WO2013025315A1 - Process for producing olefin oxide - Google Patents

Process for producing olefin oxide Download PDF

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Publication number
WO2013025315A1
WO2013025315A1 PCT/US2012/047961 US2012047961W WO2013025315A1 WO 2013025315 A1 WO2013025315 A1 WO 2013025315A1 US 2012047961 W US2012047961 W US 2012047961W WO 2013025315 A1 WO2013025315 A1 WO 2013025315A1
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Prior art keywords
oxide
catalyst
oxygen
olefin
metal
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PCT/US2012/047961
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French (fr)
Inventor
Yoshihiko Ohishi
Anusorn Seubsai
Selim Senkan
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Sumitomo Chemical Company, Limited
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Publication of WO2013025315A1 publication Critical patent/WO2013025315A1/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

Definitions

  • the present invention relates to a process for producing an olefin oxide.
  • Olefin oxides such as propylene oxide
  • the present invention provides:
  • a process for producing an olefin oxide comprising: a first step of reacting an olefin with oxygen in the presence of a catalyst comprising metal oxides consisting of one or both of a copper oxide and a ruthenium oxide;
  • the present invention provides a process for producing an olefin oxide comprising:
  • the catalyst comprises metal oxides consisting of one or both of a copper oxide and a ruthenium oxide.
  • the catalyst preferably comprises a copper oxide, and more preferably comprises a copper oxide and a ruthenium oxide.
  • the copper oxide is generally composed of an oxygen atom and copper, and examples thereof include CU2O and CuO, and CuO is preferable.
  • the ruthenium oxide is generally composed of an oxygen atom and ruthenium, and examples thereof include RUO4 and RUO2 , and RUO2 is preferable.
  • the catalyst may comprise a metal oxide other than the copper oxide and the ruthenium oxide.
  • the other metal oxides include manganese oxides, tellurium oxides, bismuth oxides, antimony oxides, chromium oxides, rhenium oxides, cobalt oxides, nickel oxides, osmium oxides, cerium oxides, germanium oxides, tin oxides, tungsten oxides, thallium oxides, indium oxides, iridium oxides, lanthanum oxides, iron oxides, molybdenum oxides, selenium oxides, vanadium oxides and niobium oxides.
  • the tellurium oxide is generally composed of an oxygen atom and tellurium, and examples thereof include TeO, TeC> 2 and Te0 3 , and Te0 2 is preferable.
  • the manganese oxide is generally composed of an oxygen atom and manganese, and examples thereof include MnO, MnC> 2 , Mn 2 0 3 and ⁇ 3 ⁇ 4 , and ⁇ 2 ⁇ 3 is preferable.
  • the bismuth oxide is generally composed of an oxygen atom and bismuth, and examples thereof include BiO, B1O 2 , Bi 2 0 and Bi 2 0 3 .
  • the antimony oxide is generally composed of an oxygen atom and antimony, and examples thereof include Sb0 2 , Sb 2 ⁇ 0 3 , Sb 2 ⁇ 0 4 and Sb 2 ⁇ 0 5 , and SbC> 2 and Sb 2 ⁇ 0 3 are preferable.
  • the chromium oxide is generally composed of an oxygen atom and chromium, and examples thereof include Cr0 3 and (3 ⁇ 4(3 ⁇ 4, and Cr 2 0 3 is preferable.
  • the rhenium oxide is generally composed of an oxygen atom and rhenium, and examples thereof include ReC> 2 , e03 and Re 2 ⁇ 07, and ReC> 2 and ReC>3 are preferable.
  • the cobalt oxide is generally composed of an oxygen atom and cobalt, and examples thereof include CoO, C0 3 O 4 and C0 2 O 3 , and C0 3 O 4 is preferable.
  • the nickel oxide is generally composed of an oxygen atom and nickel, and examples thereof include NiO.
  • the osmium oxide is generally composed of an oxygen atom and osmium, and examples thereof include OSO 2 and OSO 4 , and OSO 2 is preferable.
  • the cerium oxide is generally composed of an oxygen atom and cerium, and examples thereof include Ce 2 ⁇ 03 and Ce0 2 , and Ce0 2 is preferable.
  • the germanium oxide is generally composed of an oxygen atom and germanium, and examples thereof include GeO and GeC> 2 , and Ge0 2 is preferable.
  • the tin oxide is generally composed of an oxygen atom and tin, and examples thereof include SnC> 2 , SnO, Sn 2 0 3 and Sn 3 0 4 , and Sn0 2 and SnO are preferable.
  • the tungsten oxide is generally composed of an oxygen atom and tungsten, and examples thereof include W 3 0, W 17 O 47 , W 5 O 14 , WO 2 and WO 3 , and WO 2 and WO 3 are preferable.
  • the thallium oxide is generally composed of an oxygen atom and thallium, and examples thereof include T1 2 0, TI 2 O 3 and TI 4 O 3 , and TI 4 O 3 is preferable.
  • the indium oxide is generally composed of an oxygen atom and indium, and examples thereof include ⁇ 2 ⁇ 3.
  • the iridium oxide is generally composed of an oxygen atom and iridium, and examples thereof include Ir0 2 .
  • the lanthanum oxide is generally composed of an oxygen atom and lanthanum, and examples thereof include La 2 0 3 .
  • the iron oxide is generally composed of an oxygen atom and lanthanum, and examples thereof include FeO, Fe 2 ⁇ 03 and Fe3 ⁇ D4, and Fe 2 ⁇ 0 3 is preferable.
  • the molybdenum oxide is generally composed of an oxygen atom and molybdenum, and examples thereof include M0O 2 or M0O3.
  • the selenium oxide is generally composed of an oxygen atom and selenium, and examples thereof include Se03 and Se0 2 , and Se0 2 is preferable.
  • the vanadium oxide is generally composed of an oxygen atom and vanadium, and examples thereof include VO, VO 2 , V 2 O 3 , V 6 O1 3 and V 2 0 5 , and V 2 0 5 is preferable.
  • the niobium oxide is generally composed of an oxygen atom and niobium, and examples thereof include NbO, M0O 2 and b 2 0s.
