WO2003022827A1 - Procede de synthese d'oxydes olefiniques - Google Patents

Procede de synthese d'oxydes olefiniques Download PDF

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Publication number
WO2003022827A1
WO2003022827A1 PCT/US2002/020981 US0220981W WO03022827A1 WO 2003022827 A1 WO2003022827 A1 WO 2003022827A1 US 0220981 W US0220981 W US 0220981W WO 03022827 A1 WO03022827 A1 WO 03022827A1
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WO
WIPO (PCT)
Prior art keywords
metal oxide
bromine
recycling
reacting
carried out
Prior art date
Application number
PCT/US2002/020981
Other languages
English (en)
Inventor
Xiao Ping Zhou
Galen D. Stucky
Jeffrey H. Sherman
Original Assignee
Grt, Inc.
The Regents Of The University Of California
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/951,581 external-priority patent/US6403840B1/en
Application filed by Grt, Inc., The Regents Of The University Of California filed Critical Grt, Inc.
Publication of WO2003022827A1 publication Critical patent/WO2003022827A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
    • C07D301/26—Y being hydrogen

Definitions

  • This invention relates generally to the synthesis of olefin oxides, and more particularly to an economical and safe process for synthesizing propylene oxide and other olefin oxides .
  • Co-pending application serial number 09/886,078 filed June 20, 2001 and assigned to the assignee hereof is incorporated herein by reference.
  • the co-pending application discloses and claims a process for synthesizing alcohols and ethers from alkanes .
  • the process involves reacting an alkane with bromine to form the corresponding alkyl bromide and hydrogen bromide.
  • the alkyl bromide and the hydrogen bromide are reacted with a metal oxide to produce the corresponding alcohol and/or ether, and metal bromide.
  • the metal bromide is oxidized to form the original metal oxide and bromine, both of which are recycled.
  • the present invention employs a similar procedure to synthesize olefin oxides, particularly propylene oxide.
  • Propylene oxide has heretofore been produced using a wide variety of procedures, none of which is particularly satisfactory.
  • propylene chlorohydrin The oldest and most widely used procedure for preparing propylene oxide is the propylene chlorohydrin process.
  • An early propylene chlorohydrin technique involved electrolyzation of propylene in aqueous potassium chloride to prepare propylene chlorohydrin which was then dehydrohalogenated to produce propylene oxide.
  • propylene oxide is prepared by reacting propylene with chlorine/water to prepare propylene chlorohydrin, then reacting the propylene chlorohydrin with aqueous calcium hydroxide, sodium hydroxide or calcium carbonate to obtain propylene oxide.
  • a major drawback to the propylene chlorohydrin process involves the fact that the manufacture of a given quantity of propylene oxide necessarily results in the manufacture of a like or greater quantity of various salts which have little commercial value.
  • a further disadvantage of the propylene chlorohydrin process is the fact that the propylene oxide product must be separated from large quantities of water, generally through steam stripping.
  • Propylene oxide can also be manufactured utilizing the ethylbenzene process.
  • the ethylbenzene process involves reacting ethylbenzene with oxygen to generate ethylbenzene hydroperoxide which is then reacted with propylene to obtain propylene oxide and alpha phenylethano1.
  • the alpha phenylethanol is then converted to styrene by dehydration.
  • the major drawbacks to the ethylbenzene process involves the production of styrene in equal quantities with the desired propylene oxide and the use of ethylbenzene hydroperoxide, which is both explosive and subject to decomposition. Cumene can also be used to manufacture propylene oxide.
  • the cumene is oxidized to produce cumene hydroperoxide which is then reacted with propylene to form propylene oxide and cumyl alcohol.
  • the cumyl alcohol is reduced to cumene by reaction with hydrogen over a catalyst and is recycled.
  • the drawbacks to the cumene process include the use of large amounts of cumene hydroperoxide which is highly explosive and the consumption of expensive hydrogen.
  • a fourth process for manufacturing propylene oxide is known as the tert-butane hydroperoxide process.
  • isobutane is oxidized by reaction with oxygen to obtain tertiary butane hydroperoxide, which is then reacted with propylene to form propylene oxide and tert-BuOH.
  • the drawbacks to the process include the direct reaction of butane with oxygen, the use of dangerous tert-butane hydroperoxide, and the production of tert-BuOH as a byproduct.
  • Still another process for producing propylene oxide is known as the hydrogen ⁇ peroxide process .
  • propylene is reacted with hydrogen peroxide in a solvent such as methanol over a catalyst.
  • Drawbacks to the process include the fact that the reaction rate is very slow and the fact that expensive hydrogen is necessarily consumed to form hydrogen peroxide .
  • a sixth method of synthesizing propylene oxide involves direct oxidation of propylene.
  • propylene is reacted with oxygen over a catalyst to generate propylene oxide.
  • safety considerations dictate that the process is very carefully controlled.
  • Other drawbacks include low conversion rates, typically below 10% and low selectivity, typically below 40%.
  • the present invention comprises a method of synthesizing propylene oxide and other olefin oxides which overcomes the foregoing and other difficulties that have long since characterized the prior art.
  • an olefin bromohydrin or an alkane dibromide is reacted with a metal oxide to form olefin oxide and metal bromide.
  • the metal bromide is converted to obtain the original metal oxide and bromine, both of which are recycled.
  • an olefin bromohydrin and/or an alkane dibromide (such as propylene bromohydrin and/or 1, 2-dibromopropane) is reacted with a metal oxide to synthesize olefin oxide
  • Cu(N0 3 ) 2 (0.5M, 6.8ml) solution was mixed with BaBr 2 (0.5M, 1.2ml). A clear solution was obtained. The solution was added into Zr solution (0.5M, 8.0ml) (as prepared above) . After stirring for a few seconds, a gel was obtained. The gel was dried at 110 2 C for 4 hours, then heated to 500 S C within 6 hours, and calcined at 500 2 C for 4 hours. BaBr 2 CuO/Zr0 2 metal oxide (M2) was obtained. M3 Cu(N0 3 ) 2 (0.5M, 7.6ml) solution was mixed with CaBr 2 (0.5M,
  • Propylene bromohydrin (1.00ml/hour) and helium (2.0ml/minute) were passed through a reactor that was packed with 3.0000 gram Ml, which was heated to 100 2 C.
  • Propylene bromohydrin (0.50ml/hour) and nitrogen (5. Oml/minute) were passed through a reactor that packed with 0.8286 gram M3, which was heated to 120 2 C. Within the first 1.5 hours, an average propylene bromohydrin conversion of 50%, with 41% propylene oxide average selectivity was obtained. 1,2-dibromopropane 1, 2-dibromopropane (1. OOml/hour) (0.50ml/hour) and nitrogen (5. Oml/minute) were passed through a reactor that packed with 0.8286 gram M3 , which was heated to 100 ⁇ C. Within the first 1.5 hours, an average propylene bromohydrin conversion of 40%, with 59% propylene oxide average selectivity was obtained.
  • the metal oxide can be an oxide of the following metals: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
  • the reactions can be carried out at a temperature range of between about 50 2 C to about 600 2 C.
  • the reactions pressure can be from about 1 to about 200 atm.
  • the reaction can be carried out with or without helium.
  • the metal bromide resulting from the process can be converted in oxygen or in air to obtain the original metal oxide and bromine, both of which are recycled.
  • the conversion reaction takes place at a temperature range of between about 50 to about 700 2 C and a pressure range from about 1 to 300atm.
  • the method of the present invention operates on ' a continuous or batch basis to convert olefin bromohydrins and/or alkane dibromides to olefins oxides.
  • the method of the present invention operates at relatively low temperatures and at low pressures and is therefore economical in use.
  • the favorable economics of the method also result from the fact that only the bromohydrin and/or dibromide reactants and oxygen are consumed. " The method does not involve direct contact between the reactants and oxygen and is therefore relatively safe.

