WO2003062196A2 - Procede en phase gazeuse et catalyseur pour la preparation d'un oxyde de propylene - Google Patents

Procede en phase gazeuse et catalyseur pour la preparation d'un oxyde de propylene Download PDF

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Publication number
WO2003062196A2
WO2003062196A2 PCT/US2003/001873 US0301873W WO03062196A2 WO 2003062196 A2 WO2003062196 A2 WO 2003062196A2 US 0301873 W US0301873 W US 0301873W WO 03062196 A2 WO03062196 A2 WO 03062196A2
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WO
WIPO (PCT)
Prior art keywords
catalyst
gas
phase process
bimetallic compound
platinum
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PCT/US2003/001873
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English (en)
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WO2003062196A3 (fr
Inventor
Michiel Makkee
Aalbert Zwijnenburg
Jacob Adriaan Moulijn
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Huntsman International Llc
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Application filed by Huntsman International Llc filed Critical Huntsman International Llc
Priority to AU2003209327A priority Critical patent/AU2003209327A1/en
Publication of WO2003062196A2 publication Critical patent/WO2003062196A2/fr
Publication of WO2003062196A3 publication Critical patent/WO2003062196A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • 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
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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

  • This invention relates to a gas-phase process for the preparation of propylene oxide, also called hydro-oxidation of propylene with hydrogen and oxygen or epoxidation of propylene using hydrogen and oxygen.
  • the invention also relates to a catalyst that can be used for the preparation of propylene oxide.
  • WO 00/59633 described the preparation of gold catalysts for the epoxidation of propylene, wherein the gold is at least partially oxidized; and WO 00/59632 disclosed a process for the hydro-oxidation of propylene to propylene oxide using catalysts containing both titanium and at least partially oxidized gold and with a propylene conversion of 3.5% and a selectivity to propylene oxide of 92.6% (see example 7).
  • an object of this invention is to provide a process that enables the preparation of propylene oxide with a high selectivity to propylene oxide and a reduced water production.
  • the invention resides in a gas-phase process for the preparation of propylene oxide comprising contacting propylene with oxygen and hydrogen in the presence of a catalyst comprising a bimetallic compound supported on a titanium containing support, wherein the bimetallic compound comprises gold and a metal M selected from the group consisting of platinum, tin, and rhodium.
  • the bimetallic compound comprises platinum and gold and has a platinum: gold molar ratio in the range from 0.01:0.99 to 0.10:0.90, and preferably of about 0.05:0.95.
  • the bimetallic compound is deposited on the titanium-containing support by a deposition-precipitation method.
  • the invention also resides in a catalyst for the preparation of propylene oxide, comprising a bimetallic compound supported on a titanium containing support, wherein the bimetallic compound comprises gold and a metal M selected from the group consisting of platinum, tin and rhodium.
  • Figure 1 represents micrographs of a catalyst of the invention (b) and a control catalyst (a) .
  • Figure 2 is a graph showing the yield of propylene oxide and the water/propylene oxide molar ratio as a function of the Au fraction in the Pt-Au bimetallic compound of a catalyst of the invention at 75°C.
  • Figure 3 is a graph showing the yield of propylene oxide and the water/propylene oxide molar ratio as a function of the Au fraction in the Pt-Au bimetallic compound of the catalyst of the invention at 100 °C.
  • Figure 4 is a graph showing the yield of propylene oxide as a function of the yield of water, when using various bimetallic compounds in the catalyst for the epoxidation of propylene.
  • Figure 5 is a graph showing the yield of propylene oxide as a function of the yield of propane, when using various bimetallic compounds in the catalyst for the epoxidation of propylene.
  • a gas-phase process for the preparation of propylene oxide comprising contacting propylene with oxygen and hydrogen in the presence of a catalyst comprising a bimetallic compound supported on a titanium containing support.
  • the titanium-containing support may take a variety of forms.