  • the catalyst preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide, manganese oxide, tellurium oxide, bismuth oxide, antimony oxide, chromium oxide, rhenium oxide, cobalt oxide, nickel oxide, osmium oxide, cerium oxide, germanium oxide, tin oxide, tungsten oxide, thallium oxide, indium oxide, iridium oxide, lanthanum oxide, iron oxide, molybdenum oxide, selenium oxide, vanadium oxide and niobium oxide.
  • the catalyst more preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide, tellurium oxide, manganese oxide, bismuth oxide, antimony oxide, cerium oxide, germanium oxide and tin oxide.
  • the catalyst still more preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide, tellurium oxide, manganese oxide and tin oxide.
  • the catalyst especially preferably consists of copper oxide and one or both of ruthenium oxide and tellurium oxide.
  • the catalyst may comprise a composite metal oxide.
  • the composite metal oxide examples include those composed of copper, ruthenium and oxygen; those composed of copper, sodium and oxygen; those composed of sodium, ruthenium and oxygen; those composed of copper, ruthenium, sodium and any other metals and oxygen; those composed of copper, any other metals and oxygen; and those composed of ruthenium, any other metals and oxygen; those composed of sodium and any other metals and oxygen. If the catalyst comprises the composite metal oxide, it may be supported on the support or any of the other components.
  • the catalyst preferably contains a support, such as a porous support and a non-porous support.
  • a support such as a porous support and a non-porous support.
  • One or both of a copper oxide and a ruthenium oxide are preferably supported on a support, more preferably supported on a porous support.
  • the non-porous support include a non-porous support comprising S1O 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 a copper oxide and a ruthenium oxide.
  • the porous support preferably comprises AI 2 O 3 , S1O 2 , T1O 2 , or ZrC> 2 , more preferably Si0 2 .
  • Examples of the porous support comprising S1O 2 include mesoporous silica.
  • Such porous supports may also comprise zeolites.
  • the support may be in form of powder, or shaped to a desired structure as necessary.
  • the catalyst preferably comprises one or more selected from the group consisting of an alkaline metal component and an alkaline earth metal component.
  • the alkaline metal component may be an alkaline metal-containing compound, and may be an alkaline metal ion.
  • the alkaline earth metal component may be an alkaline earth metal-containing compound, and may be an alkaline earth metal ion .
  • Examples of the alkaline metal-containing compound include compounds containing an alkaline metal such as Na, K, Rb and Cs .
  • the alkaline metal component maybe an alkaline metal oxide.
  • Example of the alkaline metal oxide include Na 2 0, Na 2 0 2 , K 2 0, K0 2 , K 2 0 2 , Rb 2 0, Rb 2 0 2 , Cs 2 0, Cs 2 0 2 , Cs0 2 , Cs0 3 , Cs 2 0 3 , Csu0 3 , CS 4 O and CS 7 O.
  • Examples of the alkaline metal ion include Na + , K + , Rb + and Cs + .
  • alkaline earth metal-containing compound examples include compounds containing an alkaline earth metal such as Ca, Mg, Sr and Ba .
  • the alkaline earth metal component may be an alkaline metal earth oxide.
  • examples of the alkaline earth metal oxide include CaO, Ca0 2 , MgO, Mg0 2 , SrO, Sr0 2 , BaO and Ba0 2 .
  • Examples of the alkaline earth metal ion include Ca 2+ , Mg 2+ , Sr 2+ and Ba 2+ .
  • the alkaline metal-containing compound is preferable, and a sodium-containing compound is more preferable.
  • the alkaline metal-containing compound is preferably an alkaline metal salt.
  • the alkaline earth metal-containing compound is preferably an alkaline earth metal salt.
  • the alkaline metal salt comprises the alkaline metal ion as mentioned above and an anion.
  • the alkaline earth metal salt comprises the alkaline earth metal ion as mentioned above and an anion. Examples of anions in such salts include F ⁇ , Cl ⁇ , Br " , I ⁇ , OH ⁇ , N0 3 " , S0 4 2" , CO3 2" , HCO3 " and SO3 2" .
  • Such salt is preferably an alkaline metal salt containing a halogen such as an alkaline metal halide, or an alkaline earth metal-containing salt containing a halogen such as an alkaline earth metal halide, and an alkaline metal salt containing a halogen is more preferable, and an alkaline metal chloride is still more preferable .
  • the alkaline metal component or the alkaline earth metal component may be supported on the support as mentioned above.
  • the catalyst may contain a halogen component besides metal oxides and an alkaline metal or alkaline earth metal component.
  • the halogen component is generally a halogen-containing compound. Examples of the halogen include chlorine, fluorine, iodine and bromine.
  • halogen-containing compound examples include halides of copper, ruthenium or any other metals of metal oxides and oxyhalides of copper, ruthenium or any other metals of metal oxides.
  • the catalyst comprises the halogen component
  • the component may be supported on the porous support as mentioned above .
  • the total content of these components is preferably 0.01 to 80 parts by weight relative to 100 parts by weight of a 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 part by weight, still more preferably 0.1 part by weight relative to 100 parts by weight of a support .
  • the upper limit of the total content is more preferably 50 parts by weight, still more preferably 30 parts by weight relative to 100 parts by weight of a support.
  • the catalyst preferably comprises one or more selected from the group consisting of an alkaline metal component and an alkaline earth metal component.
  • 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 0.1/1, still more preferably 0.2/1
  • the upper limit of the molar ratio is more preferably 5/1, still more preferably 1/1.
  • 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.
  • alkaline metal or alkaline earth metal component/ruthenium 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 other component/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 10/1, still more preferably 5/1.
  • the other component/ruthenium 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 10/1, still more preferably 5/1.
  • the catalyst can be produced according to the conventional methods .
  • the catalyst When each of the metal oxides is supported on a support, the catalyst can be obtained by impregnating a support with a solution containing a copper and/or ruthenium ion to prepare a composition, followed by calcining the composition.
  • the catalyst comprises an alkaline metal or alkaline earth metal component or any other components as mentioned above
  • the catalyst can be obtained in the same procedure as mentioned above except that solution further contains an alkaline metal or alkaline earth metal-containing ion, a halogen ion or an metal ion of any other metal which forms any of the metal oxides as mentioned above.
  • the solution containing a copper and/or ruthenium ion can be prepared by dissolving a copper metal salt and/or a ruthenium metal salt in a solvent.
