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WO2012094122A1 - Process for producing olefin oxide - Google Patents

Process for producing olefin oxide 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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WO
WIPO (PCT)
Prior art keywords
catalyst
oxide
copper
process according
component
Prior art date
Application number
PCT/US2011/065167
Other languages
French (fr)
Inventor
Yoshihiko Ohishi
Anusorn Seubsai
Selim Senkan
Original Assignee
Sumitomo Chemical Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Publication of WO2012094122A1 publication Critical patent/WO2012094122A1/en

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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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Abstract

A process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising a copper oxide and a sulfur-containing component.

Description

DESCRIPTION
PROCESS FOR PRODUCING OLEFIN OXIDE CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to and the benefit of U.S. Provisional Application No. 61/430,048, 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. 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. 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 .
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 and a sulfur-containing component.
[2] The process according to [1], wherein the catalyst further comprises a ruthenium oxide.
[3] The process according to [1] or [2] , wherein the catalyst further comprises an alkaline metal or alkaline earth metal component .
[4] The process according to any one of [1] to [3], wherein the catalyst further comprises a tellurium component.
[5] The process according to any one of [1] to [4], wherein the catalyst further comprises a halogen component.
[6] The process according to any one of [1] to [5], wherein the sulfur-containing component is a sulfur-containing ion.
[7] The process according to any one of [3] to [5], wherein the alkaline metal or alkaline earth metal component is a sodium-containing compound.
[8] The process according to any one of [1] to [7], wherein the copper oxide and the sulfur-containing component are supported on a porous support in the catalyst.
[9] The process according to any one of [2] to [8], wherein the copper oxide, the sulfur-containing component and the ruthenium oxide are supported on a porous support in the catalyst .
[10] The process according to [8] or [9], wherein the porous support comprises AI2O3, S1O2, T1O2 or ZrC>2.
[11] The process according to [8] or [9], wherein the porous support comprises Si02.
[12] The process according to any one of [1] to [11], wherein the phosphorus/copper molar ratio in the catalyst is 0.01/1 to 50/1.
[13] The process according to any one of [2] to [12], wherein the ruthenium/copper molar ratio in the catalyst is 0.01/1 to 50/1.
[14] The process according to any one of [3] to [13], wherein the alkaline or alkaline earth metal/copper molar ratio in the catalyst is 0.001/1 to 50/1.
[15] The process according to [8], wherein the total amount of the copper oxide and the sulfur-containing component is 0.01 to 80 weight parts relative to 100 weight parts of the porous support.
[16] The process according to [8] or [9] , wherein the catalyst is obtained by impregnating a porous support with a solution containing a copper ion and a sulfur-containing ion to prepare a composition, followed by calcining the composition.
[17] The process according to [9], wherein the catalyst is obtained by impregnating a porous support with a solution containing a copper ion, a sulfur-containing ion and a ruthenium ion to prepare a composition, followed by calcining the composition .
[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 and a sulfur-containing component.
[21] The catalyst according to [20], wherein the catalyst further comprises a ruthenium oxide.
[22] The catalyst according to [20] or [21], wherein the catalyst further comprises an alkaline metal or alkaline earth metal component.
[23] The process according to [20] or [21], wherein the catalyst further comprises a tellurium component.
[24] The process according to any one of [20] to [23] , wherein the catalyst further comprises a halogen component.
[25] The catalyst according to any one of [20] to [24] , wherein the sulfur-containing component is a sulfur-containing ion.
[26] The catalyst according to any one of [22] to [23] , wherein the alkaline metal or alkaline earth metal component is a sodium-containing compound. [27] The catalyst according to any one of [20] to [26] , wherein the copper oxide and the sulfur-containing component are supported on a porous support in the catalyst.
[28] The catalyst according to any one of [21] to [26] , wherein the copper oxide, the sulfur-containing component and the ruthenium oxide are supported on a porous support in the catalyst .
[29] The catalyst according to [27] or [28 ], wherein the porous support comprises AI2O3, S1O2, T1O2 or ZrC>2.
