2 S0 4 .
  • the catalyst comprises Na + and SC ⁇ 2- , it can show excellent olefin oxide selectivity.
  • the sulfur/copper molar ratio in the catalyst is preferably 0.001/1 to 50/1 based on their atoms .
  • the lower limit of the molar ratio is more preferably 0.01/1, still more preferably 0.05/1.
  • the upper limit of the molar ratio is more preferably 5/1, still more preferably 1/1.
  • the ruthenium/copper molar ratio in the catalyst is preferably 0.01/1 to 50/1 based on their atoms .
  • the lower limit of the molar ratio is more preferably 0.1 /l , still more preferably 0.2 /l .
  • the upper limit of the molar ratio is more preferably 5/1, still more preferably 1/1.
  • the alkaline metal or alkaline earth metal /copper molar ratio in the catalyst is preferably 0.001/1 to 50/1 based on their atoms.
  • 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 tellurium/copper molar ratio in the catalyst is preferably 0.001/1 to 50/1 basedon their atoms.
  • the lower limit of the molar ratio is more preferably 0.01/1, still more preferably 0.05/1.
  • the upper limit of the molar ratio is more preferably 1/1, still more preferably 0.5/1.
  • 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 a halogen component .
  • the halogen component means a component other than the halogen ion which forms an alkaline metal halide.
  • the halogen component may be a halogen ion or a halogen-containing compound.
  • Examples of the halogen for the halogen component include chlorine, fluorine, iodine and bromine.
  • halogen-containing compound examples include halides of copper, ruthenium or tellurium and oxyhalides of copper, ruthenium or tellurium.
  • halogen-containing compound examples include copper halides such as CuCl and CuCl 2 , tellurium halides such as eCl 2 and eCl 4 , ruthenium halides such as RUCI 3 and copper oxyhalides such as CuOCl 2 , CuC10 4 , C10 2 Cu (C10 4 ) 3 and Cu 2 0 (C10 4 ) 2, tellurium oxyhalides such as e 6 0nCli 2 , ruthenium oxyhalides such as RU2OCI4, RU2OCI5 and RU2OCI6.
  • the component may be supported on the porous support or the other components as mentioned above.
  • the catalyst may further comprise a composite oxide including those composed of copper, tellurium and oxygen, such as CuTe0 4 , CuTe0 3 and Cu 3 Te0 6 , those composed of tellurium, sodium and oxygen, such as a 2 e0 3 , a 2 Te0 4 , Na 2 Te 4 ⁇ D 9 , andNa 4 TeOs, and those composed of sodium, copper and oxygen, such as NaCu0 2 , Na 2 CuC> 2 , NaCuO and Na 6 Cu 2 ⁇ 0 6 , those composed of ruthenium, tellurium and oxygen, those composed of ruthenium, copper and oxygen such as RuCu 2 0 2 , RuCuC10 3 , Ru 2 Cu0 6 , Ru 2 Cu 2 0 2 , and those composed of ruthenium, sodium and oxygen.
  • a composite oxide including those composed of copper, tellurium and oxygen, such as CuTe0 4 , CuTe0 3 and Cu 3 Te0 6 , those composed of tellurium, sodium and oxygen, and
  • the component may be supported on the porous support or any of the 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.
  • the catalyst can be obtained by impregnating a porous support with a solution containing a copper ion and a sulfur-containing ion, and optionally a ruthenium ion, a tellurium ion, an alkaline metal or alkaline earth metal ion or a halogen ion, to prepare a composition, followed by calcining the composition .
  • the composition obtained by impregnating the porous support with the solution 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.
  • the solution containing the copper ion, and the sulfur-containing ion, and the optional components can be prepared by dissolving a copper metal salt and a
  • sulfur-containing salt and optionally a ruthenium metal salt, a tellurium metal salt, an alkaline metal or alkaline earth metal salt or a halogen-containing salt in a solvent.
  • Examples of the copper metal salt include copper acetate, copper ammonium chloride, copper bromide, copper carbonate, copper ethoxide, copper hydroxide, copper iodide, copper isobutyrate, copper isopropoxide, copper oxalate, copper oxychroride, copper oxide, copper nitrates, and copper chlorides, and copper nitrates and copper chlorides are preferable .
