WO2012009054A1 - Procédé de production d'oxyde oléfinique - Google Patents

Procédé de production d'oxyde oléfinique Download PDF

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Publication number
WO2012009054A1
WO2012009054A1 PCT/US2011/038521 US2011038521W WO2012009054A1 WO 2012009054 A1 WO2012009054 A1 WO 2012009054A1 US 2011038521 W US2011038521 W US 2011038521W WO 2012009054 A1 WO2012009054 A1 WO 2012009054A1
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Prior art keywords
oxide
ruthenium
alkaline
metal
catalyst
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PCT/US2011/038521
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English (en)
Inventor
Yoshihiko Ohishi
Anusorn Seubsai
Selim Senkan
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Sumitomo Chemical Company, Limited
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Publication date
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Priority to JP2012532160A priority Critical patent/JP2013505993A/ja
Publication of WO2012009054A1 publication Critical patent/WO2012009054A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • 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 which comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) ruthenium metal or a ruthenium oxide, (b) bismuth oxide and (c) alkaline metal component or alkaline earth metal component .
  • (b) bismuth oxide is B1 2 O 3 .
  • a catalyst for production of an olefin oxide which comprises (a) ruthenium metal or a ruthenium oxide, (b) bismuth oxide and (c) alkaline metal component or alkaline earth metal component. [20] The catalyst according to [19] which comprises (d) halogen component .
  • alkaline metal component or alkaline earth metal component is an alkaline metal-containing compound or an alkaline earth metal-containing compound.
  • a catalyst for producing an olefin oxide comprising (a) ruthenium metal or a ruthenium oxide, (b) bismuth oxide and (c) alkaline metal component or alkaline earth metal component.
  • the process of the present invention comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) ruthenium metal or a ruthenium oxide, (b) bismuth oxide and (c) alkaline metal component or alkaline earth metal component.
  • the components (a) , (b) and (c) may be supported on a porous support or a non-porous support.
  • the non-porous support include a non-porous support comprising Si0 2 such as CAB-O-SIL (registered trademark) .
  • the components (a) , (b) and (c) are preferably supported on a porous support.
  • This catalyst is valuable for production of olefin oxides, which is one aspect of the present invention.
  • the porous support has pores capable of supporting the components (a) , (b) and (c) .
  • the porous support comprises preferably AI2O3, S1O2, T1O2 or ZrC>2, more preferably Si0 2 .
  • Examples of the porous support comprising S1O 2 include mesoporous silica.
  • Such a porous support may also comprise zeolites .
  • olefin oxides can be prepared with good yield and good selectivity.
  • the catalyst may comprise one or more kinds of (a) ruthenium metal or a ruthenium oxide.
  • the ruthenium oxide is usually composed of ruthenium and oxygen.
  • Examples of the component (a) include ruthenium metal, RUO 2 and RUO 4 .
  • the component (a) is preferably RUO 2 .
  • the catalyst may comprise one or more kinds of (b) bismuth oxide.
  • the bismuth oxide is usually composed of bismuth and oxygen. Examples of the bismuth oxide include BiO, Bi0 2 , Bi 2 0 and B1 2 O 3 .
  • the bismuth oxide is preferably B1 2 O 3 .
  • the catalyst may comprise one or more kinds of (c) alkaline metal component or alkaline earth metal component.
  • the (c) component may be an alkaline metal-containing compound, an alkaline earth metal-containing compound, an alkaline metal ion or an alkaline earth metal ion.
  • alkaline metal-containing compound examples 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 Ca 2+ , Mg 2+ , Sr 2+ and Ba 2+ .
  • the alkaline metal component may be an alkaline metal oxide.
  • 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.
  • the alkaline earth metal component may be 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 .
  • 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 with an anion.
  • the alkaline earth metal salt comprises the alkaline earth metal ion as mentioned above with an anion. Examples of anions in such salts include F ⁇ , Cl ⁇ , Br ⁇ , I “ , OH “ , N0 3 " , S0 4 2” , CO3 2" HCO3 " and S0 3 2" .
  • Such salts are preferably an alkaline metal salt with a halogen, such as an alkaline metal halide, or an alkaline earth metal-containing salt with a halogen, such as an alkaline earth metal halide, more preferably an alkaline metal salt with a halogen, still more preferably an alkaline metal chloride.
  • the (c) component is preferably an alkaline metal-containing compound or an alkaline earth metal-containing compound, more preferably a sodium-containing compound.
  • the catalyst comprises preferably Ru0 2 , B1 2 O 3 and an alkaline metal-containing salt, still more preferably RUO 2 , B1 2 O 3 and a sodium-containing salt, because the olefin oxide yield and selectivity can be improved by adopting such a combination to the production of an olefin oxide.
  • the catalyst comprises NaCl as the (c) component , it can show excellent olefin oxide selectivity.
  • the ruthenium/bismuth metal molar ratio in the catalyst is preferably 1/99 to 99/1. When the metal molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved.
  • the lower limit of the molar ratio is more preferably 2/98 , still more preferably 3/ 97 , further preferably 10/90, particularly preferably 20/80.
  • the upper limit of the molar ratio is more preferably 98/2, still more preferably 97/3, further preferably 90/10, particularly preferably 80/20.
  • the ruthenium/ (c) component molar ratio in the catalyst is preferably 1/99 to 99/1. 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 2/98, still more preferably 3/97.
  • the upper limit of the molar ratio is more preferably 98/2, still more preferably 97/3.
  • the "(c) component" of the molar ratio represents the alkaline metal or alkaline earth metal existing in the (c) component and the alkaline metal or alkaline earth metal ion existing in the (c) component.
  • the total content of the components (a) , (b) and (c) is preferably 0.01 to 80% by weight of the amount of the catalyst.
  • the lower limit of the total content is more preferably 0.05% by weight, still more preferably 0.1% by weight of the amount of the catalyst.
  • the upper limit of the total content is more preferably 50% by weight, still more preferably 30% by weight of the amount of the catalyst.
  • the catalyst may comprise (d) halogen component besides the components (a) , (b) and (c) .
  • the component (d) is generally a halogen-containing compound. Examples of the halogen include chlorine, fluorine, iodine and bromine.
  • halogen-containing compound examples include ruthenium halides such as RUCI 3 , bismuth halides such as BiCl 3 , ruthenium oxyhalides such as R.U 2 OCI 4 , R.U 2 OCI 5 and R.U 2 OCI 6 , and bismuth oxyhalides such as BiOCl, BiOC10 4 , and BisC ⁇ Cl, preferably BiOCl .
  • the component (d) may be supported on any of the components (a), (b) and (c) or the porous support.