[30] The catalyst according to [27] or [28 ], wherein the porous support comprises Si02.
[31] The catalyst according to any one of [20] to [30], wherein the phosphorus/copper molar ratio in the catalyst is 0.001/1 to 50/1.
[32] The catalyst according to any one of [21] to [31] , wherein the ruthenium/copper molar ratio in the catalyst is 0.01/1 to 50/1.
[33] The catalyst according to any one of [22] to [32] , wherein the alkaline or alkaline earth metal/copper molar ratio in the catalyst is 0.001/1 to 50/1.
[34] The catalyst according to [27] , wherein the total amount of the copper oxide and the sulfur-containing component is 0.01 to 80 weight parts relative to 100 weight parts of the porous support .
[35] The catalyst according to [27] or [28] which is obtained impregnating a porous support with a solution containing a copper ion and a sulfur-containing ion to prepare a composition, followed by calcining the composition.
[36] The catalyst according to [28] which is obtained by impregnating a porous support with a solution containing a copper ion, a sulfur-containing ion and a ruthenium ion to prepare a composition, followed by calcining the composition.
[37] The catalyst according to any one of [20] to [36], 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 and a sulfur-containing component.
In the catalyst, 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 2O3 , S 1O2 , T1 O2 , or Zr02, more preferably Si02. Examples of the porous support comprising S1O2 include mesoporous silica. Such porous supports may also comprise zeolites.
Examples of the non-porous support include a non-porous support comprising S1O2 such as CAB-O-SIL (registered trademark) .
The support may be in form of powder or may be shaped to a desired structure.
If the catalyst comprises S1O2 as a support, olefin oxides can be prepared with good yield and good selectivity.
The catalyst comprises one or more kinds of 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
sulfur-containing components.
The sulfur-containing component is, for example, a sulfur-containing ion. Examples of the sulfur-containing ion include sulphate ions such as SC^2-, sulfite ions such as HS03~, SC>32~ . 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. Examples of the cation include H , NH4 , or the alkaline metal or alkaline earth metal ions as described below . Examples of the sulfur-containing salt include H2S04, NaHS04, Na2S04 , (NH4)HS04or (NH4)2S04, preferably H2S04 or Na2S04, more preferably H2S04.
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 Ru204, Ru2Os, RU3O5, RU3O6, Ru04, and Ru02. The ruthenium oxide is preferably Ru02.
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 Ca2+, Mg2+, Sr2+ and Ba2+.
The alkaline metal component may be an alkaline metal oxide. Examples of the alkaline metal oxide include Na20, Na202, K20, K202, Rb20, Rb202, Cs20, andCs202. 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.
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 halogen ions such as Cl~, Br" or I", F"; OH"; N03 "; S04 2"; C03 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
tellurium-containing compound or tellurium ion. Examples of the tellurium-containing compound include tellurium oxide such as TeO, Te02, Te03 or Te20s, and tellurium salt with anion such as CI", Br", I", F", OH-, N03 " or C03 2". Examples of the tellurium ion include Te , Te , Te , Te . The tellurium component is preferably tellurium oxide, more preferably one comprising tellurium and an oxygen atom, still more preferably Te02.
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 H2S04.
Particularly if 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 . When the molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved. The lower limit of the molar ratio is more preferably 0.01/1, still more preferably 0.05/1. The upper limit of the molar ratio is more preferably 5/1, still more preferably 1/1.
If the catalyst comprises the ruthenium oxide, the ruthenium/copper molar ratio in the catalyst is preferably 0.01/1 to 50/1 based on their atoms . When the molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved. The lower limit of the molar ratio is more preferably 0.1 /l , still more preferably 0.2 /l . The upper limit of the molar ratio is more preferably 5/1, still more preferably 1/1.
If the catalyst comprises the alkaline metal or alkaline earth metal component, 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. 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.
If the catalyst comprises the tellurium component, the tellurium/copper molar ratio in the catalyst is preferably 0.001/1 to 50/1 basedon their atoms. When the molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved. The lower limit of the molar ratio is more preferably 0.01/1, still more preferably 0.05/1. The upper limit of the molar ratio is more preferably 1/1, still more preferably 0.5/1.
When the copper oxide and the sulfur-containing component, and optionally any of the ruthenium oxide, the tellurium oxide and the alkaline metal or alkaline earth metal component are supported on a porous 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. The catalyst may comprise a halogen component . Here, 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.
