US20120283454A1 - Process for producing olefin oxide - Google Patents

Process for producing olefin oxide Download PDF

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US20120283454A1
US20120283454A1 US13/516,222 US201013516222A US2012283454A1 US 20120283454 A1 US20120283454 A1 US 20120283454A1 US 201013516222 A US201013516222 A US 201013516222A US 2012283454 A1 US2012283454 A1 US 2012283454A1
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catalyst
ruthenium
oxide
alkaline
metal component
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Selim SENKAN
Anusorn Seubsai
Yoshihiko Ohishi
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • 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
    • C07D301/10—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 with catalysts containing silver or gold
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
  • a catalyst comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
  • the catalyst according to [21] which is obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion and an alkaline metal or alkaline earth metal ion to prepare a composition, followed by calcining the composition.
  • the catalyst according to [21] or [22] which is obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion, an alkaline metal or alkaline earth metal ion and halogen ion to prepare a composition, followed by calcining the composition.
  • FIG. 1 is a graph showing the result of Example 1.
  • FIG. 2 is a graph showing the result of Example 2.
  • FIG. 3 is a graph showing the result of Example 3.
  • FIG. 4 is a graph showing the result of Example 4.
  • FIG. 5 is a graph showing the result of Example 5.
  • FIG. 6 is a graph showing the XRD patterns of Example 6.
  • the process of the present invention comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
  • a catalyst comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
  • 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 Al 2 O 3 , SiO 2 , TiO 2 , or ZrO 2 , more preferably SiO 2 .
  • Examples of the porous support comprising SiO 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) copper oxide.
  • the (a) copper oxide is usually composed of copper and oxygen.
  • Examples of the copper oxide include Cu 2 O and CuO.
  • the copper oxide is preferably CuO.
  • the catalyst may comprise one or more kinds of (b) ruthenium metal or ruthenium oxide.
  • the (b) ruthenium oxide is usually composed of ruthenium and oxygen. Examples of the ruthenium oxide include RuO 4 , and RuO 2 .
  • the component (b) is preferably RuO 2 .
  • the catalyst may comprise one or more kinds of (c) alkaline metal component or alkaline earth metal component.
  • the component (c) may be an alkaline metal-containing compound, an alkaline earth metal-containing compound, an alkaline metal ion or an alkaline earth metal ion.
  • Examples of the alkaline metal-containing compound include compounds containing an alkaline metal such as Na, K, Rb and Cs.
  • Examples of the alkaline earth metal-containing compound include compounds containing an alkaline earth metal such as Ca, Mg, Sr and Ba.
  • Examples of the alkaline metal ion include Na + , K + , Rb + and Cs + .
  • Examples of the alkaline earth metal ion include such as Ca 2+ , Mg 2+ , Sr 2+ and Ba 2+ .
  • the component (c) is preferably an alkaline metal-containing compound, an alkaline metal or both of them, more preferably an alkaline metal-containing compound, still more preferably a sodium-containing compound or a potassium-containing compound.
  • the olefin oxide selectivity is excellent at reaction temperature not more than 270° C.
  • the alkaline metal-containing compound and alkaline earth metal-containing compound are preferably an alkaline metal salt and an alkaline earth metal salt.
  • the alkaline metal salt comprises the alkaline metal ion as mentioned above with an anion.
  • the alkaline earth metal salt comprises the alkaline earth metal ion as mentioned above with an anion. Examples of anions in such salts include Cl ⁇ , Br ⁇ , I ⁇ , NO 3 ⁇ , SO 4 2 ⁇ and CO 3 2 ⁇ .
  • Such salts are preferably an alkaline metal salt with a halogen, such as an alkaline metal halide, or an alkaline earth metal-containing salt with a halogen, such as an alkaline earth metal halide, more preferably an alkaline metal salt with a halogen, still more preferably an alkaline metal chloride.
  • the catalyst comprises preferably CuO, RuO 2 and an alkaline metal-containing compound, still more preferably CuO, RuO 2 and a sodium-containing compound, because the olefin oxide yield and selectivity can be improved by adopting such combination to the production of an olefin oxide.
  • the catalyst comprises NaCl, as the (c) component, it can show excellent olefin oxide selectivity and yield.
  • the copper/ruthenium 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.
  • the upper limit of the molar ratio is more preferably 98/2, still more preferably 97/3.
  • 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 halides of copper or ruthenium and oxyhalides of copper or ruthenium. If the catalyst comprises the component (d), 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 copper ion, a ruthenium ion and an alkaline metal or alkaline earth metal-containing 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 component (c) which is an alkaline metal salt with a halogen or alkaline earth metal salt with a halogen, and the component (d) supported on the porous support, the catalyst can be obtained in the same procedure as mentioned above except that solution contains copper ion, a ruthenium ion, an alkaline metal or alkaline earth metal-containing ion and a halogen ion.
  • the solution containing a copper ion, a ruthenium ion and an alkaline metal or alkaline earth metal ion can be prepared by dissolving a copper metal salt, a ruthenium metal salt and an alkaline metal or alkaline earth 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 oxychloride, copper nitrates, and copper chlorides.
  • the alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the (c) component.
  • the alkaline metal or alkaline earth metal salt include alkaline metal nitrates, alkaline earth metal nitrates, alkaline metal halides and alkaline earth metal halides, preferably alkaline metal halides and alkaline metal nitrates, more preferably NaNO 3 , NaCl, KCl and KNO 3 .
  • 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 (c) component such as NaCl and the (d) component such as halides and oxyhalides of Cu or Ru.
  • the solution may contain acidic or basic compounds in order to control its pH.
  • the acid compound may be any of an inorganic acid and an organic acid.
  • the inorganic acid include hydrochloric acid, nitric acid, nitrous acid and perchloric acid etc.
  • the organic acid include aliphatic carboxylic acids such as acetic acid, oxalic acid, propionic acid, butyric acid, citric acid, maleic acid, fumaric acid and tartaric acid etc.; and aromatic carboxylic acids such as benzoic acid, dicarboxybenzene, tricarboxybenzene, dicarboxynaphthalene and dicarboxyanthracene etc.
  • Examples of the base compound include alkaline metal hydroxides, amine compounds, imine compounds, hydrazine or hydrazine compounds, ammonia, hydroxylamine, hydroxyamine and ammonium hydroxides.
  • alkaline metal hydroxides include sodium hydroxide, potassium hydroxide etc.