  • 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 nitrates, and copper chlorides.
  • the solvent contains an alkaline metal or alkaline earth metal ion, it can be prepared by adding an alkaline metal or alkaline earth metal salt to a solvent.
  • the alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the alkaline metal component or the alkaline earth metal component.
  • 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 earth metal hydrogen carbonates, alkaline metal hydroxides, alkaline earth
  • Such a halogen ion may form the alkaline metal or alkaline earth metal component such as NaCl and the haolgen component such as halides and oxyhalides of Cu or Ru.
  • the solution may contain acidic or basic compounds in order to control its pH.
  • Examples of the solvent for the solution include water and alcohols such as methanol or ethanol .
  • 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 approximately 40°C to approximately 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. After drying, the composition can be shaped to a desired structure as necessary.
  • the method of calcining the composition is not limited, and calcining the composition is preferably performed under a gas atmosphere containing oxygen.
  • a gas atmosphere containing oxygen 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.
  • 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 and copper oxide. Accordingly, the calcination temperature is typically 200°C to 800°C, preferably 400°C to 600°C.
  • 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 process for producing an olefin oxide comprising: a first step of reacting an olefin with oxygen in the presence of a catalyst comprising metal oxides consisting of one or both of a copper oxide and a ruthenium oxide;
  • the first step is the reaction of an olefin with oxygen in the presence of the catalyst as described above.
  • the olefin may have a linear or branched structure.
  • the olefin usually contains 2 to 10 carbon atoms, and preferably contains 2 to 8 carbon atoms.
  • Examples of the olefin include ethylene, propylene, butene, pentene, hexene, heptene, octene, and butadiene, ethylene, propylene and butane are preferable, and propylene is more preferable.
  • the reaction is generally performed in the gas phase.
  • the olefin and oxygen may be fed in the form of a gas, respectively.
  • Olefin and oxygen gases can be fed in the form of their mixed gas.
  • Olefin and oxygen gases may be fed with diluent gases.
  • diluent gases include nitrogen, rare gases such as argon and helium, carbon dioxide, water vapor, methane, ethane and propane.
  • Preferable diluent gases are nitrogen, carbon dioxide and the both thereof.
  • oxygen source pure oxygen may be used, or a mixed gas containing pure oxygen and a gas inactive to the reaction, such as air, may be used.
  • gas inactive to the reaction include nitrogen, rare gases such as argon and helium, carbon dioxide, water vapor, methane, ethane and propane.
  • gases inactive to the reaction are nitrogen, carbon dioxide and the both thereof.
  • the amount of oxygen used varies depending on the reaction type, the kind of catalyst, the reaction temperature or the like.
  • the amount of oxygen is typically 0.01 mol to 100 mole, and preferably 0.03 mole to 30 mole, and more preferably 0.05 mole to 10 mole, and especially preferably 0.25 mole to 10 mole, with respect to 1 mol of the olefin.
  • the reaction is usually performed at a temperature of 100°C to 350°C, preferably of 120°C to 330°C, and more preferably of 170°C to 310°C.
  • 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 reaction may be carried out as a batch reaction or a continuous reaction, preferably as a continuous 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. Adiabatic type or heat exchange type may also be used.
  • the olefin oxide can be produced.
  • the olefin oxide may have a linear or branched structure.
  • the olefin oxide usually contains 2 to 10 carbon atoms, and preferably contains 2 to 8 carbon atoms.
  • Examples of the olefin oxides include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, and 3, 4-epoxy-l-butene, and ethylene oxide, propylene oxide and butene oxide are preferable, and propylene oxide is more preferable .
  • the olefin oxide as obtained can be collected by a method known in the art such as separation by distillation.
  • the second step is a step of contacting the catalyst after the first step with oxygen at a temperature higher than a reaction temperature of the first step.
  • the second step may be conducted after confirming the decrease of the yield of the olefin oxide, the decrease of the conversion of the olefin, and/or the decrease of the selectivity of the olefin oxide in the first step.
  • the contact of the catalyst after the first step with oxygen is preferably carried out at a temperature higher than a reaction temperature of the first step to 650°C.
  • the contact is more preferably carried out at a temperature being 10°C higher than a reaction temperature of the first step to 650°C in the second step, still more preferably carried out at a temperature being 50°C higher than a reaction temperature of the first step to 650°C in the second step, and especially preferably carried out at a temperature being 100°C higher than a reaction temperature of the first step to 650°C in the second step.
  • the contact is preferably conducted at a temperature of 300°C to 650°C, more preferably 350°C to 600°C, still more preferably 400°C to 550°C.
  • the contacting time is usually 0.1 hour to 24 hours, preferably 0.3 hour to 10 hours and more preferably 0.5 hour to 5 hours.
  • the pressure at contacting the catalyst after the first step with oxygen is typically in the range of reduced pressure to increased pressure, preferably in the range of 0.01 MPa to 3 MPa, more preferably in the range of 0.02 MPa to 2 MPa, still more preferably atmospheric pressure in the absolute pressure.
  • oxygen air, pure oxygen and other gaseous oxidants containing oxygen can be used.
  • the other gaseous oxidants may be used after being mixed oxygen or air with a diluting gas such as nitrogen, helium, argon, and water vapor, at an appropriate ratio .
  • the feed amount of oxygen is generally 0.1% by volume to 100% by volume in the total feed gas volume, preferably 1% by volume to 100% by volume in the total feed gas volume, more preferably 10% by volume to 100% by volume in the total feed gas volume.
  • the catalyst after the first step may be contacted with oxygen in the presence of olefin of which amount is 1% by volume or less to 100% by volume in the total feed gas volume, and preferably contacted with oxygen in the presence of olefin of which amount is 500 ppm by volume or less to 100% by volume in the total feed gas volume, and more preferably contacted with oxygen in the absence of olefin in the total feed gas.
  • the third step is a step of reacting an olefin with oxygen in the presence of the catalyst obtained in the above-mentioned second step, and an olefin oxide can be produced.
  • Examples of the olefin and the olefin oxide include the same as described in the above-mentioned first step, respectively .
  • the third step can be conducted in the same manner of the first step described above.