  • the ruthenium metal salt examples include 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 0) 4 ] CI , an ammine complex such as [Ru(NH 3 )5H 2 0]Cl2, [Ru(NH 3 ) 5 Cl]Cl 2 , [Ru (NH 3 ) 6 ] Cl 2 and
  • a carbonyl complex such as Ru (CO) 5 and Ru 3 (CO) 12
  • tellurium metal salt examples include a halide such as eF 6 , eBr 4 , eCl 4 and Tel 4 , an oxyhalide, oxide such as Te0 2 and Te0 3 , an alkoxide such as Te(OC 2 H 5 ) 4 , a tellurate such as H 2 Te0 3 and H 6 Te0 6 .
  • a halide such as eF 6 , eBr 4 , eCl 4 and Tel 4
  • an oxyhalide, oxide such as Te0 2 and Te0 3
  • an alkoxide such as Te(OC 2 H 5 ) 4
  • a tellurate such as H 2 Te0 3 and H 6 Te0 6 .
  • alkaline metal salt and the alkaline earth metal salt examples include alkaline metal nitrates, alkaline earth metal nitrates, alkaline metal halides, alkaline earth metal halides, alkaline metal acetates , alkaline earth metal acetates , alkaline metal butyrates, alkaline earth metal butyrates, alkaline metal benzoates, alkaline earth metal benzoates, alkaline earth metal benzoates, alkaline metal alkoxides, alkaline earth metal alkoxides, alkaline metal carbonates, alkaline earth metal carbonates, alkaline metal citrates, alkaline earth metal citrates, alkaline metal formates, alkaline earth metal formates, alkaline metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, alkaline metal hydroxides, alkaline earth metal hydroxides, alkaline metal hypochlorites, alkaline earth metal hypochlorites, alkaline metal halates, alkaline earth metal
  • the catalyst can be produced by dissolving only the copper metal salt and the alkaline metal or alkaline earth metal salt in a solvent at preparation of the solution.
  • the catalyst comprising the metal oxides, the alkaline or alkaline earth metal, the
  • sulfur-containing component and the halogen component can be produced from a solution obtained by dissolving the metal salts, the alkaline metal or alkaline earth metal salt and the sulfur-containing salt in a solvent.
  • At least one selected from the group consisting of the above-mentioned metal salts contains preferably a halogen ion, more preferably a chloride ion.
  • a halogen ion may form an alkaline metal halide such as NaCl and the halogen component such as halides and oxyhalides of the above-mentioned metals.
  • 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.
  • 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 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.
  • a gas atmosphere containing oxygen and/or inert gas such as nitrogen, helium and argon.
  • gases include air, an oxygen gas, nitrous oxide, and other oxidizing gases.
  • the gas may be used after being mixed at an appropriate ratio with a diluting gas such as nitrogen, helium, argon, and water vapor.
  • An optimal temperature for calcination varies depending on the kind of the gas and the composition, however, a too high temperature may cause agglomeration of the copper component or the other metal salt as mentioned above. 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.
  • 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.
  • the diene include butadiene such as 1 , 3-butadiene or 1 , 2-butadiene .
  • olefin examples include preferably monoolefin, more preferably ethylene, propylene, butene, pentene, hexene, heptene and octene, still more preferably ethylene, propylene and butene, most preferably propylene.
  • the reaction is generally performed in the gas phase.
  • the olefin and oxygen may be fed respectively in the form of a gas.
  • Olefin and oxygen gases can be fed in the form of their mixed gas.
  • Olefin and oxygen gases may be fed with diluent gases. Examples of diluent gases include nitrogen, methane, ethane, propane, carbon dioxide, or rare gases, such as argon and helium.
  • oxygen source pure oxygen may be used, or a mixed gas containing a gas inactive to the reaction, such as air, may be used.
  • the amount of oxygen used varies depending on the reaction type, the catalyst, the reaction temperature or the like.
  • the amount of oxygen is typically 0.01 to 100 mol, and preferably 0.03 to 30 mol, and more preferably 0.25 to 10 mol, with respect to 1 mol of the olefin.
  • the reaction is performed at a temperature generally of
  • the reaction is usually carried out under reaction pressure in the range of reduced pressure to increased pressure .
  • Reduced pressure means a pressure lower than atmospheric pressure.
  • Increased pressure means a pressure higher than atmospheric pressure.
  • the pressure is typically in the range of 0.01 to 3 MPa, and preferably in the range of 0.02 to 2 MPa, in the absolute pressure.
  • the gaseous hourly space velocity (Liters of gas at standard temperature and pressure passing over the one liter of packed catalyst per hour) is generally in the range of from 100 Nl/(l.h) to 100000 Nl/(l.h), preferably 500 Nl/(l.h) to 50000 Nl/ (l.h) .