  • amine compounds include aliphatic amines having a carbon number of 1 to 20 and aromatic amines having a carbon number of 6 to 20, such as methylamine, ethylamine, propylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, decylamine, dodecylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, ethanolamine, dimethylethanolamine, diethylethanolamine, triethanolamine, ethylenediamine, tetramethylenediamine, pentamethylenediamine, diethylenetriamine, aniline, benzyamine and phenylenediamine etc.
  • Examples of the imine compounds include ethyleneimine, pyrrolidine, piperidine and piperazine etc.
  • Examples of the amide compounds include acetamide and benzamide etc.
  • Examples of the hydrazine compounds include methylhydrazine and phenylhydrazine etc.
  • quaternary ammonium salts examples include quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide etc.; quaternary ammonium halides such as tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, and tetraethylammonium bromide etc.; etc.
  • 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 99.5% by weight, still preferably 70 to 99.9% by weight of the catalyst as obtained.
  • 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 air or also under an inert gas atmosphere (for example, Ar, N 2 , He) at standard pressure or reduced pressure. A drying time is preferably in the range from 0.5 to 24 hours. After drying, the composition can be shaped to a desired structure as necessary.
  • Calcining the composition is not limited, but preferably may be performed under a gas atmosphere containing oxygen.
  • a gas atmosphere containing oxygen examples include air and an oxygen gas.
  • 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 ruthenium oxide and copper 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 may be a monoolefin or a diolefin.
  • the monoolefin include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, and decene.
  • the diene include butadiene such as 1,3-butadiene or 1,2-butadiene.
  • olefin examples include preferably monoolefin, more preferably ethylene, propylene, butene, pentene, hexene, heptene and octene, still more preferably ethylene, propylene and butene, most preferably propylene.
  • the reaction is generally performed in the gas phase.
  • the olefin and oxygen may be fed respectively in the form of a gas.
  • Olefin and oxygen gases can be fed in the form of their mixed gas.
  • Olefin and oxygen gases may be fed with diluent gases. Examples of diluent gases include nitrogen, methane, ethane, propane, carbon dioxide, or rare gases, such as argon and helium.
  • oxygen source pure oxygen may be used, or a mixed gas containing a gas inactive to the reaction, such as air, may be used.
  • the amount of oxygen used varies depending on the reaction type, the catalyst, the reaction temperature or the like.
  • the amount of oxygen is typically 0.01 to 100 mol, and preferably 0.03 to 30 mol, and more preferably 0.25 to 10 mol, with respect to 1 mol of the olefin.
  • the reaction is performed at a temperature generally of 100 to 350° C., preferably of 120 to 330° C., more preferably of 170 to 310° C., still more preferably of 200 to 270° C.
  • the reaction temperature is most preferably 240 to 270° C. for the reaction in a microreactor.
  • 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 may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms.
  • the olefin oxide may have one carbon-carbon double bond when the diolefin is applied for the reaction.
  • Examples of the olefin oxide having one carbon-carbon double bond include 3,4-epoxy-1-butene.
  • the olefin oxides include preferably ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide and octene oxide, more preferably ethylene oxide, propylene oxide and butene oxide, still more preferably propylene oxide.
  • the olefin oxide as obtained can be collected by a method known in the art such as separation by distillation.
  • the detected products were propylene oxide (PO), acetone (AT), acetaldehyde (AD), CO x (CO 2 and CO), and propanal+acrolein (PaL+AC).
  • PO propylene oxide
  • AT acetone
  • AD acetaldehyde
  • CO x CO 2 and CO
  • PaL+AC propanal+acrolein
  • Propylene conversions (X PR ) were determined from the following:
  • X PR ⁇ [PO+AC+AT+2AD/3+CO 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.
  • the metal salt solution was then allowed to impregnate the support for 24 hours in air.
  • the resulting material was then heated at 150° C. until dried, and calcined at 500° C. for 12 hours in air.
  • the catalyst (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 % O 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 190, 210, 230, 250, 260, 270, 290 or 310° 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 catalysts were prepared in the same manner as Example 1, except that the total metal content in the catalyst was 8% by weight.
  • Propylene oxide was prepared in the same manner as Example 1 except that the catalysts of the present example were used, the reactor temperature was 250° C., and GHSV was changed.
  • the catalysts were prepared in the same manner as Example 1, except that the total metal content in each of the catalysts was 5, 7, 10 or 12.5% by weight.
  • Propylene oxide was prepared in the same manner as Example 1 except that the catalysts of the present example were used and the reactor temperature was 250° C.
  • the catalysts were prepared in the same manner as Example 3, except that the total metal content in the catalysts was 12.5% by weight.
  • Propylene oxide was prepared in the same manner as Example 3 except that the oxygen/propylene (volume ratio) was changed.
  • the powder x-ray diffraction pattern of the catalyst obtained in Example 1 was determined with PANalytical X'Pert PRO fitted with a Ni filter and a Soller slit collimator.
  • the Cu—K ⁇ radiation at 45 kV and 40 mA was used to identify the active catalyst phase.
  • compositions were also examined in the same manner, Na 2 O (1.8 wt % Na, relative to the total of Na 2 O and SiO 2 ) supported on SiO 2 which was prepared from NaNO 3 ; CuO (3.6 wt % Cu, relative to the total of CuO and SiO 2 ) supported on SiO 2 which was prepared from Cu(NO 3 ) 2 ; RuO 2 (7.2 wt % Ru, relative to the total of RuO 2 and SiO 2 ) supported on SiO 2 which was prepared from (NH 4 ) 2 RuCl 6 ; NaCl (1.8 wt % Na, relative to the total of NaCl and SiO 2 ) supported on SiO 2 which was prepared from NaCl; and bimetallic RuO 2 +CuO supported on SiO 2 which was prepared in the same manner as the catalyst except that NaCl was not used.
  • the XRD patterns are shown in FIG. 6 .
  • the XRD pattern of the catalyst shows that the catalyst comprises CuO, RuO 2 and NaCl without forming any crystalline mixed metal oxides or alloys.
  • a catalyst is prepared in the same manner as Example 1, except that TiO 2 is used instead of SiO 2 .
  • Production of propylene oxide is carried out in the same manner as Example 1 except that the catalyst of the present example is used.
  • a reaction gas was mixed with ethane (10 Nml/min) as an external standard, and then directly introduced into the TCD-GC equipped with a column of Gaskuropack 54 (2 m). All products in the reaction gas were collected for 1 hour with double methanol traps connected in series and cooled with a dry-ice/methanol bath. The two methanol solutions were mixed together and added to anisole as an external standard, and then analyzed with two FID-GCs equipped with different columns, PoraBOND U (25 m) and PoraBOND Q (25 m).