  • the olefin oxide as obtained can be collected by 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 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 quipped with different columns, PoraBOND U (25 m) and PoraBOND Q (25 m) . The detected products were propylene oxide (PO) , acetone (AT) , C0 2 , propanal (PaL) , acrolein (AC)
  • Each metal weight was determined from the amounts of the metal salts used for preparation of catalyst.
  • 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) 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.
  • the catalysts were evaluated by using a fixed-bed reactor.
  • reaction tube made of stainless steel with 1 mL of the prepared 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, at the reaction temperature of 250°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 ) .
  • the catalyst was evaluated after the reaction for 2 hours.
  • the propylene conversion and PO selectivity of the catalyst were 5% and 13%, respectively.
  • the catalyst was evaluated, the propylene conversion and the PO selectivity of which were 2.5% and 7%, respectively. After that, the catalyst was contacted with 30 ml/min. of air at 500°C for 1 hour. The catalyst after the contacting with oxygen at 500°C for 1 hour is supplied again to the same reaction as mentioned above .
  • the propylene conversion and the PO selectivity of the catalyst after the re-reaction for 2 hours were 5.7% and 11%, respectively .
  • Example 1 The same catalyst as Example 1 was used and evaluated in the same manners as Example 1.
  • the deactivated catalyst was contacted with 30 ml/min. of air at 250°C for 1 hour.
  • the obtained catalyst is supplied again to the same reaction as mentioned above.
  • the propylene conversion and the PO selectivity of the catalyst after the re-reaction for 2 hours were 2.6% and 7%, respectively .
  • Amorphous silica powder (3.9 g; Si0 2 , Japan Aerosil, 380 m 2 /g) was added to an aqueous solution mixture containing 0.70 g of (NH 4 ) 2 uCl 6 (Aldrich) , 0.60 g of Cu(N0 3 ) 2 (Wako) and 0.20 g of NaCl (Wako) and 0.08 g of Te0 2 (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.
  • the catalysts were evaluated by using a fixed-bed reactor. Filling a 0.6-inch OD reaction tube made of quartz glass with 1 mL of the prepared catalyst, the reaction tube was supplied with 30 mL/min. of propylene, 60 mL/min. of the air, and 66 mL/min of a nitrogen gas to carry out the reaction, at the reaction temperature of 200°C under 0.1 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 ) .
  • the catalyst was evaluated after the reaction for 4 hours.
  • the propylene conversion and PO selectivity of the catalyst were 0.3% and 83%, respectively.
  • the catalyst was evaluated, the propylene conversion and the PO selectivity of which were 0.1% and 58%, respectively. After that, the catalyst was contacted with 30 ml/min. of air at 500°C for 1 hour. The catalyst after the contacting with oxygen at 500°C for 1 hour is supplied again to the same reaction as mentioned above.
  • the propylene conversion and the PO selectivity of the catalyst after the re-reaction for 4 hours were 0.3% and 84%, respectively .
  • Example 2 The same catalyst as Example 1 (5.0 mg) was placed in a well of a reactor as mentioned in Angew. Chem. Int. Ed. 38 (1999) 2794, equipped with array microreactors , wells along each reactor channel and a passivated 200 micron ID capillary sampling probe within the reactor channel.
  • the mixture gas consisting of 1 vol% propylene (C33 ⁇ 4) , 4 vol% 0 2 , and 95 vol% He was fed to the well containing the catalyst, at a gas hourly space velocity (GHSV) of 20, 000 h _1 , at a reactor temperature of 250°C.
  • GHSV gas hourly space velocity

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Abstract

A process for producing an olefin oxide comprising: a first step of reacting an olefin with oxygen in the presence of a catalyst comprising metal oxides consisting of one or both of a copper oxide and a ruthenium oxide; a second step of contacting the catalyst after the first step with oxygen at a temperature higher than a reaction temperature of the first step; and a third step of reacting an olefin with oxygen in the presence of the catalyst obtained in the second step.

Description

DESCRIPTION
PROCESS FOR PRODUCING OLEFIN OXIDE
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit under 35 U.S.C. §
119(e) of U.S. Provisional Application No . 61/524, 555, filed on August 17, 2011, the contents of which are hereby incorporated by reference in their entirety into the present disclosure. FIELD OF THE INVENTION
The present invention relates to a process for producing an olefin oxide.
BACKGROUND ART
Olefin oxides, such as propylene oxide, are important and versatile intermediates used in the production of a large variety of valuable consumer products such as polyurethane foams, polymers, alkylene glycol, cosmetics, food emulsifiers and as fumigants and insecticides.
SUMMARY OF THE INVENTION
The present invention provides:
[1] A process for producing an olefin oxide comprising: a first step of reacting an olefin with oxygen in the presence of a catalyst comprising metal oxides consisting of one or both of a copper oxide and a ruthenium oxide;
a second step of contacting the catalyst after the first step with oxygen at a temperature higher than a reaction temperature of the first step; and
a third step of reacting an olefin with oxygen in the presence of the catalyst obtained in the second step;
[2] The process according to [1], wherein the catalyst after the first step is contacted with oxygen at a temperature higher than a reaction temperature of the first step to 650°C in the second step;
[3] The process according to [1], wherein the catalyst after the first step is contacted with oxygen at a temperature being 10°C higher than a reaction temperature of the first step to 650°C in the second step;
[4] The process according to [1], [2] or [3], wherein the catalyst comprises a copper oxide;
[5] The process according to any one of [1] to [4], wherein the catalyst comprises a copper oxide and a ruthenium oxide;
[6] The process according to any one of [1] to [5], wherein the catalyst further comprises an alkaline metal component or an alkaline earth metal component;
[7] The process according to any one of [1] to [6], wherein the catalyst further comprises a halogen component.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a process for producing an olefin oxide comprising:
a first step of reacting an olefin with oxygen in the presence of a catalyst comprising metal oxides consisting of one or both of a copper oxide and a ruthenium oxide;
a second step of contacting the catalyst after the first step with oxygen at a temperature higher than a reaction temperature of the first step; and
a third step of reacting an olefin with oxygen in the presence of the catalyst obtained in the second step. The catalyst comprises metal oxides consisting of one or both of a copper oxide and a ruthenium oxide. The catalyst preferably comprises a copper oxide, and more preferably comprises a copper oxide and a ruthenium oxide.