Examples of such a halogen-containing compound include halides of copper, ruthenium or tellurium and oxyhalides of copper, ruthenium or tellurium.
Examples of such a halogen-containing compound include copper halides such as CuCl and CuCl2, tellurium halides such as eCl2 and eCl4, ruthenium halides such as RUCI3 and copper oxyhalides such as CuOCl2, CuC104, C102Cu (C104) 3 and Cu20 (C104) 2, tellurium oxyhalides such as e60nCli2, ruthenium oxyhalides such as RU2OCI4, RU2OCI5 and RU2OCI6.
If the catalyst comprises the halogen component, 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 CuTe04, CuTe03 and Cu3Te06, those composed of tellurium, sodium and oxygen, such as a2 e03 , a2Te04, Na2Te4<D9 , andNa4TeOs, and those composed of sodium, copper and oxygen, such as NaCu02, Na2CuC>2, NaCuO and Na6Cu2<06 , those composed of ruthenium, tellurium and oxygen, those composed of ruthenium, copper and oxygen such as RuCu202, RuCuC103, Ru2Cu06, Ru2Cu202, and those composed of ruthenium, sodium and oxygen.
If the catalyst comprises the composite oxide, the component may be supported on the porous support or any of the components as mentioned above.
When the catalyst contains ruthenium oxide, 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 oxides and a sulfur-containing component, and optionally the ruthenium oxide, the tellurium oxide, the alkaline metal or alkaline earth metal component or the halogen 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 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 .
Examples of the ruthenium metal salt include a halide such as ruthenium bromide, ruthenium chloride, ruthenium iodide, an oxyhalide such as RU2OCI4, RU2OCI5 and RU2OC16, a halogeno complex such as [RUCI2 (H20) 4 ] CI , an ammine complex such as [Ru(NH3)5H20]Cl2, [Ru(NH3)5Cl]Cl2, [Ru (NH3) 6] Cl2 and
[Ru (NH3) 6] CI3, a carbonyl complex such as Ru (CO) 5 and Ru3 (CO) 12, 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 (NH4)2RuCl6, and ruthenium salt containing CI is preferable.
Examples of the tellurium metal salt include a halide such as eF6, eBr4, eCl4 and Tel4, an oxyhalide, oxide such as Te02 and Te03, an alkoxide such as Te(OC2H5)4, a tellurate such as H2Te03 and H6Te06.
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 Na 03 and NaCl are more preferable .
Examples of the sulfur-containing salt include sulfate salts such as H2SO4, NaH SO4, a2S04, R2SO4 (R=alkyl group having 1 to 2 carbon atoms), (NH4)HS04 or (NH4)2S04, preferably H2S04 or Na2S04, or sulfite salts such as H2S03, (NH4)2S03, (NH4)HS03, Na2S03 or NaHS03. If an alkaline metal or alkaline earth metal salt comprises a sulfur-containing ion, 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.
If an alkaline metal halide is used as an alkaline metal or alkaline earth metal salt, 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. Such 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. 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.
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, N2, He) at standard pressure or reduced pressure. A drying time is preferably in the range from 0.5 to 24 hours. After drying, the composition can be shaped to a desired structure as necessary.
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 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.
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, still more preferably 200 to 300°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 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), COx (C02 and CO), and propanal (PaL) and acrolein (AC) .
Propylene conversions (XPR) were determined from the following:
XPR = { [PO+AC+AT+ PaL +C02/3 ] out/ [C3H6] in } χ 100%; and PO selectivities (SPo) were then calculated using the following expression:
SPO = { [ PO] / [PO+AC+AT+ PaL +C02/3] } 100% Each metal weight was determined from the amounts of the metal salts used for preparation of catalyst.
Example 1
Amorphous silica powder (1.9 g; Si02, Japan Aerosil , 380 m2/g) was added to an aqueous solution mixture containing 0.55 g of (NH4)2RuCl6 (Aldrich) , 0.30 g of Cu (N03) 2 (Wako ) , 0.57 ml of lmol/L H2S04 (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 molar ratio of Ru/Cu/Na/S: 1.3/1/1.4/0.46.
The total amount of Ru, Cu, Na and S : 15.2 weight parts relative to 100 weight parts of Si02.
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) .
Gas hourly space velocity (GHSV) =2340 (h_1)
Comparative Example 1
Catalysts having the following composition were prepared in the same manners as Example 1 except that H2S04 was not used. The molar ratio of Ru/Cu/Na: 1.3/1/1.4The total amount of Ru, Cu and Na : 14.3 weight parts relative to 100 weight parts of Si02
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.
[Table 1]
Figure imgf000026_0001
Example 2
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-butene .