  • the metal composition was prepared by a co-impregnation method.
  • a predetermined weight (1.9 g) of an amorphous silica powder (SiO 2 , Japan Aerosil, 380 m 2 /g) was added to an aqueous solution mixture containing 0.54 g of (NH 4 ) 2 RuCl 6 (Aldrich), 0.30 g of Cu(NO 3 ) 2 of (Wako) and 0.10 g NaNO, (Wako), followed by stirring for 24 hours in the air to impregnate the support with the metal salts.
  • the resulting material was then heated at 100° C. until dried, and calcined at 500° C. for 12 hours in the air to give a catalyst.
  • the catalyst was evaluated by using a fixed-bed reactor. Filling a 1 ⁇ 2-inch reaction tube made of stainless steel with 1 mL of the thus obtained catalyst, the following gases were fed to the reaction tube to carry out the reaction: 450 NmL/h of propylene, 900 NmL/h of the air, 990 NmL/h of a nitrogen gas. Such a reaction was carried out at the reaction temperature of 200° C. under the increased pressure (equivalent to 0.3 MPa in the absolute pressure).
  • the preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.64 g of (NH 4 ) 2 RuCl 6 (Aldrich), 0.35 g of Cu(NO 3 ) 2 (Wako), 0.08 g of Rb(NO 3 ) (Wako) and 2.3 g of an amorphous silica powder (SiO 2 , Japan Aerosil, 380 m 2 /g) as raw materials.
  • the preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.76 g of (NH 4 ) 2 RuCl 6 (Aldrich), 0.42 g of Cu(NO 3 ) 2 (Wako), 0.08 g of Cs(NO 3 ) (Wako) and 2.7 g of an amorphous silica powder (SiO 2 , Japan Aerosil, 380 m 2 /g) as raw materials.
  • the preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.23 g of (NH 4 ) 2 RuCl 6 (Aldrich), 0.13 g of Cu(NO 3 ) 2 (Wako), 0.1 g of Mg(NO 3 ) 2 (Wako) and 0.8 g of an amorphous silica powder (SiO 2 , Japan Aerosil, 380 m 2 /g) as raw materials.
  • the preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.86 g of (NH 4 ) 2 RuCl 6 (Aldrich), 0.47 g of Cu(NO 3 ) 2 (Wako), 0.15 g of Sr(NO 3 ) 2 (Wako) and 3.0 g of an amorphous silica powder (SiO 2 , Japan Aerosil, 380 m 2 /g) as raw materials.
  • the preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.73 g of (NH 4 ) 2 RuCl 6 (Aldrich), 0.40 g of Cu(NO 3 ) 2 (Wako), 0.10 g of Ba(NO 3 ) 2 (Wako) and 2.6 g of amorphous silica powder (SiO 2 , Japan Aerosil, 380 m 2 /g) as raw materials.
  • Example 8 9 10 11 12 13 14 alkaline metal or Na Rb Cs Mg Ca Sr Ba alkaline earth metal reaction temperature 200 200 200 200 200 200 (° C.) propylene conversion 0.7 0.6 0.3 0.6 0.4 0.4 0.5 (%) propylene oxide 22 13 8 5 8 7 9 selectivity (%)
  • a catalyst is prepared in the same manner as Example 8, except that TiO 2 is used instead of SiO 2 .
  • Production of propylene oxide is carried out in the same manner as Example 8 except that the catalyst of the present example is used.
  • the metal composition was prepared by a co-impregnation method.
  • a predetermined weight (1.9 g) of an amorphous silica powder (SiO 2 , Japan Aerosil, 380 m 2 /g) was added to an aqueous solution mixture containing 0.54 g of (NH 4 ) 2 RuCl 6 (Aldrich), 0.30 g of Cu(NO 3 ) 2 (Wako) and 0.10 g of KNO 3 (Wako), followed by stirring for 24 hours in the air to impregnate the support with the metal salts.
  • the resulting material was then heated at 100° C. until dried, and calcined at 500° C. for 12 hours in the air to give a catalyst.
  • the catalyst was evaluated by using a fixed-bed reactor, Filling a 1 ⁇ 2-inch reaction tube made of stainless steel with 1 mL of the thus obtained catalyst, the following gases were fed to the reaction tube to carry out the reaction: 450 NmL/h of propylene, 900 NmL/h of the air, 990 NmL/h of a nitrogen gas, Such a reaction was carried out at the reaction temperature of 200° C., 250° C. or 270° C. under the increased pressure (equivalent to 0.3 MPa in the absolute pressure).

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Abstract

A process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.

Description

    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.
  • Previous research on olefin epoxidation involved the use of Ag-based catalysts (Appl. Catal. A. Gen. 2001, 221, 73.), as well as silica supported Cu (J. Catal. 2005, 236, 401), various metal oxides (Appl. Catal. A. Gen. 2007, 316, 142), Au-based catalysts with H2 as a co-reactant (Ind. & Eng. Chem. Res. 1995, 34, 2298, J. Catal. 1998, 178, 566; Appl. Catal. A. Gen. 2000, 190, 43; Angew. Chem. Int. Ed. 2004, 43, 1546), titania based catalysts that deactivated quickly (Catal. Commun. 2001, 1356; Catal. Commun. 2003, 4, 385), molten salts of metal nitrates (Appl. Catal. A. Gen. 2000, 196, 217), the use of O3 (Appl. Catal. A. Gen. 2000, 196, 217) and nitrous oxide (Ind. & Eng. Chem. Res. 1995, 34, 2298) as reactants. Although these developments are scientifically interesting, they have serious drawbacks, such as low PO selectivities and/or low propylene conversions, short catalyst lifetimes, the use of higher pressures or the use of costly co-reactants (Appl. Catal. A. Gen. 2007, 316, 142).
    • SUMMARY OF THE INVENTION
  • The present invention provides:
  • [1] A process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
    [2] The process according to [1], wherein the catalyst comprises (d) halogen component.
    [3] The process according to [1], wherein (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component are supported on a porous support.
    [4] The process according to [2], wherein (a) copper oxide, (b) ruthenium metal or ruthenium oxide, (c) alkaline metal component or alkaline earth metal component and (d) halogen component are supported on a porous support.
    [5] The process according to [3] or [4], wherein the porous support comprises Al2O3, SiO2, TiO2 or ZrO2.