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

Abstract

Des bromohydrindènes oléfiniques et/ou des dibromures d'alcane sont mis à réagir avec un oxyde métallique de façon à obtenir des oxydes oléfiniques. Le bromure métallique est converti de façon à former l'oxyde et le bromure métalliques de base, les deux étant recyclés.
PCT/US2002/020981 2001-09-11 2002-06-10 Procede de synthese d'oxydes olefiniques WO2003022827A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/951,581 US6403840B1 (en) 2001-06-20 2001-09-11 Process for synthesizing olefin oxides
US09/951,581 2001-09-11

Publications (1)

Publication Number Publication Date
WO2003022827A1 true WO2003022827A1 (fr) 2003-03-20

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WO (1) WO2003022827A1 (fr)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7019182B2 (en) 2001-04-18 2006-03-28 Grt, Inc. Method of hydrocarbon preservation and environmental protection
US7148390B2 (en) 2001-06-20 2006-12-12 Grt, Inc. Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US7161050B2 (en) 2001-06-20 2007-01-09 Grt, Inc. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US7230150B2 (en) 2001-04-18 2007-06-12 Grt, Inc. Zone reactor
US7348464B2 (en) 2004-04-16 2008-03-25 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US7361794B2 (en) 2001-04-18 2008-04-22 Grt, Inc. Zone reactor
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
US7883568B2 (en) 2006-02-03 2011-02-08 Grt, Inc. Separation of light gases from halogens
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006169A (en) * 1976-02-26 1977-02-01 Smithkline Corporation Epoxidation of α,β-ethylenic ketones
US4496752A (en) * 1979-05-03 1985-01-29 The Lummus Company Production of epoxy compounds from olefinic compounds
US5486627A (en) * 1994-12-02 1996-01-23 The Dow Chemical Company Method for producing epoxides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006169A (en) * 1976-02-26 1977-02-01 Smithkline Corporation Epoxidation of α,β-ethylenic ketones
US4496752A (en) * 1979-05-03 1985-01-29 The Lummus Company Production of epoxy compounds from olefinic compounds
US5486627A (en) * 1994-12-02 1996-01-23 The Dow Chemical Company Method for producing epoxides

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7230150B2 (en) 2001-04-18 2007-06-12 Grt, Inc. Zone reactor
US7019182B2 (en) 2001-04-18 2006-03-28 Grt, Inc. Method of hydrocarbon preservation and environmental protection
US7361794B2 (en) 2001-04-18 2008-04-22 Grt, Inc. Zone reactor
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US7148390B2 (en) 2001-06-20 2006-12-12 Grt, Inc. Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US7161050B2 (en) 2001-06-20 2007-01-09 Grt, Inc. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US8415512B2 (en) 2001-06-20 2013-04-09 Grt, Inc. Hydrocarbon conversion process improvements
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7880041B2 (en) 2004-04-16 2011-02-01 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US7348464B2 (en) 2004-04-16 2008-03-25 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US7883568B2 (en) 2006-02-03 2011-02-08 Grt, Inc. Separation of light gases from halogens
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US8415517B2 (en) 2008-07-18 2013-04-09 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems

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