FR3039544B1 - Procede de metathese des olefines utilisant un catalyseur contenant du silicium et du molybdene incorpores au moyen d'au moins deux precurseurs - Google Patents

Procede de metathese des olefines utilisant un catalyseur contenant du silicium et du molybdene incorpores au moyen d'au moins deux precurseurs Download PDF

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Publication number
FR3039544B1
FR3039544B1 FR1557368A FR1557368A FR3039544B1 FR 3039544 B1 FR3039544 B1 FR 3039544B1 FR 1557368 A FR1557368 A FR 1557368A FR 1557368 A FR1557368 A FR 1557368A FR 3039544 B1 FR3039544 B1 FR 3039544B1
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metathesis
olefins
precursors
incorporated
molybdene
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FR3039544A1 (fr
Inventor
Audrey Bonduelle
Alexandra Chaumonnot
Damien Delcroix
Christophe Vallee
Souad RAFIK-CLEMENT
Severine FORGET
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Priority to FR1557368A priority Critical patent/FR3039544B1/fr
Priority to CN201680044735.1A priority patent/CN108136378B/zh
Priority to PCT/EP2016/067830 priority patent/WO2017021233A1/fr
Priority to US15/749,298 priority patent/US10758892B2/en
Priority to TW105124186A priority patent/TW201714860A/zh
Publication of FR3039544A1 publication Critical patent/FR3039544A1/fr
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/28Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04Alumina
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08Silica
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/30Tungsten
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/881Molybdenum and iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/882Molybdenum and cobalt
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/883Molybdenum and nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/885Molybdenum and copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64Pore diameter
    • B01J35/6472-50 nm
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • B01J37/0203Impregnation the impregnation liquid containing organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • B01J37/0213Preparation of the impregnating solution
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0236Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/024Multiple impregnation or coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/082Decomposition and pyrolysis
    • B01J37/086Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • B01J35/615100-500 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63Pore volume
    • B01J35/633Pore volume less than 0.5 ml/g
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04Alumina
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08Silica
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24Chromium, molybdenum or tungsten
    • C07C2523/28Molybdenum
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nanotechnology (AREA)

Abstract

L'invention concerne un procédé de métathèse des oléfines mis en œuvre avec un catalyseur comprenant une matrice mésoporeuse et au moins les éléments molybdène et silicium, lesdits éléments étant incorporés à ladite matrice au moyen d'au moins deux précurseurs dont au moins un précurseur contient du molybdène et au moins un précurseur contient du silicium.
FR1557368A 2015-07-31 2015-07-31 Procede de metathese des olefines utilisant un catalyseur contenant du silicium et du molybdene incorpores au moyen d'au moins deux precurseurs Active FR3039544B1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
FR1557368A FR3039544B1 (fr) 2015-07-31 2015-07-31 Procede de metathese des olefines utilisant un catalyseur contenant du silicium et du molybdene incorpores au moyen d'au moins deux precurseurs
CN201680044735.1A CN108136378B (zh) 2015-07-31 2016-07-26 使用含有借助至少两种前体并入的硅和钼的催化剂的烯烃复分解方法
PCT/EP2016/067830 WO2017021233A1 (fr) 2015-07-31 2016-07-26 Procede de metathese des olefines utilisant un catalyseur contenant du silicium et du molybdene incorpores au moyen d'au moins deux precurseurs
US15/749,298 US10758892B2 (en) 2015-07-31 2016-07-26 Olefin metathesis method using a catalyst containing silicon and molybdenum incorporated by means of at least two precursors
TW105124186A TW201714860A (zh) 2015-07-31 2016-07-29 使用包含藉由至少二種前驅物併入之矽及鉬之催化劑進行烯烴歧化之方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1557368A FR3039544B1 (fr) 2015-07-31 2015-07-31 Procede de metathese des olefines utilisant un catalyseur contenant du silicium et du molybdene incorpores au moyen d'au moins deux precurseurs
FR1557368 2015-07-31

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Publication Number Publication Date
FR3039544A1 FR3039544A1 (fr) 2017-02-03
FR3039544B1 true FR3039544B1 (fr) 2020-02-28

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FR1557368A Active FR3039544B1 (fr) 2015-07-31 2015-07-31 Procede de metathese des olefines utilisant un catalyseur contenant du silicium et du molybdene incorpores au moyen d'au moins deux precurseurs

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US (1) US10758892B2 (fr)
CN (1) CN108136378B (fr)
FR (1) FR3039544B1 (fr)
TW (1) TW201714860A (fr)
WO (1) WO2017021233A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3039544B1 (fr) 2015-07-31 2020-02-28 IFP Energies Nouvelles Procede de metathese des olefines utilisant un catalyseur contenant du silicium et du molybdene incorpores au moyen d'au moins deux precurseurs
CN113019449B (zh) * 2020-06-24 2022-10-14 上海应用技术大学 一种芳香氧化偶氮化合物的催化制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2437532A (en) * 1942-12-24 1948-03-09 Union Oil Co Process for the catalytic reforming of hydrocarbons
US2722504A (en) * 1950-12-04 1955-11-01 Union Oil Co Silicone coated catalyst and use thereof
FR2787040B1 (fr) * 1998-12-10 2001-01-19 Inst Francais Du Petrole Hydrotraitement de charges hydrocarbonees dans un reacteur en lit bouillonnant
FR2826880B1 (fr) * 2001-07-04 2004-06-18 Inst Francais Du Petrole Composition amelioree de catalyseur pour la metathese des olefines
DE102004009805A1 (de) * 2004-02-28 2005-09-15 Basf Ag Trägerkatalysator definierter Porenverteilung im Bereich der Mesoporen
AR078212A1 (es) * 2008-09-04 2011-10-26 Basf Catalysts Llc Catalizador para isomerizacion y metatesis de olefinas
CN102335631B (zh) * 2010-07-16 2015-05-13 中国石油天然气股份有限公司 一种低碳烯烃歧化用介孔催化剂及其应用
CN102614867B (zh) * 2011-01-30 2015-04-29 中国石油化工股份有限公司 一种烯烃歧化用催化剂及其制备方法
FR2977890B1 (fr) * 2011-07-15 2013-07-19 IFP Energies Nouvelles Procede de metathese des olefines utilisant un catalyseur a base d'un materiau spherique comprenant des particules metalliques oxydes piegees dans une matrice mesostructuree
FR3007029B1 (fr) * 2013-06-17 2015-07-24 IFP Energies Nouvelles Procede de metathese des olefines utilisant un catalyseur a base d'un materiau spherique a porosite hierarchisee comprenant des particules metalliques oxydes piegees dans une matrice comprenant de l'oxyde de silicium
FR3039544B1 (fr) 2015-07-31 2020-02-28 IFP Energies Nouvelles Procede de metathese des olefines utilisant un catalyseur contenant du silicium et du molybdene incorpores au moyen d'au moins deux precurseurs

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WO2017021233A1 (fr) 2017-02-09
CN108136378B (zh) 2022-05-24
FR3039544A1 (fr) 2017-02-03
CN108136378A (zh) 2018-06-08
TW201714860A (zh) 2017-05-01
US10758892B2 (en) 2020-09-01
US20180221854A1 (en) 2018-08-09

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