  • the titanium in the support exists essentially as non-metallic titanium. Details concerning the titanium-containing support that may be used in the invention can be found in WO 00/59632 (page 8, line 27 to page 15, line 27) , which is herein incorporated by reference.
  • the bimetallic compound supported by the titanium-containing support comprises gold and a metal M selected from the group consisting of platinum, tin and rhodium.
  • a generally advantageous metal M:gold molar ratio is in the range from 0.01:0.99 to
  • the metal M is platinum.
  • the deposition-precipitation method is generally preferred. This method is described, for example, by R. Meiers, U. Dingerdissen and W.F. H ⁇ lderich in Journal of Catalysis, 176,376(1998).
  • the bimetallic compound loading of the support can be any amount that yields an active catalyst in the process of this invention.
  • the bimetallic compound loading is in the range from 0.1 to 5 and preferably from 0.5 to 1.5 weight percent, based on the total weight of the catalyst.
  • the quantity of propylene employed can vary over a wide range.
  • the quantity of propylene depends upon the specific process features, including, for example, the design of the reactor and economic and safety considerations. Those skilled in the art know how to determine a suitable range of propylene concentrations for the specific process features.
  • Oxygen is also required for the process, and any source of oxygen is acceptable, including air or essentially pure molecular oxygen. Other sources of oxygen may be suitable, including ozone and nitrogen oxides, such as nitrous oxide. Molecular oxygen is preferred. The quantity of oxygen employed can vary over a wide range provided that the quantity is sufficient for producing the desired propylene oxide .
  • Hydrogen is also required for the process, and any source of hydrogen can be used in the process, including, for example molecular hydrogen obtained from the dehydrogenation of hydrocarbons or alcohols.
  • the hydrogen may be generated in si tu in the propylene oxidation reactor, for example, by dehydrogenating propane. Any quantity of hydrogen can be employed in the process provided that the amount is sufficient to produce propylene oxide.
  • a diluent beneficially provides a means of removing and dissipating the heat produced.
  • the diluent provides an expanded concentration regime in which the reactants are non-flammable.
  • the diluent can be any gas that does not inhibit the process. Suitable diluents include, but are not limited to, helium, nitrogen, argon, methane, carbon dioxide, steam, and mixtures thereof. Most of these gases are essentially inert with respect to the process disclosed herein.
  • the process may be conducted in a reactor of any conventional design suitable for gas-phase processes.
  • the process conditions for the epoxidation can vary considerably. Usually, the process is conducted at a temperature that ranges from 50°C to 250°C, and preferably from 75°C to 225°C. Usually, the pressure ranges from about atmospheric to 30bar.a and preferably from atmospheric to 20bar.a
  • the residence time of the reactants and the molar ratio of reactants to catalyst are determined by the space velocity.
  • the weight hourly space velocity (WHSV) is greater than 0.2 .propylene/g. catalyst/hr preferably greater than 0.6 g .propylene/g . catalys /hr .
  • the most preferred embodiment of the process of the invention comprises the following features: (a) the bimetallic compound comprises platinum and gold and has a platinum: gold molar ratio of about 0.5:0.95; (b) the titanium-containing support comprises titanium oxide and silicon oxide; and (c) the bimetallic compound is deposited on the support by the deposition-precipitation method. Additional preferred features may also be the following ones: (a) the catalyst comprises about 1 weight percent of bimetallic compound, based on the total weight of the catalyst; and (b) the process is carried out in the presence of nitrogen as a diluent gas and at a temperature around 100°C.
  • the catalyst comprises a bimetallic compound supported on a titanium containing support, wherein the bimetallic compound comprises gold and a metal M selected from the group consisting of platinum, tin and rhodium.