  • the linear velocity is generally in the range of from 0.0001 m/s to 500 m/s, and preferably in range of 0.001 to 50 m/s.
  • the reaction may be carried out as a batch reaction or a continuous flow reaction, preferably as a continuous flow reaction for industrial application.
  • the reaction of the present invention may be carried out by mixing an olefin and oxygen and then contacting the mixture with the catalyst under reduced pressure to the increased pressure.
  • the reactor type is not limited. Examples of the reactor type are fluid bed reactor, fixed bed reactor, moving bed reactor, and the like, preferably fixed bed reactor. In the case of using fixed bed reactor, single tube reactor or multi tube reactor can be employed. 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.
  • 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-l-butene .
  • olefin oxides examples 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.
  • Example 1 In Example 1 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 a dry-ice/methanol 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) .
  • Amorphous silica powder (1.9 g; Si0 2 , Japan Aerosil , 380 m 2 /g) was added to an aqueous solution mixture containing 0.55 g of (NH 4 ) 2 RuCl 6 (Aldrich) , 0.30 g of Cu (N0 3 ) 2 (Wako ) , 0.57 ml of lmol/L H 2 S0 4 (KANTO CHEMICAL) and 0.10 g of NaCl(Wako) . The obtained mixture was stirred for 24 hours in air, at room temperature .
  • the resulting material was then heated at 100 °C until dried, and calcined at 500 °C for 12 hours in air to obtain the catalyst having the following composition.
  • the total amount of Ru, Cu, Na and S 15.2 weight parts relative to 100 weight parts of Si0 2 .
  • the catalysts were evaluated by using a fixed-bed reactor. Filling a 1/2-inch OD reaction tube made of stainless steel with 1 mL of the catalyst, the reaction tube was supplied with 7.5 mL/min. of propylene, 15 mL/min. of the air, and 16.5 mL/min. of a nitrogen gas to carry out the reaction for 2 hours, at the reaction temperature of 250 and 270°C under 0.3 MPa in the absolute pressure.
  • the feed ratio of propylene to oxygen was 2.4 (molar ratio, propylene/oxygen) .
  • Catalysts having the following composition were prepared in the same manners as Example 1 except that H 2 S0 4 was not used.
  • the molar ratio of Ru/Cu/Na 1.3/1/1.4
  • the total amount of Ru, Cu and Na 14.3 weight parts relative to 100 weight parts of Si0 2
  • Example 1 The catalysts were evaluated in the same manners as Example 1. The results of Example 1 and Comparative Example 1 are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un procédé de préparation d'un oxyde d'oléfine consistant à faire réagir une oléfine avec de l'oxygène en présence d'un catalyseur comprenant un oxyde de cuivre et un composant contenant du soufre.
PCT/US2011/065167 2011-01-05 2011-12-15 Procédé de préparation d'un oxyde d'oléfine Ceased WO2012094122A1 (fr)

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US201161430048P 2011-01-05 2011-01-05
US61/430,048 2011-01-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105498847A (zh) * 2014-09-26 2016-04-20 神华集团有限责任公司 负载型铜催化剂及其制备方法和应用以及丙烯氧化制备环氧丙烷的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4007135A (en) * 1973-05-12 1977-02-08 Imperial Chemical Industries Limited Promoted silver catalyst for producing alkylene oxides
US6362349B1 (en) * 1998-04-15 2002-03-26 The Dow Chemical Company Process for the direct oxidation of olefins to olefin oxides
US20090234143A1 (en) * 2004-12-06 2009-09-17 Sumitomo Chemical Company, Limited Process for producing titanium-containing silicon oxide catalyst, the catalyst, and process for producing olefin compound with the catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4007135A (en) * 1973-05-12 1977-02-08 Imperial Chemical Industries Limited Promoted silver catalyst for producing alkylene oxides
US6362349B1 (en) * 1998-04-15 2002-03-26 The Dow Chemical Company Process for the direct oxidation of olefins to olefin oxides
US20090234143A1 (en) * 2004-12-06 2009-09-17 Sumitomo Chemical Company, Limited Process for producing titanium-containing silicon oxide catalyst, the catalyst, and process for producing olefin compound with the catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105498847A (zh) * 2014-09-26 2016-04-20 神华集团有限责任公司 负载型铜催化剂及其制备方法和应用以及丙烯氧化制备环氧丙烷的方法
CN105498847B (zh) * 2014-09-26 2019-05-03 神华集团有限责任公司 负载型铜催化剂及其制备方法和应用以及丙烯氧化制备环氧丙烷的方法

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