  • the catalyst may comprise (e) composite oxides, including those composed of ruthenium, bismuth and oxygen, such as Bi 3 Ru30n and Bii 2 RuO 20/ those composed of sodium, bismuth and oxygen, such as aBi0 3 , and those composed of sodium, ruthenium and oxygen, such as aRu0 4 and a 4 Ru0 4 .
  • the catalyst comprises the component (d) or (e)
  • the component may be supported on the porous support as mentioned above .
  • Production of the catalyst is not restricted to a specific process, examples of which include the conventional methods.
  • the catalyst can be obtained by impregnating a porous support with a solution containing a ruthenium ion, a bismuth ion and an alkaline metal or alkaline earth metal ion to prepare a composition, followed by calcining the composition.
  • the support can be in form of powder, or shaped to a desired structure as necessary.
  • the catalyst comprises the component (c) which is an alkaline metal salt with a halogen or alkaline earth metal salt with a halogen, and/or the component (d) supported on the porous support
  • the catalyst can be obtained in the same procedure as mentioned above except that the solution contains a ruthenium ion, a bismuth ion, an alkaline metal or alkaline earth metal-containing ion and a halogen ion.
  • the solution containing a ruthenium ion, a bismuth ion and an alkaline metal or alkaline earth metal ion can be prepared by dissolving a ruthenium metal salt or a ruthenium oxide, a bismuth metal salt or a bismuth oxide, and an alkaline metal or alkaline earth metal salt or an alkaline metal or alkaline earth metal oxide in a solvent.
  • the solution is preferably prepared by dissolving a ruthenium metal salt, a bismuth metal salt and an alkaline metal or alkaline earth metal salt in a solvent.
  • the bismuth metal salt include bismuth carbonate, bismuth nitrate, bismuth sulfate, bismuth bromide, bismuth chloride, bismuth iodide, bismuth oxychloride, and bismuth acetate .
  • the alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the (c) component.
  • alkaline metal or 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 halates
  • At least one of the metal salts for the solvent contains preferably a halogen ion, more preferably a chloride ion.
  • a halogen ion may form the (c) components such as alkaline metal halides and alkaline earth metal halides, or the (d) components such as ruthenium oxyhalides, ruthenium hilides, bismuth halides and oxyhalides.
  • 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 total amount of the porous support is preferably 20 to 99.99 % by weight, more preferably 50 to 99.95% by weight, still preferably 70 to 99.9% by weight of the catalyst as obtained .
  • 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 is preferably 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.
  • the method of calcining the composition is not limited, and calcining the composition is preferably may be performed under a gas atmosphere containing oxygen.
  • a gas atmosphere containing oxygen examples include air, oxygen, 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 bismuth oxide or ruthenium oxide. Accordingly, the calcination temperature is typically 200 to 800 ° C, preferably 400 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 olefin may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms.
  • the olefin include preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, and butadiene, more preferably ethylene, propylene and butene, still more 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.
  • diluent gases include nitrogen or, 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 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 0.05 to 10 mol and especially preferably 0.25 to 10 mol, with respect to 1 mol of the olefin.
  • the reaction is performed at a temperature generally of 100 to 350 ° C, preferably of 120 to 330 ° C, more preferably of 170 to 310 ° C.
  • the present reaction is 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 reaction 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 of the present invention 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 increased pressure.
  • the reactor type is not limited. Examples of the reactor types 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 reactors 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 be also used.
  • the olefin oxide may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms.
  • the olefin oxides include preferably ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, and 3, 4-epoxy-l-butene, more preferably ethylene oxide, propylene oxide and butene oxide, still more preferably propylene oxide.
  • the olefin oxide as obtained can be collected by a method known in the art such as separation by distillation.
  • Example 1 data analysis 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 quipped with different columns, PoraBOND U (25 m) and PoraBOND Q (25 m) .
  • the detected products were propylene oxide (PO) , acetone (AT), CO x (C0 2 and CO), propanal (PaL) , acrolein (AC) .
  • Catalysts were prepared by a co-impregnation method. This was accomplished by the parallel co-impregnation of a predetermined weight (1.9 g) of amorphous silica powder (Si0 2 , Japan Aerosil, 380 m 2 /g) by an aqueous solution mixture containing 0.55 g of (NH 4 ) 2 uCl 6 (Aldrich) , 0.12 g of BiCl 3 and 0.10 g of NaCl(Wako) . The aqueous solution mixture was allowed to impregnate the support with stirring for 24 hours in the air. 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 thus obtained catalyst, the reaction tube was supplied with 450 NmL/h of propylene, 900 NmL/h of the air, and 990 NmL/h of a nitrogen gas to carry out the reaction at the reaction temperature of 200, 250 and 270°C under increased pressure (equivalent to 0.3 MPa in the absolute pressure) .
  • Example 1 The catalyst obtained in 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 (C 3 H 6 ) , 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
  • Gas sampling was accomplished by withdrawing reactor exit gases using the passivated 200 micron ID capillary sampling probe.
  • the detected products were propylene oxide (PO) , acetone (AT) , acetaldehyde (AD) , CO x (C0 2 and CO) , and propanal + acrolein (PaL+AC) .
  • XPR ⁇ [PO+AC+AT+2AD/3+C0 2 /3]out/[C 3 H 6 ] in ⁇ ⁇ 100%;
  • PaL+AC are reported together since the two compounds appear at the same retention time, although the PaL is typically only found in trace amounts.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Epoxy Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'un oxyde oléfinique qui consiste à faire réagir une oléfine telle que du propylène avec de l'oxygène en présence d'un catalyseur comprenant: (a) du métal de ruthénium ou un oxyde de ruthénium, (b) de l'oxyde de bismuth et (c) un composant de métal alcalin ou un composant de métal alcalino-terreux sur un support poreux. Un support poreux peut comprendre un hylogène et des oxydes d'aluminium, de silicium, de titane ou de zirconium.
PCT/US2011/038521 2010-07-10 2011-05-31 Procédé de production d'oxyde oléfinique WO2012009054A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012532160A JP2013505993A (ja) 2010-07-10 2011-05-31 酸化オレフィンの製造方法