  • the catalyst of the invention may have some or all of the advantageous features as aforementioned in connection with the gas-phase process of the invention and which are summarized as follows: (a) the metal M of the bimetallic compound is platinum; (b) in the bimetallic compound, the molar ratio metal M:gold is in the range from 0.01:0.99 to 0.10:0.90, and preferably is about 0.05:0.95; (c) the titanium containing support comprises titanium oxide and silicon oxide; (d) the bimetallic compound has been deposited on the titanium-containing support by a deposition-precipitation method; (e) the catalyst comprises from 0.1 to 5 and preferably from 0.5 to 1.5 weight percent of bimetallic compound, based on the total weight of the catalyst .
  • the most preferred catalyst of the invention comprises the following features: (a) the bimetallic compound comprises platinum and gold and has a platinum:gold molar ratio of about 0.5:0.95; (b) the titanium-containing support comprises titanium oxide and silicon oxide; and (c) the bimetallic compound is deposited on the support by the deposition-precipitation method.
  • An additional preferred feature may also be the bimetallic compound content of about 1 weight percent based on the total weight of the catalyst .
  • Example 1 Preparation of a Pt-Au/Ti0 2 /Si0 2 catalyst Gold and platinum were deposited on a Ti0 2 /Si0 2 support by the deposition-precipitation method as follows.
  • a 1.6 wt . % Ti0 2 (0.1 monolayer) Ti0 2 /Si0 2 support was prepared by reaction of titanium (IV) ethoxide (Fluka, 97 %) in 2-propanol with surface hydroxyls of Si0 2 (Aldrich Davisil 646) based on the method described by Rajadhyaksha and co-workers in Applied Catalysis, 51,67(1989).
  • Example 2 (control) : Preparation of a Pd-Au/Ti0 2 /Si0 2 catalyst A Pd-Au/Ti0 2 /Si0 2 catalyst was prepared in the same way as in Example 1, except that PdCl 2 was used instead of the Pt salt. This catalyst comprised 1 weight percent of bimetallic (palladium-gold) compound, based on the total weight of the catalyst.
  • Example 3 (comparative) : Micrographs of the catalysts
  • TEM Transmission electron microscopy
  • micrographs are given in Figure 1, wherein the micrograph (a) corresponds to the control catalyst of Example 2 and the micrograph (b) corresponds to the catalyst according to the invention as prepared in Example 1.
  • the micrographs show homogeneously distributed metal particles up to 5 nm. No separate Pt or Pd metal particles were found.
  • XRF X-ray fluorescence
  • EDX energy dispersive X-ray analysis
  • Example 4 Preparation of an Au/Ti0 2 /Si0 2 catalyst
  • a Au/Ti0 2 /Si0 2 catalyst was prepared in the same way as in example 1, except that the aqueous solution contained only AuCl 3 .
  • This catalyst comprised 1 weight percent of gold, based on the total weight of the catalyst.
  • Propane (%) means the moles of obtained propane/moles of fed propylene expressed as a percentage
  • H 2 0/P0 means the number of moles of water obtained/number of moles of PO obtained
  • conversion is herein defined as the mole percentage of propylene that reacts to form products .
  • selectiveivity is herein defined as the mole percentage of reacted propylene that forms a particular product, desirably propylene oxide.
  • Example 6 Effect of Pt concentration The PO yield and water/PO mole ratio were measured as a function of the Pt concentration. The following table summarizes the results obtained at 75 °C.
  • Propane (%) means the moles of obtained propane/moles of fed propylene expressed as a percentage
  • H 2 0/PO means the number of moles of water obtained/number of moles of PO obtained
  • Propane (%) means the moles of obtained propane/moles of fed propylene expressed as a percentage
  • H 2 0/PO means the number of moles of water obtained/number of moles of PO obtained
  • gas-phase process of the invention is more effective at 100°C than at 75°C.
  • the catalyst of example 4 (supported Au only) was compared to other catalysts prepared as in Example 1, having a metal :Au ratio of 0.05:0.95 and a bimetallic content of 1 wt% based on the total weight of the catalyst.
  • the tested metals were Pt, Pd, Sn, Rh, Cd, Ag, Ir, Hg, Zn, Pb and Cu.
  • the PO and water yields (%) were measured in the following conditions :
  • Rh-Au catalysts give satisfactory results in terms of relatively high PO yield and low water yield, Pt-Au being the most satisfactory bimetallic compound.
  • Example 4 (supported Au only) was compared to other catalysts prepared as in Example 1, having a metal: Au ratio of 0.05:0.95 and a bimetallic content of 1 wt% based on the total weight of the catalyst.
  • the tested metals were Pt, Pd, Sn, Rh, Cd, Ag, Ir, Hg, Zn, Pb and Cu.
  • the PO and water yields (%) were measured in the following conditions :