The copper oxide is generally composed of an oxygen atom and copper, and examples thereof include CU2O and CuO, and CuO is preferable.
The ruthenium oxide is generally composed of an oxygen atom and ruthenium, and examples thereof include RUO4 and RUO2 , and RUO2 is preferable.
The catalyst may comprise a metal oxide other than the copper oxide and the ruthenium oxide. Examples of the other metal oxides include manganese oxides, tellurium oxides, bismuth oxides, antimony oxides, chromium oxides, rhenium oxides, cobalt oxides, nickel oxides, osmium oxides, cerium oxides, germanium oxides, tin oxides, tungsten oxides, thallium oxides, indium oxides, iridium oxides, lanthanum oxides, iron oxides, molybdenum oxides, selenium oxides, vanadium oxides and niobium oxides.
The tellurium oxide is generally composed of an oxygen atom and tellurium, and examples thereof include TeO, TeC>2 and Te03, and Te02 is preferable.
The manganese oxide is generally composed of an oxygen atom and manganese, and examples thereof include MnO, MnC>2, Mn203 and Μη3θ4, and Μη2θ3 is preferable.
The bismuth oxide is generally composed of an oxygen atom and bismuth, and examples thereof include BiO, B1O2, Bi20 and Bi203.
The antimony oxide is generally composed of an oxygen atom and antimony, and examples thereof include Sb02, Sb2<03, Sb2<04 and Sb2<05, and SbC>2 and Sb2<03 are preferable.
The chromium oxide is generally composed of an oxygen atom and chromium, and examples thereof include Cr03 and (¾(¾, and Cr203 is preferable. The rhenium oxide is generally composed of an oxygen atom and rhenium, and examples thereof include ReC>2, e03 and Re2<07, and ReC>2 and ReC>3 are preferable.
The cobalt oxide is generally composed of an oxygen atom and cobalt, and examples thereof include CoO, C03O4 and C02O3, and C03O4 is preferable.
The nickel oxide is generally composed of an oxygen atom and nickel, and examples thereof include NiO.
The osmium oxide is generally composed of an oxygen atom and osmium, and examples thereof include OSO2 and OSO4, and OSO2 is preferable.
The cerium oxide is generally composed of an oxygen atom and cerium, and examples thereof include Ce2<03 and Ce02, and Ce02 is preferable.
The germanium oxide is generally composed of an oxygen atom and germanium, and examples thereof include GeO and GeC>2, and Ge02 is preferable.
The tin oxide is generally composed of an oxygen atom and tin, and examples thereof include SnC>2, SnO, Sn203 and Sn304, and Sn02 and SnO are preferable.
The tungsten oxide is generally composed of an oxygen atom and tungsten, and examples thereof include W30, W17O47, W5O14, WO2 and WO3, and WO2 and WO3 are preferable.
The thallium oxide is generally composed of an oxygen atom and thallium, and examples thereof include T120, TI2O3 and TI4O3, and TI4O3 is preferable.
The indium oxide is generally composed of an oxygen atom and indium, and examples thereof include Ιη2θ3.
The iridium oxide is generally composed of an oxygen atom and iridium, and examples thereof include Ir02.
The lanthanum oxide is generally composed of an oxygen atom and lanthanum, and examples thereof include La203. The iron oxide is generally composed of an oxygen atom and lanthanum, and examples thereof include FeO, Fe2<03 and Fe3<D4, and Fe2<03 is preferable.
The molybdenum oxide is generally composed of an oxygen atom and molybdenum, and examples thereof include M0O2 or M0O3.
The selenium oxide is generally composed of an oxygen atom and selenium, and examples thereof include Se03 and Se02, and Se02 is preferable.
The vanadium oxide is generally composed of an oxygen atom and vanadium, and examples thereof include VO, VO2, V2O3, V6O13 and V205, and V205 is preferable.
The niobium oxide is generally composed of an oxygen atom and niobium, and examples thereof include NbO, M0O2 and b20s. The catalyst preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide, manganese oxide, tellurium oxide, bismuth oxide, antimony oxide, chromium oxide, rhenium oxide, cobalt oxide, nickel oxide, osmium oxide, cerium oxide, germanium oxide, tin oxide, tungsten oxide, thallium oxide, indium oxide, iridium oxide, lanthanum oxide, iron oxide, molybdenum oxide, selenium oxide, vanadium oxide and niobium oxide. The catalyst more preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide, tellurium oxide, manganese oxide, bismuth oxide, antimony oxide, cerium oxide, germanium oxide and tin oxide. The catalyst still more preferably consists of copper oxide and one or two metal oxides selected from the group consisting of ruthenium oxide, tellurium oxide, manganese oxide and tin oxide. The catalyst especially preferably consists of copper oxide and one or both of ruthenium oxide and tellurium oxide. The catalyst may comprise a composite metal oxide. Examples of the composite metal oxide include those composed of copper, ruthenium and oxygen; those composed of copper, sodium and oxygen; those composed of sodium, ruthenium and oxygen; those composed of copper, ruthenium, sodium and any other metals and oxygen; those composed of copper, any other metals and oxygen; and those composed of ruthenium, any other metals and oxygen; those composed of sodium and any other metals and oxygen. If the catalyst comprises the composite metal oxide, it may be supported on the support or any of the other components.
The catalyst preferably contains a support, such as a porous support and a non-porous support. One or both of a copper oxide and a ruthenium oxide 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 S1O2 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 a copper oxide and a ruthenium oxide. The porous support preferably comprises AI2O3, S1O2, T1O2, or ZrC>2, more preferably Si02. Examples of the porous support comprising S1O2 include mesoporous silica. Such porous supports may also comprise zeolites.
The support may be in form of powder, or shaped to a desired structure as necessary.
The catalyst preferably comprises one or more selected from the group consisting of an alkaline metal component and an alkaline earth metal component. The alkaline metal component may be an alkaline metal-containing compound, and may be an alkaline metal ion. The alkaline earth metal component may be an alkaline earth metal-containing compound, and may be an alkaline earth metal ion .