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US36322610P 2010-07-10 2010-07-10
US61/363,226 2010-07-10

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WO2012009054A1 true WO2012009054A1 (fr) 2012-01-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115668553A (zh) * 2020-05-21 2023-01-31 学校法人同志社 氧催化剂、使用了该氧催化剂的电极和电化学测定方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5739075A (en) * 1995-10-06 1998-04-14 Shell Oil Company Process for preparing ethylene oxide catalysts
US5905053A (en) * 1997-09-02 1999-05-18 Scientific Design Company, Inc. Ethylene oxide catalyst
US6362349B1 (en) * 1998-04-15 2002-03-26 The Dow Chemical Company Process for the direct oxidation of olefins to olefin oxides
US20040102643A1 (en) * 2002-11-27 2004-05-27 Tway Cathy L. Process for preparing a catalyst for the oxidation and ammoxidation of olefins
US20100150805A1 (en) * 2008-12-17 2010-06-17 Uop Llc Highly stable and refractory materials used as catalyst supports

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5739075A (en) * 1995-10-06 1998-04-14 Shell Oil Company Process for preparing ethylene oxide catalysts
US5905053A (en) * 1997-09-02 1999-05-18 Scientific Design Company, Inc. Ethylene oxide catalyst
US6362349B1 (en) * 1998-04-15 2002-03-26 The Dow Chemical Company Process for the direct oxidation of olefins to olefin oxides
US20040102643A1 (en) * 2002-11-27 2004-05-27 Tway Cathy L. Process for preparing a catalyst for the oxidation and ammoxidation of olefins
US20100150805A1 (en) * 2008-12-17 2010-06-17 Uop Llc Highly stable and refractory materials used as catalyst supports

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115668553A (zh) * 2020-05-21 2023-01-31 学校法人同志社 氧催化剂、使用了该氧催化剂的电极和电化学测定方法
CN115668553B (zh) * 2020-05-21 2023-12-29 学校法人同志社 氧催化剂、使用了该氧催化剂的电极和电化学测定方法

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