Claims

WHAT WE CLAIM ARE:
1. A process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising a copper oxide and a sulfur-containing component.
2. The process according to claim 1, wherein the catalyst further comprises a ruthenium oxide.
3. The process according to claim 1 or 2, wherein the catalyst further comprises an alkaline metal or alkaline earth metal component.
4. The process according to claim 1 or 2, wherein the catalyst further comprises a tellurium component.
5. The process according to claim 1 or 2, wherein the catalyst further comprises a halogen component.
6. The process according to claim 1 or 2, wherein sulfur-containing component is a sulfur-containing ion.
7. The process according to claim 3, wherein the alkaline metal or alkaline earth metal component is a sodium-containing compound .
8. The process according to claim 1, wherein the copper oxide and the sulfur-containing component are supported on a porous support in the catalyst.
9. The process according to claim 2, wherein the copper oxide, the sulfur-containing component and the ruthenium oxide are supported on a porous support in the catalyst.
10. The process according to claim 8 or 9, wherein the porous support comprises A1203, Si02, Ti02 or Zr02.
11. The process according to claim 8 or 9, wherein the porous support comprises Si02.
12. The process according to claim 1, wherein the phosphorus/copper molar ratio in the catalyst is 0.01/1 to 50/1.
13. The process according to claim 2, wherein the ruthenium/copper molar ratio in the catalyst is 0.01/1 to 50/1.
14. The process according to claim 3, wherein the alkaline or alkaline earth metal/copper molar ratio in the catalyst is 0.001/1 to 50/1.
15. The process according to claim 8, wherein the total amount of the copper oxide and the sulfur-containing component is 0.01 to 80 weight parts relative to 100 weight parts of the porous support .
16. A catalyst for production of an olefin oxide which comprises a copper oxide and a sulfur-containing component.
17. The catalyst according to claim 16, wherein the catalyst further comprises a ruthenium oxide.
18. The catalyst according to claim 16 or 17, wherein the catalyst further comprises an alkaline metal or alkaline earth metal component.
19. The process according to claim 16 or 17, wherein the catalyst further comprises a tellurium component.
20. The process according to claim 16 or 17, wherein the catalyst further comprises a halogen component.
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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

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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

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Publication number Priority date Publication date Assignee Title
CN105498847A (en) * 2014-09-26 2016-04-20 神华集团有限责任公司 Supported copper catalyst and preparation method and application thereof and propylene oxidation preparation method of epoxypropane
CN105498847B (en) * 2014-09-26 2019-05-03 神华集团有限责任公司 Supported copper catalyst, preparation method and application thereof, and method for preparing propylene oxide by oxidation of propylene

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