Examples of the alkaline metal-containing compound include compounds containing an alkaline metal such as Na, K, Rb and Cs . The alkaline metal component maybe an alkaline metal oxide. Example of the alkaline metal oxide include Na20, Na202, K20, K02, K202, Rb20, Rb202, Cs20, Cs202, Cs02, Cs03, Cs203, Csu03, CS4O and CS7O. Examples of the alkaline metal ion include 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 . The alkaline earth metal component may be an alkaline metal earth oxide. Examples of the alkaline earth metal oxide include CaO, Ca02, MgO, Mg02, SrO, Sr02, BaO and Ba02. Examples of the alkaline earth metal ion include Ca2+, Mg2+, Sr2+ and Ba2+.
The alkaline metal-containing compound is preferable, and a sodium-containing compound is more preferable.
The alkaline metal-containing compound is preferably an alkaline metal salt. The alkaline earth metal-containing compound is preferably an alkaline earth metal salt. The alkaline metal salt comprises the alkaline metal ion as mentioned above and an anion. The alkaline earth metal salt comprises the alkaline earth metal ion as mentioned above and an anion. Examples of anions in such salts include F~, Cl~, Br", I~, OH~, N03 ", S04 2", CO32", HCO3" and SO32". Such salt is preferably an alkaline metal salt containing a halogen such as an alkaline metal halide, or an alkaline earth metal-containing salt containing a halogen such as an alkaline earth metal halide, and an alkaline metal salt containing a halogen is more preferable, and an alkaline metal chloride is still more preferable .
The alkaline metal component or the alkaline earth metal component may be supported on the support as mentioned above.
The catalyst may contain a halogen component besides metal oxides and an alkaline metal or alkaline earth metal component. The halogen component is generally a halogen-containing compound. Examples of the halogen include chlorine, fluorine, iodine and bromine.
Examples of the halogen-containing compound include halides of copper, ruthenium or any other metals of metal oxides and oxyhalides of copper, ruthenium or any other metals of metal oxides. If the catalyst comprises the halogen component, the component may be supported on the porous support as mentioned above . When one or both of a copper oxide and a ruthenium oxide, and optionally any of the components are supported on a porous support in the catalyst, the total content of these components is preferably 0.01 to 80 parts by weight relative to 100 parts by weight of a 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 part by weight, still more preferably 0.1 part by weight relative to 100 parts by weight of a support . The upper limit of the total content is more preferably 50 parts by weight, still more preferably 30 parts by weight relative to 100 parts by weight of a support.
The catalyst preferably comprises one or more selected from the group consisting of an alkaline metal component and an alkaline earth metal component.
When both of a copper oxide and a ruthenium oxide are included, 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 0.1/1, still more preferably 0.2/1 The upper limit of the molar ratio is more preferably 5/1, still more preferably 1/1.
When a copper oxide and alkaline metal or alkaline earth metal are included, 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.
When a ruthenium oxide and alkaline metal or alkaline earth metal component are included, alkaline metal or alkaline earth metal 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.
When a copper oxide and other oxide except ruthenium oxide are included, the other component/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 10/1, still more preferably 5/1.
When a ruthenium oxide and other oxide except copper oxide are included, the other 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 0.05/1. The upper limit of the molar ratio is more preferably 10/1, still more preferably 5/1.
The catalyst can be produced according to the conventional methods .
When each of the metal oxides is supported on a support, the catalyst can be obtained by impregnating a support with a solution containing a copper and/or ruthenium ion to prepare a composition, followed by calcining the composition.
If the catalyst comprises an alkaline metal or alkaline earth metal component or any other components as mentioned above, the catalyst can be obtained in the same procedure as mentioned above except that solution further contains an alkaline metal or alkaline earth metal-containing ion, a halogen ion or an metal ion of any other metal which forms any of the metal oxides as mentioned above.
The solution containing a copper and/or ruthenium ion can be prepared by dissolving a copper metal salt and/or a ruthenium metal 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 nitrates, and copper chlorides. Examples of the ruthenium metal salt include, for example, a halide such as ruthenium bromide, ruthenium chloride, ruthenium iodide, an oxyhalide such as RU2OCI4, RU2OCI5 and RU2OC16, a halogeno complex such as [RuCl2 (H20) 4] CI, an ammine complex such as [Ru (NH3) 5H20] Cl2, [Ru (NH3) 5CI ] 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) β (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, and ammonium salt such as (NH4) 2RuCl6.
If the solvent contains an alkaline metal or alkaline earth metal ion, it can be prepared by adding an alkaline metal or alkaline earth metal salt to a solvent.
The alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the alkaline metal component or the alkaline earth metal component. Examples of the alkaline metal salt and the alkaline earth metal salt include alkaline metal nitrates, alkaline earth metal nitrates, alkaline metal halides, alkaline earth metal halides, alkaline metal acetates, alkaline earth metal acetates, alkaline metal butyrates, alkaline earth metal butyrates, alkaline metal benzoates, alkaline earth metal benzoates, alkaline metal alkoxides, alkaline earth metal alkoxides, alkaline metal carbonates, alkaline earth metal carbonates, alkaline metal citrates, alkaline earth metal citrates, alkaline metal formates, alkaline earth metal formates, alkaline metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, alkaline metal hydroxides, alkaline earth metal hydroxides, alkaline metal hypochlorites, alkaline earth metal hypochlorites, alkaline metal halates, alkaline earth metal halates, alkaline metal nitrites, alkaline earth metal nitrites, alkaline metal oxalates, alkaline earth metal oxalates, alkaline metal perhalates, alkaline earth metal perhalates, alkaline metal propionates, alkaline earth metal propionates, alkaline metal tartrates and alkaline earth metal tartrates, preferably alkaline metal halides and alkaline metal nitrates, more preferably a 03 and NaCl. At least one of the metal salts for the solvent contains preferably a halogen ion, more preferably a chloride ion.
Such a halogen ion may form the alkaline metal or alkaline earth metal component such as NaCl and the haolgen component such as halides and oxyhalides of Cu or Ru. The solution may contain acidic or basic compounds in order to control its pH.
Examples of the solvent for the solution include water and alcohols such as methanol or ethanol .
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 approximately 40°C to approximately 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. After drying, the composition can be shaped to a desired structure as necessary.
The method of calcining the composition is not limited, and calcining the composition is preferably performed under a gas atmosphere containing oxygen. 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 and copper oxide. Accordingly, the calcination temperature is typically 200°C to 800°C, preferably 400°C to 600°C.