    [6] The process according to [3] or [4], wherein the porous support comprises SiO2.
    [7] The process according to any one of [1] to [6], wherein the total amount of (a) copper oxide, (b) ruthenium metal or rutheniumoxide and (c) alkaline metal component or alkaline earth metal component is 0.01 to 80% by weight of the amount of the catalyst.
    [8] The process according to any one of [1] to [7], wherein the copper/ruthenium metal molar ratio in the catalyst is 1/99 to 99/1.
    [9] The process according to any one of [1] to [8], wherein the ruthenium/(c) component metal molar ratio in the catalyst is 1/99 to 99/1.
    [10] The process according to any one of [1] to [9], wherein (a) copper oxide is CuO.
    [11] The process according to any one of [1] to [10], wherein (b) ruthenium metal or rutheniumoxide is RuO2.
    [12] The process according to any one of [1] to [11], wherein (c) alkaline metal component or alkaline earth metal component is an alkaline metal-containing compound.
    [13] The process according to any one of [1] to [12], wherein (c) alkaline metal component or alkaline earth metal component is a sodium-containing compound.
    [14] The process according to [1] to [12], wherein (c) alkaline metal component or alkaline earth metal component is a potassium-containing compound.
    [15] The process according to [3], wherein the catalyst is obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion and an alkaline metal or alkaline earth metal ion to prepare a composition, followed by calcining the composition.
    [16] The process according to [3] or [4], wherein the catalyst is obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion, an alkaline metal or alkaline earth metal ion and a halogen ion to prepare a composition, followed by calcining the composition.
    [17] The process according to any one of [1] to [16], wherein the olefin is propylene and the olefin oxide is propylene oxide.
    [18] The process according to any one of [1] to [17], which comprises reacting an olefin with oxygen at a temperature of 100 to 350° C.
    [19] A catalyst for production of an olefin oxide which comprises (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
    [20] The catalyst according to [19] which comprises (d) halogen component.
    [21] The catalyst according to [19], wherein (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component are supported on a porous support.
    [22] The catalyst according to [20], wherein (a) copper oxide, (b) ruthenium metal or ruthenium oxide, (c) alkaline metal component or alkaline earth metal component and (d) halogen component are supported on a porous support.
    [23] The catalyst according to [21] which is obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion and an alkaline metal or alkaline earth metal ion to prepare a composition, followed by calcining the composition.
    [24] The catalyst according to [21] or [22] which is obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion, an alkaline metal or alkaline earth metal ion and halogen ion to prepare a composition, followed by calcining the composition.
    [25] The catalyst according to any one of [19] to [24], wherein (c) alkaline metal component or alkaline earth metal component is an alkaline metal-containing compound.
    [26] The catalyst according to [19] to [24], wherein (c) alkaline metal component or alkaline earth metal component is a sodium-containing compound.
    [27] The catalyst according to [19] to [24], wherein (c) alkaline metal component or alkaline earth metal component is a potassium-containing compound.
    [28] The catalyst according to any one of [21] to [27], wherein the porous support comprises Al2O3, SiO2, TiO2 or ZrO2.
    [29] The catalyst according to anyone of [21] to [28], wherein the porous support comprises SiO2.
    [30] The catalyst according to anyone of [19] to [29], wherein the olefin oxide is propylene oxide.
    [31] Use of a catalyst for producing an olefin oxide, said catalyst comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
    [32] The use of a catalyst according to [31], wherein the olefin oxide is propylene oxide.
    • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1 is a graph showing the result of Example 1.
  • FIG. 2 is a graph showing the result of Example 2.
  • FIG. 3 is a graph showing the result of Example 3.
  • FIG. 4 is a graph showing the result of Example 4.
  • FIG. 5 is a graph showing the result of Example 5.
  • FIG. 6 is a graph showing the XRD patterns of Example 6.
    •  DETAILED DESCRIPTION OF THE INVENTION
  • The process of the present invention comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component. In the catalyst, 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 Al2O3, SiO2, TiO2, or ZrO2, more preferably SiO2. Examples of the porous support comprising SiO2 include mesoporous silica. Such a porous support may also comprise zeolites.
  • If the catalyst comprises SiO2 as a support, olefin oxides can be prepared with good yield and good selectivity.
  • The catalyst may comprise one or more kinds of (a) copper oxide.
  • The (a) copper oxide is usually composed of copper and oxygen.
  • Examples of the copper oxide include Cu2O and CuO. The copper oxide is preferably CuO.
  • The catalyst may comprise one or more kinds of (b) ruthenium metal or ruthenium oxide. The (b) ruthenium oxide is usually composed of ruthenium and oxygen. Examples of the ruthenium oxide include RuO4, and RuO2. The component (b) is preferably RuO2.
  • The catalyst may comprise one or more kinds of (c) alkaline metal component or alkaline earth metal component.
  • The component (c) may be an alkaline metal-containing compound, an alkaline earth metal-containing compound, an alkaline metal ion or an alkaline earth metal ion.
  • Examples of the alkaline metal-containing compound include compounds containing an alkaline metal such as Na, K, Rb and Cs. Examples of the alkaline earth metal-containing compound include compounds containing an alkaline earth metal such as Ca, Mg, Sr and Ba. Examples of the alkaline metal ion include Na+, K+, Rb+ and Cs+. Examples of the alkaline earth metal ion include such as Ca2+, Mg2+, Sr2+ and Ba2+.
  • The component (c) is preferably an alkaline metal-containing compound, an alkaline metal or both of them, more preferably an alkaline metal-containing compound, still more preferably a sodium-containing compound or a potassium-containing compound.
  • When the compound (c) is a potassium-containing compound or potassium ion, preferably a potassium-containing compound, the olefin oxide selectivity is excellent at reaction temperature not more than 270° C.
  • The alkaline metal-containing compound and alkaline earth metal-containing compound are preferably an alkaline metal salt and an alkaline earth metal salt. The alkaline metal salt comprises the alkaline metal ion as mentioned above with an anion. The alkaline earth metal salt comprises the alkaline earth metal ion as mentioned above with an anion. Examples of anions in such salts include Cl−, Br−, I−, NO3 −, SO4 2− and CO3 2−. Such salts are preferably an alkaline metal salt with a halogen, such as an alkaline metal halide, or an alkaline earth metal-containing salt with a halogen, such as an alkaline earth metal halide, more preferably an alkaline metal salt with a halogen, still more preferably an alkaline metal chloride.