Abstract

La présente invention concerne un procédé en phase gazeuse pour la préparation d'un oxyde de propylène comportant la mise en contact du propylène avec de l'oxygène et de l'hydrogène en présence d'un catalyseur comprenant un composé bimétallique supporté sur un support contenant du titane, le composé bimétallique comprenant de l'or et un métal M choisi parmi le groupe constitué du platine, de l'étain et du rhodium. L'invention concerne également le catalyseur.
PCT/US2003/001873 2002-01-23 2003-01-22 Procede en phase gazeuse et catalyseur pour la preparation d'un oxyde de propylene WO2003062196A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003209327A AU2003209327A1 (en) 2002-01-23 2003-01-22 Gas-phase process and catalyst for the preparation of propylene oxide

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US35111102P 2002-01-23 2002-01-23
US60/351,111 2002-01-23

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8183399B2 (en) 2007-04-05 2012-05-22 Dow Global Technologies Llc Integrated hydro-oxidation process with separation of an olefin oxide product stream
US8288311B2 (en) 2006-11-17 2012-10-16 Dow Global Technologies Llc Hydro-oxidation process using a catalyst prepared from a gold cluster complex
WO2015162562A1 (fr) 2014-04-22 2015-10-29 Sabic Global Technologies B.V. Procédé de synthèse de nanoparticules d'or (au) sur support pour des réactions d'époxydation
WO2018160650A1 (fr) * 2017-02-28 2018-09-07 Vaon, Llc Capteurs chimiques à base d'oxyde de métal à dopage bimétallique
US11203183B2 (en) 2016-09-27 2021-12-21 Vaon, Llc Single and multi-layer, flat glass-sensor structures
CN113912570A (zh) * 2020-07-10 2022-01-11 中国石油化工股份有限公司 以降低稀释气为目的的丙烯直接环氧化反应以制备环氧丙烷的方法
CN113912568A (zh) * 2020-07-10 2022-01-11 中国石油化工股份有限公司 可提高极限氧含量的制环氧丙烷的方法
CN113912573A (zh) * 2020-07-10 2022-01-11 中国石油化工股份有限公司 丙烯直接环氧化制备环氧丙烷的方法
US11467138B2 (en) 2016-09-27 2022-10-11 Vaon, Llc Breathalyzer

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5821394A (en) * 1994-11-24 1998-10-13 Solvay Process for converting a chlorinated alkane into a less chlorinated alkene

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5821394A (en) * 1994-11-24 1998-10-13 Solvay Process for converting a chlorinated alkane into a less chlorinated alkene

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8288311B2 (en) 2006-11-17 2012-10-16 Dow Global Technologies Llc Hydro-oxidation process using a catalyst prepared from a gold cluster complex
US8183399B2 (en) 2007-04-05 2012-05-22 Dow Global Technologies Llc Integrated hydro-oxidation process with separation of an olefin oxide product stream
WO2015162562A1 (fr) 2014-04-22 2015-10-29 Sabic Global Technologies B.V. Procédé de synthèse de nanoparticules d'or (au) sur support pour des réactions d'époxydation
US11203183B2 (en) 2016-09-27 2021-12-21 Vaon, Llc Single and multi-layer, flat glass-sensor structures
US11467138B2 (en) 2016-09-27 2022-10-11 Vaon, Llc Breathalyzer
WO2018160650A1 (fr) * 2017-02-28 2018-09-07 Vaon, Llc Capteurs chimiques à base d'oxyde de métal à dopage bimétallique
US10802008B2 (en) 2017-02-28 2020-10-13 Vaon, Llc Bimetal doped-metal oxide-based chemical sensors
CN113912570A (zh) * 2020-07-10 2022-01-11 中国石油化工股份有限公司 以降低稀释气为目的的丙烯直接环氧化反应以制备环氧丙烷的方法
CN113912568A (zh) * 2020-07-10 2022-01-11 中国石油化工股份有限公司 可提高极限氧含量的制环氧丙烷的方法
CN113912573A (zh) * 2020-07-10 2022-01-11 中国石油化工股份有限公司 丙烯直接环氧化制备环氧丙烷的方法
CN113912573B (zh) * 2020-07-10 2023-07-04 中国石油化工股份有限公司 丙烯直接环氧化制备环氧丙烷的方法
CN113912570B (zh) * 2020-07-10 2023-09-29 中国石油化工股份有限公司 以降低稀释气为目的的丙烯直接环氧化反应以制备环氧丙烷的方法
CN113912568B (zh) * 2020-07-10 2023-12-29 中国石油化工股份有限公司 可提高极限氧含量的制环氧丙烷的方法

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AU2003209327A1 (en) 2003-09-02

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