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 process for producing an olefin oxide comprising: a first step of reacting an olefin with oxygen in the presence of a catalyst comprising metal oxides consisting of one or both of a copper oxide and a ruthenium oxide;
a second step of contacting the catalyst after the first step with oxygen at a temperature higher than a reaction temperature of the first step; and
a third step of reacting an olefin with oxygen in the presence of the catalyst obtained in the second step.
The first step is the reaction of an olefin with oxygen in the presence of the catalyst as described above.
The olefin may have a linear or branched structure. The olefin usually contains 2 to 10 carbon atoms, and preferably contains 2 to 8 carbon atoms. Examples of the olefin include ethylene, propylene, butene, pentene, hexene, heptene, octene, and butadiene, ethylene, propylene and butane are preferable, and propylene is more preferable.
The reaction is generally performed in the gas phase. In the reaction, the olefin and oxygen may be fed in the form of a gas, respectively. 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, rare gases such as argon and helium, carbon dioxide, water vapor, methane, ethane and propane. Preferable diluent gases are nitrogen, carbon dioxide and the both thereof.
As the oxygen source, pure oxygen may be used, or a mixed gas containing pure oxygen and a gas inactive to the reaction, such as air, may be used. Examples of the gas inactive to the reaction include nitrogen, rare gases such as argon and helium, carbon dioxide, water vapor, methane, ethane and propane. Preferable gases inactive to the reaction are nitrogen, carbon dioxide and the both thereof. The amount of oxygen used varies depending on the reaction type, the kind of catalyst, the reaction temperature or the like. The amount of oxygen is typically 0.01 mol to 100 mole, and preferably 0.03 mole to 30 mole, and more preferably 0.05 mole to 10 mole, and especially preferably 0.25 mole to 10 mole, with respect to 1 mol of the olefin.
The reaction is usually performed at a temperature of 100°C to 350°C, preferably of 120°C to 330°C, and more preferably of 170°C to 310°C.
The reaction is usually carried out under reaction pressure in the range of reduced pressure to increased pressure . By carrying out the reaction under such a reaction pressure condition, the productivity and selectivity of olefin oxides can be improved. Reduced pressure means a pressure lower than atmospheric pressure. Increased pressure means a pressure higher than atmospheric pressure. The pressure is typically in the range of 0.01 to 3 MPa, and preferably in the range of 0.02 to 2 MPa, in the absolute pressure. The reaction may be carried out as a batch reaction or a continuous reaction, preferably as a continuous 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. Adiabatic type or heat exchange type may also be used.
In the first step, the olefin oxide can be produced. The olefin oxide may have a linear or branched structure. The olefin oxide usually contains 2 to 10 carbon atoms, and preferably contains 2 to 8 carbon atoms. Examples of the olefin oxides include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, and 3, 4-epoxy-l-butene, and ethylene oxide, propylene oxide and butene oxide are preferable, and propylene oxide is more preferable .
The olefin oxide as obtained can be collected by a method known in the art such as separation by distillation.
The second step is a step of contacting the catalyst after the first step with oxygen at a temperature higher than a reaction temperature of the first step.
The second step may be conducted after confirming the decrease of the yield of the olefin oxide, the decrease of the conversion of the olefin, and/or the decrease of the selectivity of the olefin oxide in the first step.
The contact of the catalyst after the first step with oxygen is preferably carried out at a temperature higher than a reaction temperature of the first step to 650°C. The contact is more preferably carried out at a temperature being 10°C higher than a reaction temperature of the first step to 650°C in the second step, still more preferably carried out at a temperature being 50°C higher than a reaction temperature of the first step to 650°C in the second step, and especially preferably carried out at a temperature being 100°C higher than a reaction temperature of the first step to 650°C in the second step.
The contact is preferably conducted at a temperature of 300°C to 650°C, more preferably 350°C to 600°C, still more preferably 400°C to 550°C.
The contacting time is usually 0.1 hour to 24 hours, preferably 0.3 hour to 10 hours and more preferably 0.5 hour to 5 hours.
The pressure at contacting the catalyst after the first step with oxygen is typically in the range of reduced pressure to increased pressure, preferably in the range of 0.01 MPa to 3 MPa, more preferably in the range of 0.02 MPa to 2 MPa, still more preferably atmospheric pressure in the absolute pressure.
As oxygen, air, pure oxygen and other gaseous oxidants containing oxygen can be used. The other gaseous oxidants may be used after being mixed oxygen or air with a diluting gas such as nitrogen, helium, argon, and water vapor, at an appropriate ratio .
The feed amount of oxygen is generally 0.1% by volume to 100% by volume in the total feed gas volume, preferably 1% by volume to 100% by volume in the total feed gas volume, more preferably 10% by volume to 100% by volume in the total feed gas volume.
The catalyst after the first step may be contacted with oxygen in the presence of olefin of which amount is 1% by volume or less to 100% by volume in the total feed gas volume, and preferably contacted with oxygen in the presence of olefin of which amount is 500 ppm by volume or less to 100% by volume in the total feed gas volume, and more preferably contacted with oxygen in the absence of olefin in the total feed gas.
The third step is a step of reacting an olefin with oxygen in the presence of the catalyst obtained in the above-mentioned second step, and an olefin oxide can be produced.
Examples of the olefin and the olefin oxide include the same as described in the above-mentioned first step, respectively .
The third step can be conducted in the same manner of the first step described above. The olefin oxide as obtained can be collected by 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 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 quipped with different columns, PoraBOND U (25 m) and PoraBOND Q (25 m) . The detected products were propylene oxide (PO) , acetone (AT) , C02, propanal (PaL) , 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 (SP0) 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) 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.
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 prepared 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, at the reaction temperature of 250°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) .
The catalyst was evaluated after the reaction for 2 hours. The propylene conversion and PO selectivity of the catalyst were 5% and 13%, respectively.
Twenty-three (23) hours after beginning the reaction, the catalyst was evaluated, the propylene conversion and the PO selectivity of which were 2.5% and 7%, respectively. After that, the catalyst was contacted with 30 ml/min. of air at 500°C for 1 hour. The catalyst after the contacting with oxygen at 500°C for 1 hour is supplied again to the same reaction as mentioned above .