  • The catalyst comprises preferably CuO, RuO2 and an alkaline metal-containing compound, still more preferably CuO, RuO2 and a sodium-containing compound, because the olefin oxide yield and selectivity can be improved by adopting such combination to the production of an olefin oxide. Particularly if the catalyst comprises NaCl, as the (c) component, it can show excellent olefin oxide selectivity and yield. The copper/ruthenium 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. The upper limit of the molar ratio is more preferably 98/2, still more preferably 97/3.
  • 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.
  • When the components (a), (b) and (c) are supported on a porous support in the catalyst, the total content of the components (a), (b) and (c) is preferably 0.01 to 80% by weight of the amount of the catalyst. 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% 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.
  • Examples of such a halogen-containing compound include halides of copper or ruthenium and oxyhalides of copper or ruthenium. If the catalyst comprises the component (d), 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.
  • When the components (a), (b) and (c) are supported on a porous support in the catalyst, the catalyst can be obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion and an alkaline metal or alkaline earth metal-containing 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. If the catalyst comprises component (c) which is an alkaline metal salt with a halogen or alkaline earth metal salt with a halogen, and the component (d) supported on the porous support, the catalyst can be obtained in the same procedure as mentioned above except that solution contains copper ion, a ruthenium ion, an alkaline metal or alkaline earth metal-containing ion and a halogen ion.
  • The solution containing a copper ion, a ruthenium ion and an alkaline metal or alkaline earth metal ion can be prepared by dissolving a copper metal salt, a ruthenium metal salt and an alkaline metal or alkaline earth 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 oxychloride, 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 Ru2OCl4, Ru2OCl5 and Ru2OC16, a halogeno complex such as [RuCl2(H2O)4]Cl, an ammine complex such as [Ru(NH3)5H2O]Cl2, [Ru(NH3)5Cl]Cl2, [Ru(NH3)6]Cl2 and [Ru(NH3)6]Cl3, a carbonyl complex such as Ru(CO)5 and Ru3(CO)12, a carboxylate complex such as [Ru3O(OCOCH3)6(H2O)3], ruthenium nitrosylchloride, and [Ru2(OCOR)4]Cl (R=alkyl group having 1 to 3 carbon atoms), a nitrosyl complex such as [Ru(NH3)5(NO)]Cl3, [Ru(OH)(NH3)4(NO)](NO3)2 and [Ru(NO)](NO3)3, an amine complex, an acetylacetonate complex, and ammonium salt such as (NH4)2RuCl6. The alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the (c) component. Examples of the alkaline metal or alkaline earth metal salt include alkaline metal nitrates, alkaline earth metal nitrates, alkaline metal halides and alkaline earth metal halides, preferably alkaline metal halides and alkaline metal nitrates, more preferably NaNO3, NaCl, KCl and KNO3. 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 (c) component such as NaCl and the (d) component such as halides and oxyhalides of Cu or Ru. The solution may contain acidic or basic compounds in order to control its pH.
  • The acid compound may be any of an inorganic acid and an organic acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, nitrous acid and perchloric acid etc. Examples of the organic acid include aliphatic carboxylic acids such as acetic acid, oxalic acid, propionic acid, butyric acid, citric acid, maleic acid, fumaric acid and tartaric acid etc.; and aromatic carboxylic acids such as benzoic acid, dicarboxybenzene, tricarboxybenzene, dicarboxynaphthalene and dicarboxyanthracene etc.
  • Examples of the base compound include alkaline metal hydroxides, amine compounds, imine compounds, hydrazine or hydrazine compounds, ammonia, hydroxylamine, hydroxyamine and ammonium hydroxides.
  • Examples of the alkaline metal hydroxides include sodium hydroxide, potassium hydroxide etc. Examples of the amine compounds include aliphatic amines having a carbon number of 1 to 20 and aromatic amines having a carbon number of 6 to 20, such as methylamine, ethylamine, propylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, decylamine, dodecylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, ethanolamine, dimethylethanolamine, diethylethanolamine, triethanolamine, ethylenediamine, tetramethylenediamine, pentamethylenediamine, diethylenetriamine, aniline, benzyamine and phenylenediamine etc.
  • Examples of the imine compounds include ethyleneimine, pyrrolidine, piperidine and piperazine etc. Examples of the amide compounds include acetamide and benzamide etc. Examples of the hydrazine compounds include methylhydrazine and phenylhydrazine etc. Examples of the quaternary ammonium salts include quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide etc.; quaternary ammonium halides such as tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, and tetraethylammonium bromide etc.; etc.
  • 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 99.5% by weight, still preferably 70 to 99.9% by weight of the catalyst as obtained.
  • 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 air or also under an inert gas atmosphere (for example, Ar, N2, He) at standard pressure or reduced pressure. A drying time is preferably in the range from 0.5 to 24 hours. After drying, the composition can be shaped to a desired structure as necessary.
  • Calcining the composition is not limited, but preferably may be performed under a gas atmosphere containing oxygen. Examples of such a gas stream include air and an oxygen gas. 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 ruthenium oxide and copper 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.
  • Next, the following explains a reaction of an olefin with oxygen in the presence of the catalyst as described above.
  • In the present invention, the olefin may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms. The olefin may be a monoolefin or a diolefin. Examples of the monoolefin include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, and decene. Examples of the diene include butadiene such as 1,3-butadiene or 1,2-butadiene. Examples of the olefin include preferably monoolefin, more preferably ethylene, propylene, butene, pentene, hexene, heptene and octene, still more preferably ethylene, propylene and butene, most preferably propylene.
  • The reaction is generally performed in the gas phase. In the reaction, the olefin and oxygen may be fed respectively in the form of a gas. Olefin and oxygen gases can be fed in the form of their mixed gas. Olefin and oxygen gases may be fed with diluent gases. Examples of diluent gases include nitrogen, methane, ethane, propane, carbon dioxide, or rare gases, such as argon and helium.
  • As the oxygen source, pure oxygen may be used, or a mixed gas containing a gas inactive to the reaction, such as air, may be used. The amount of oxygen used varies depending on the reaction type, the catalyst, the reaction temperature or the like. The amount of oxygen is typically 0.01 to 100 mol, and preferably 0.03 to 30 mol, and more preferably 0.25 to 10 mol, with respect to 1 mol of the olefin.
  • The reaction is performed at a temperature generally of 100 to 350° C., preferably of 120 to 330° C., more preferably of 170 to 310° C., still more preferably of 200 to 270° C. In particular, the reaction temperature is most preferably 240 to 270° C. for the reaction in a microreactor.
  • 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 present invention, the olefin oxide may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms. The olefin oxide may have one carbon-carbon double bond when the diolefin is applied for the reaction. Examples of the olefin oxide having one carbon-carbon double bond include 3,4-epoxy-1-butene. Examples of the olefin oxides include preferably ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide and octene oxide, more preferably ethylene oxide, propylene oxide and butene oxide, still more preferably propylene oxide.
  • The olefin oxide as obtained can be collected by a method known in the art such as separation by distillation.
    • EXAMPLES
  • In Examples 1 to 5, each measurement was performed according to the following method:
  • Data analysis for sample gases 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).
  • The detected products were propylene oxide (PO), acetone (AT), acetaldehyde (AD), COx (CO2 and CO), and propanal+acrolein (PaL+AC).
  • The propylene conversion, product selectivity, and yield (calculated as selectivity of product×propylene conversion) of products were calculated on the basis of carbon balance. Propylene conversions (XPR) were determined from the following:

  • XPR={[PO+AC+AT+2AD/3+CO2/3]out/[C3H6]in}×100%;
  • and PO selectivities (SPO) were then calculated using the following expression:

  • SPO={[PO]/[PO+AC+AT+2AD/3+CO2/3]}×100%
  • Note: 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.
    • Example 1
  • Aqueous solutions of Ru[(NH4)2RuCl6, Aldrich] and Cu [Cu(NO3)2, Alfa Aesar, ACS, 98.0%-102.0%] and Na[NaNO3, Alfa Aesar, ACS, 99.0%] were mixed at a metal weight ratio of 4:2:1 (=Ru:Cu:Na), to prepare a metal salt solution for achieving 12.5 wt % (by metal atomic weight, relative to the amount of the catalyst) loading on a SiO2 support powder (surface area 145 m2/g). The metal salt solution was then allowed to impregnate the support for 24 hours in air. The resulting material was then heated at 150° C. until dried, and calcined at 500° C. for 12 hours in air.
  • The catalyst (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 (C3H6), 4 vol % O2, 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 190, 210, 230, 250, 260, 270, 290 or 310° C.
  • Gas sampling was accomplished by withdrawing reactor exit gases using the passivated 200 micron ID capillary sampling probe.
  • The results are shown in FIG. 1.
    • Example 2
  • The catalysts were prepared in the same manner as Example 1, except that the total metal content in the catalyst was 8% by weight. Propylene oxide was prepared in the same manner as Example 1 except that the catalysts of the present example were used, the reactor temperature was 250° C., and GHSV was changed.
  • The results are shown in FIG. 2.
    • Example 3
  • The catalysts were prepared in the same manner as Example 1, except that the total metal content in each of the catalysts was 5, 7, 10 or 12.5% by weight. Propylene oxide was prepared in the same manner as Example 1 except that the catalysts of the present example were used and the reactor temperature was 250° C.
  • The results are shown in FIG. 3.
    • Example 4
  • The catalysts were prepared in the same manner as Example 3, except that the total metal content in the catalysts was 12.5% by weight. Propylene oxide was prepared in the same manner as Example 3 except that the oxygen/propylene (volume ratio) was changed.
  • The results are shown in FIG. 4.
    • Example 5
  • Time-on-stream testing was conducted with the catalyst. The catalyst was prepared in the same manner as Example 4. Propylene oxide was prepared in the same manner as Example 3 except that the reactor temperature was 250° C. or 265° C.
  • The results are shown in FIG. 5.
    • Example 6
  • The powder x-ray diffraction pattern of the catalyst obtained in Example 1 was determined with PANalytical X'Pert PRO fitted with a Ni filter and a Soller slit collimator.
  • The Cu—Kα radiation at 45 kV and 40 mA was used to identify the active catalyst phase.
  • The following compositions were also examined in the same manner, Na2O (1.8 wt % Na, relative to the total of Na2O and SiO2) supported on SiO2 which was prepared from NaNO3; CuO (3.6 wt % Cu, relative to the total of CuO and SiO2) supported on SiO2 which was prepared from Cu(NO3)2; RuO2 (7.2 wt % Ru, relative to the total of RuO2 and SiO2) supported on SiO2 which was prepared from (NH4)2RuCl6; NaCl (1.8 wt % Na, relative to the total of NaCl and SiO2) supported on SiO2 which was prepared from NaCl; and bimetallic RuO2+CuO supported on SiO2 which was prepared in the same manner as the catalyst except that NaCl was not used.
  • The XRD patterns are shown in FIG. 6. The XRD pattern of the catalyst shows that the catalyst comprises CuO, RuO2 and NaCl without forming any crystalline mixed metal oxides or alloys.
    • Example 7
  • A catalyst is prepared in the same manner as Example 1, except that TiO2 is used instead of SiO2. Production of propylene oxide is carried out in the same manner as Example 1 except that the catalyst of the present example is used.
  • In Examples 8 to 15, 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 into the TCD-GC equipped with a column of Gaskuropack 54 (2 m). All products in the reaction gas were collected for 1 hour with double methanol traps connected in series and cooled with a dry-ice/methanol bath. The two methanol solutions were mixed together and added to anisole as an external standard, and then analyzed with two FID-GCs equipped with different columns, PoraBOND U (25 m) and PoraBOND Q (25 m).
  • The propylene conversion, product selectivity, and yield of products were calculated in the same manner as Examples 1 to 5.
    • Example 8
  • The metal composition was prepared by a co-impregnation method. A predetermined weight (1.9 g) of an amorphous silica powder (SiO2, Japan Aerosil, 380 m2/g) was added to an aqueous solution mixture containing 0.54 g of (NH4)2RuCl6 (Aldrich), 0.30 g of Cu(NO3)2 of (Wako) and 0.10 g NaNO, (Wako), followed by stirring for 24 hours in the air to impregnate the support with the metal salts. The resulting material was then heated at 100° C. until dried, and calcined at 500° C. for 12 hours in the air to give a catalyst.
  • The catalyst was evaluated by using a fixed-bed reactor. Filling a ½-inch reaction tube made of stainless steel with 1 mL of the thus obtained catalyst, the following gases were fed to the reaction tube to carry out the reaction: 450 NmL/h of propylene, 900 NmL/h of the air, 990 NmL/h of a nitrogen gas. Such a reaction was carried out at the reaction temperature of 200° C. under the increased pressure (equivalent to 0.3 MPa in the absolute pressure).