The propylene conversion and the PO selectivity of the catalyst after the re-reaction for 2 hours were 5.7% and 11%, respectively .
Comparative Example 1
The same catalyst as Example 1 was used and evaluated in the same manners as Example 1.
After the reaction for 16 hours, the catalyst was obtained, the propylene conversion and the PO selectivity of which were 3% and 9%, respectively.
After that, the deactivated catalyst was contacted with 30 ml/min. of air at 250°C for 1 hour. The obtained catalyst is supplied again to the same reaction as mentioned above.
The propylene conversion and the PO selectivity of the catalyst after the re-reaction for 2 hours were 2.6% and 7%, respectively .
Example 2
Amorphous silica powder (3.9 g; Si02, Japan Aerosil, 380 m2/g) was added to an aqueous solution mixture containing 0.70 g of (NH4)2 uCl6 (Aldrich) , 0.60 g of Cu(N03)2 (Wako) and 0.20 g of NaCl (Wako) and 0.08 g of Te02 (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.
The catalysts were evaluated by using a fixed-bed reactor. Filling a 0.6-inch OD reaction tube made of quartz glass with 1 mL of the prepared catalyst, the reaction tube was supplied with 30 mL/min. of propylene, 60 mL/min. of the air, and 66 mL/min of a nitrogen gas to carry out the reaction, at the reaction temperature of 200°C under 0.1 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) .
The catalyst was evaluated after the reaction for 4 hours. The propylene conversion and PO selectivity of the catalyst were 0.3% and 83%, respectively.
Sixteen (16) hours after beginning the reaction, the catalyst was evaluated, the propylene conversion and the PO selectivity of which were 0.1% and 58%, respectively. After that, the catalyst was contacted with 30 ml/min. of air at 500°C for 1 hour. The catalyst after the contacting with oxygen at 500°C for 1 hour is supplied again to the same reaction as mentioned above.
The propylene conversion and the PO selectivity of the catalyst after the re-reaction for 4 hours were 0.3% and 84%, respectively .
Reference Example 1
The same catalyst as Example 1 (5.0 mg) was placed in a well of a reactor as mentioned in Angew. Chem. Int. Ed. 38 (1999) 2794, equipped with array microreactors , wells along each reactor channel and a passivated 200 micron ID capillary sampling probe within the reactor channel. The mixture gas consisting of 1 vol% propylene (C3¾) , 4 vol% 02, and 95 vol% He was fed to the well containing the catalyst, at a gas hourly space velocity (GHSV) of 20, 000 h_1, at a reactor temperature of 250°C. Gas sampling was accomplished by withdrawing reactor exit gases using the passivated 200 micron ID capillary sampling probe The products analysis was conducted by an on-line Micro-Gas Chromatograph (Varian, CP-4900) equipped with a thermal conductivity detector (TCD) , PoraPLOT U (10M) and Molecular sieve 13X (10M) . After the reaction of propylene with oxygen in the presence of the catalyst for 2 - 3.5 hours, the used catalyst was contacted with air of 5 ml/min at 250°C for 1 hour. Then, the reaction was conducted again. This operation was repeated three times. The result is shown in Fig. 1.
Fig. 1
PO selectivity Propylene conversion
Figure imgf000022_0001
6 10 12
time / h

Claims

WHAT WE CLAIM ARE:
1. A process for producing an olefin oxide comprising: a first step of reacting an olefin with oxygen in the presence of a catalyst comprising metal oxides consisting of one or both of a copper oxide and a ruthenium oxide;
a second step of contacting the catalyst after the first step with oxygen at a temperature higher than a reaction temperature of the first step; and
a third step of reacting an olefin with oxygen in the presence of the catalyst obtained in the second step.
2. The process according to claim 1, wherein the catalyst after the first step is contacted with oxygen at a temperature higher than a reaction temperature of the first step to 650°C in the second step.
3. The process according to claim 1, wherein the catalyst after the first step is contacted with oxygen at a temperature being 10°C higher than a reaction temperature of the first step to 650°C in the second step.
4. The process according to claim 1, wherein the catalyst comprises a copper oxide.
5. The process according to claim 1, wherein the catalyst comprises a copper oxide and a ruthenium oxide.
6. The process according to claim 1, wherein the catalyst further comprises an alkaline metal component or an alkaline earth metal component.
7. The process according to claim 1, wherein the catalyst further comprises a halogen component.
PCT/US2012/047961 2011-08-17 2012-07-24 Process for producing olefin oxide WO2013025315A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3668257A (en) * 1966-08-08 1972-06-06 Union Oil Co Oxidation of olefins
US3716562A (en) * 1970-06-12 1973-02-13 Montedison Spa Process for preparing olefin oxides
US6323350B1 (en) * 1997-12-22 2001-11-27 The Dow Chemical Company Process for the oxidation of olefins to olefin oxides
US6362349B1 (en) * 1998-04-15 2002-03-26 The Dow Chemical Company Process for the direct oxidation of olefins to olefin oxides
WO2010130610A1 (en) * 2009-05-12 2010-11-18 Basf Se Process for producing propylene oxide
US20110152546A1 (en) * 2009-12-17 2011-06-23 Sumitomo Chemical Company, Limited Process for producing olefin oxide
JP2011162499A (en) * 2010-02-12 2011-08-25 Sumitomo Chemical Co Ltd Method for producing olefin oxide

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3668257A (en) * 1966-08-08 1972-06-06 Union Oil Co Oxidation of olefins
US3716562A (en) * 1970-06-12 1973-02-13 Montedison Spa Process for preparing olefin oxides
US6323350B1 (en) * 1997-12-22 2001-11-27 The Dow Chemical Company Process for the oxidation of olefins to olefin oxides
US6362349B1 (en) * 1998-04-15 2002-03-26 The Dow Chemical Company Process for the direct oxidation of olefins to olefin oxides
WO2010130610A1 (en) * 2009-05-12 2010-11-18 Basf Se Process for producing propylene oxide
US20110152546A1 (en) * 2009-12-17 2011-06-23 Sumitomo Chemical Company, Limited Process for producing olefin oxide
JP2011162499A (en) * 2010-02-12 2011-08-25 Sumitomo Chemical Co Ltd Method for producing olefin oxide

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