  • The result is shown in Table 1.
    • Example 9
  • The preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.64 g of (NH4)2RuCl6 (Aldrich), 0.35 g of Cu(NO3)2 (Wako), 0.08 g of Rb(NO3) (Wako) and 2.3 g of an amorphous silica powder (SiO2, Japan Aerosil, 380 m2/g) as raw materials.
  • The result is shown in Table 1.
    • Example 10
  • The preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.76 g of (NH4)2RuCl6 (Aldrich), 0.42 g of Cu(NO3)2 (Wako), 0.08 g of Cs(NO3) (Wako) and 2.7 g of an amorphous silica powder (SiO2, Japan Aerosil, 380 m2/g) as raw materials.
  • The result is shown in Table 1.
    • Example 11
  • The preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.23 g of (NH4)2RuCl6 (Aldrich), 0.13 g of Cu(NO3)2 (Wako), 0.1 g of Mg(NO3)2 (Wako) and 0.8 g of an amorphous silica powder (SiO2, Japan Aerosil, 380 m2/g) as raw materials.
  • The result is shown in Table 1.
    • Example 12
  • The preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 1.0 g of (NH4)2RuCl6 (Aldrich), 0.58 g of Cu(NO3)2 (Wako), 0.08 g of Ca(NO3)2 (Wako) and 3.7 g of an amorphous silica powder (SiO2, Japan Aerosil, 380 m2/g) as raw materials. The result is shown in Table 1.
    • Example 13
  • The preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.86 g of (NH4)2RuCl6 (Aldrich), 0.47 g of Cu(NO3)2 (Wako), 0.15 g of Sr(NO3)2 (Wako) and 3.0 g of an amorphous silica powder (SiO2, Japan Aerosil, 380 m2/g) as raw materials.
  • The result is shown in Table 1.
    • Example 14
  • The preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.73 g of (NH4)2RuCl6 (Aldrich), 0.40 g of Cu(NO3)2 (Wako), 0.10 g of Ba(NO3)2 (Wako) and 2.6 g of amorphous silica powder (SiO2, Japan Aerosil, 380 m2/g) as raw materials.
  • The result is shown in Table 1.
  • TABLE 1
    Example
    8 9 10 11 12 13 14
    alkaline metal or Na Rb Cs Mg Ca Sr Ba
    alkaline earth metal
    reaction temperature 200 200 200 200 200 200 200
    (° C.)
    propylene conversion 0.7 0.6 0.3 0.6 0.4 0.4 0.5
    (%)
    propylene oxide 22 13 8 5 8 7 9
    selectivity (%)
    • Example 15
  • A catalyst is prepared in the same manner as Example 8, except that TiO2 is used instead of SiO2. Production of propylene oxide is carried out in the same manner as Example 8 except that the catalyst of the present example is used.
    • Examples 16-18
  • The metal composition was prepared by a co-impregnation method. A predetermined weight (1.9 g) of an amorphous silica powder (SiO2, Japan Aerosil, 380 m2/g) was added to an aqueous solution mixture containing 0.54 g of (NH4)2RuCl6 (Aldrich), 0.30 g of Cu(NO3)2 (Wako) and 0.10 g of KNO3 (Wako), followed by stirring for 24 hours in the air to impregnate the support with the metal salts. The resulting material was then heated at 100° C. until dried, and calcined at 500° C. for 12 hours in the air to give a catalyst.
  • The catalyst was evaluated by using a fixed-bed reactor, Filling a ½-inch reaction tube made of stainless steel with 1 mL of the thus obtained catalyst, the following gases were fed to the reaction tube to carry out the reaction: 450 NmL/h of propylene, 900 NmL/h of the air, 990 NmL/h of a nitrogen gas, Such a reaction was carried out at the reaction temperature of 200° C., 250° C. or 270° C. under the increased pressure (equivalent to 0.3 MPa in the absolute pressure).
  • The result is shown in Table 2.
  • TABLE 2
    Example 16 17 18
    alkaline metal K K K
    reaction temperature 200 250 270
    (° C.)
    propylene conversion (%) 0.8 3.3 3.5
    propylene oxide 8 13 15
    selectivity (%)
    STY* 17 102 126
    *STY, i.e., space time yield, represents “(The amount of propylene oxide (μmol)/{the amount of catalyst(ml)*hour}”.
    • Example 19
  • The preparation and the reaction are conducted in the same manner as Example 8, except that 1,3-butadiene is used instead of propylene to give 3,4-epoxy-butene.

Claims (32)

1. A process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
2. The process according to claim 1, wherein the catalyst comprises (d) halogen component.
3. The process according to claim 1, wherein (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component are supported on a porous support.
4. The process according to claim 2, wherein (a) copper oxide, (b) ruthenium metal or ruthenium oxide, (c) alkaline metal component or alkaline earth metal component and (d) halogen component are supported on a porous support.
5. The process according to claim 3 or 4, wherein the porous support comprises Al2O3, SiO2, TiO2 or ZrO2.
6. The process according to claim 3 or 4, wherein the porous support comprises SiO2.
7. The process according to claim 1 or 2, wherein the total amount of (a) copper oxide, (b) ruthenium metal or rutheniumoxide and (c) alkaline metal component or alkaline earth metal component is 0.01 to 80% by weight of the amount of the catalyst.
8. The process according to claim 1 or 2, wherein the copper/ruthenium metal molar ratio in the catalyst is 1/99 to 99/1.
9. The process according to claim 1 or 2, wherein the ruthenium/(c) component metal molar ratio in the catalyst is 1/99 to 99/1.
10. The process according to claim 1 or 2, wherein (a) copper oxide is CuO.
11. The process according to claim 1 or 2, wherein (b) ruthenium metal or rutheniumoxide is RuO2.
12. The process according to claim 1 or 2, wherein (c) alkaline metal component or alkaline earth metal component is an alkaline metal-containing compound.
13. The process according to claim 1 or 2, wherein (c) alkaline metal component or alkaline earth metal component is a sodium-containing compound.
14. The process according to claim 1 or 2, wherein (c) alkaline metal component or alkaline earth metal component is a potassium-containing compound.
15. The process according to claim 3, wherein the catalyst is obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion and an alkaline metal or alkaline earth metal ion to prepare a composition, followed by calcining the composition.
16. The process according to claim 3 or 4, wherein the catalyst is obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion, an alkaline metal or alkaline earth metal ion and a halogen ion to prepare a composition, followed by calcining the composition.
17. The process according to claim 1 or 2, wherein the olefin is propylene and the olefin oxide is propylene oxide.
18. The process according to claim 1 or 2, which comprises reacting an olefin with oxygen at a temperature of 100 to 350° C.
19. A catalyst for production of an olefin oxide which comprises (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
20. The catalyst according to claim 19, which comprises (d) halogen component.
21. The catalyst according to claim 19, wherein (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component are supported on a porous support.
22. The catalyst according to claim 20, wherein (a) copper oxide, (b) ruthenium metal or ruthenium oxide, (c) alkaline metal component or alkaline earth metal component and (d) halogen component are supported on a porous support.
23. The catalyst according to claim 21 which is obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion and an alkaline metal or alkaline earth metal ion to prepare a composition, followed by calcining the composition.
24. The catalyst according to claim 21 or 22 which is obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion, an alkaline metal or alkaline earth metal ion and a halogen ion to prepare a composition, followed by calcining the composition.
25. The catalyst according to claim 19 or 20, wherein (c) alkaline metal component or alkaline earth metal component is an alkaline metal-containing compound.
26. The catalyst according to claim 19 or 20, wherein (c) alkaline metal component or alkaline earth metal component is a sodium-containing compound.
27. The catalyst according to claim 19 or 20, wherein (c) alkaline metal component or alkaline earth metal component is a potassium-containing compound.
28. The catalyst according to claim 21 or 22, wherein the porous support comprises Al2O3, SiO2, TiO2 or ZrO2.
29. The catalyst according to claim 21 or 22, wherein the porous support comprises SiO2.
30. The catalyst according to claim 19 or 20, wherein the olefin oxide is propylene oxide.
31. Use of a catalyst for producing an olefin oxide, said catalyst comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
32. The use of a catalyst according to claim 31, wherein the olefin oxide is propylene oxide.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8765981B2 (en) 2011-01-05 2014-07-01 Sumitomo Chemical Company, Limited Process for producing olefin oxide
US8829211B2 (en) 2011-01-24 2014-09-09 Sumitomo Chemical Company, Limited Direct conversion of olefin to olefin oxide by molecular oxygen
WO2021126947A1 (en) * 2019-12-16 2021-06-24 Calera Corporation Electrochemical, bromination, and oxybromination systems and methods to form propylene oxide or ethylene oxide

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110152547A1 (en) * 2009-12-17 2011-06-23 Sumitomo Chemical Company, Limited Process for producing olefin oxide
WO2013025316A1 (en) * 2011-08-17 2013-02-21 Sumitomo Chemical Company, Limited Process for producing olefin oxide
WO2013025315A1 (en) * 2011-08-17 2013-02-21 Sumitomo Chemical Company, Limited Process for producing olefin oxide
WO2013062791A1 (en) * 2011-10-24 2013-05-02 Sumitomo Chemical Company, Limited Process for producing olefin oxide
WO2014003209A1 (en) * 2012-06-29 2014-01-03 Sumitomo Chemical Company, Limited Process for producing olefin oxide
US10508032B2 (en) 2015-03-20 2019-12-17 Northwestern University Catalysts and related methods for photocatalytic production of H2O2 and thermocatalytic reactant oxidation
EP3117898A1 (en) * 2015-07-15 2017-01-18 i2 Gesellschaft für Innovation mbH Preparation of a mixed catalyst
CN106732593B (en) * 2016-12-30 2019-11-22 天津市长芦化工新材料有限公司 Copper-based solid-phase catalyst and its preparation method and application
EP3642177A1 (en) 2017-06-23 2020-04-29 Haldor Topsøe A/S A process for oxidation of a lower alkane at low temperatures in ammonia-containing gas mixtures
EA202090118A1 (en) 2017-06-23 2020-05-22 Хальдор Топсёэ А/С METHOD FOR OXIDATION OF LOWER ALKENE AT LOW TEMPERATURES IN GAS MIXTURES CONTAINING AMMONIA
US10800981B2 (en) 2019-02-13 2020-10-13 Saudi Arabian Oil Company Process for producing diesel fuel from olefinic refinery feedstreams

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4497908A (en) * 1984-03-23 1985-02-05 Shell Oil Company Copper-alkali metal-ruthenium/silica catalyst for converting syngas to linear alpha-olefins
US5957221A (en) 1996-02-28 1999-09-28 Baker Hughes Incorporated Downhole core sampling and testing apparatus
EP1073649B1 (en) * 1998-04-15 2003-09-10 Dow Global Technologies, Inc. Process for the direct oxidation of olefins to olefin oxides
DE10024096A1 (en) * 2000-05-18 2001-11-22 Bayer Ag Hydrocarbon epoxidation is catalysed by a mixture of two or more metals on a support so as to allow direct oxygen or air oxidation of propylene to propylene oxide
JP2002371074A (en) 2001-04-13 2002-12-26 Mitsubishi Chemicals Corp Method for producing oxysilane compound
US6472572B1 (en) 2001-06-20 2002-10-29 Grt, Inc. Integrated process for synthesizing alcohols and ethers from alkanes
US6765101B1 (en) 2001-05-01 2004-07-20 Union Carbide Chemicals & Plastics Technology Corporation Synthesis of lower alkylene oxides and lower alkylene glycols from lower alkanes and/or lower alkenes
DE10208254A1 (en) * 2002-02-26 2003-09-04 Bayer Ag catalyst
GB0227081D0 (en) * 2002-11-20 2002-12-24 Exxonmobil Res & Eng Co Methods for preparing catalysts
US7348444B2 (en) 2003-04-07 2008-03-25 Shell Oil Company Process for the production of an olefin oxide
US20060016722A1 (en) * 2004-07-08 2006-01-26 Conocophillips Company Synthetic hydrocarbon products
US20110152547A1 (en) 2009-12-17 2011-06-23 Sumitomo Chemical Company, Limited Process for producing olefin oxide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Aldrich , Catalog Handbook of Fine Chemicals, 1998-1999, p.438,442,1473-1474 ( a total of five pages). *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8765981B2 (en) 2011-01-05 2014-07-01 Sumitomo Chemical Company, Limited Process for producing olefin oxide
US8829211B2 (en) 2011-01-24 2014-09-09 Sumitomo Chemical Company, Limited Direct conversion of olefin to olefin oxide by molecular oxygen
WO2021126947A1 (en) * 2019-12-16 2021-06-24 Calera Corporation Electrochemical, bromination, and oxybromination systems and methods to form propylene oxide or ethylene oxide

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