EP1478464A2 - Compositions de tamis moleculaires, catalyseur de celles-ci, leur preparation et utilisation dans des procedes de conversion - Google Patents

Compositions de tamis moleculaires, catalyseur de celles-ci, leur preparation et utilisation dans des procedes de conversion

Info

Publication number
EP1478464A2
EP1478464A2 EP03743673A EP03743673A EP1478464A2 EP 1478464 A2 EP1478464 A2 EP 1478464A2 EP 03743673 A EP03743673 A EP 03743673A EP 03743673 A EP03743673 A EP 03743673A EP 1478464 A2 EP1478464 A2 EP 1478464A2
Authority
EP
European Patent Office
Prior art keywords
catalyst composition
oxide
molecular sieve
metal oxide
elements
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP03743673A
Other languages
German (de)
English (en)
Inventor
Doron Levin
James C. Vartuli
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
ExxonMobil Chemical Patents Inc
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 US10/215,511 external-priority patent/US6906232B2/en
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Publication of EP1478464A2 publication Critical patent/EP1478464A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
    • 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
    • B01J37/08—Heat treatment
    • 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
    • B01J21/10—Magnesium; 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/76—Catalysts 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
    • B01J23/83—Catalysts 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 rare earths or actinides
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • B01J35/19—
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J35/60—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/10—Magnesium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/83—Aluminophosphates (APO compounds)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the present invention relates to molecular sieve compositions and catalysts containing the same, to the synthesis of such compositions and catalysts and to the use of such compositions and catalysts in conversion processes to produce olefin(s).
  • Olefins are traditionally produced from petroleum feedstocks by catalytic or steam cracking processes. These cracking processes, especially steam cracking, produce light olefin(s), such as ethylene and/or propylene, firom a variety of hydrocarbon feedstocks. Ethylene and propylene are important commodity petrochemicals useful in a variety of processes for making plastics and other chemical compounds.
  • SAPO silicoaluminophosphate
  • Silicoaluminophosphate molecular sieves contain a three-dimensional microporous crystalline framework structure of [SiO 4 ], [AlO 4 ] and [PO 4 ] corner sharing tetrahedral units.
  • U.S. Patent No. 5,417,949 relates to a process for converting noxious nitrogen oxides in an oxygen containing effluent into nitrogen and water using a molecular sieve and a metal oxide binder, where the preferred binder is titania and the molecular sieve is an aluminosilicate.
  • EP-A-312981 discloses a process for cracking vanadium-containing hydrocarbon feed streams using a catalyst composition comprising a physical mixture of a zeolite embedded in an inorganic refractory matrix material and at least one oxide of beryllium, magnesium, calcium, strontium, barium or lanthanum, preferably magnesium oxide, on a silica-containing support material.
  • Kang and Inui Effects of decrease in number of acid sites located on the external surface ofNi-SAPO-34 crystalline catalyst by the mechanochemical method, Catalysis Letters 53, pages 171-176 (1998) disclose that the shape selectivity can be enhanced and the coke formation mitigated in the conversion of methanol to ethylene over Ni-SAPO-34 by milling the catalyst with MgO, CaO, BaO or Cs 2 O on microspherical non-porous silica, with BaO being most preferred.
  • WO 98/29370 discloses the conversion of oxygenates to olefins over a small pore non-zeolitic molecular sieve containing a metal selected from the group consisting of a lanthanide, an actinide, scandium, yttrium, a Group 4 metal, a Group 5 metal or combinations thereof.
  • the invention resides in a catalyst composition comprising a molecular sieve and at least one oxide of a metal selected from Group 3 of the Periodic Table of Elements, the Lanthanide series of elements and the Actinide series of elements, wherein said metal oxide has an uptake of carbon dioxide at 100°C of at least 0.03, and typically at least 0.04 mg/m 2 of the metal oxide.
  • the catalyst composition also includes at least one of a binder and a matrix material different from said metal oxide.
  • said metal oxide is selected from lanthanum oxide, yttrium oxide, scandium oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, thorium oxide and mixtures thereof.
  • the molecular sieve conveniently comprises a silicoaluminophosphate.
  • the invention resides in a molecular sieve catalyst composition
  • a molecular sieve catalyst composition comprising a Group 3 metal oxide and/or an oxide of the Lanthanide or Actinide series elements, a binder, a matrix material, and a silicoaluminophosphate molecular sieve.
  • the invention resides in a method for making a catalyst composition, the method comprising physically mixing first particles comprising a molecular sieve with second particles comprising at least one oxide of a metal selected from Group 3 of the Periodic Table of Elements, the Lanthanide series of elements and the Actinide series of elements, wherein said metal oxide has an uptake of carbon dioxide at 100°C of at least 0.03 mg/m 2 of the metal oxide particles.
  • said second particles are produced by causing a hydrated precursor of the metal oxide to precipitate from a solution containing ions of the metal, hydrothermally treating the hydrated precursor at a temperature of at least 80°C for up to 10 days and then calcining the hydrated precursor at a temperature in the range of from 400°C to 900°C.
  • the invention is directed to a process for producing olefin(s) by converting a feedstock, such as an oxygenate, conveniently an alcohol, for example methanol, into one or more olefin(s) in the presence of a catalyst composition a molecular sieve and at least one oxide of a metal selected from Group 3 of the Periodic Table of Elements, the Lanthanide series of elements and the Actinide series of elements, wherein said metal oxide has an uptake of carbon dioxide at 100°C of at least 0.03 mg/m 2 of the metal oxide.
  • the catalyst composition has a Lifetime
  • Enhancement Index greater than 1, such as greater than 1.5.
  • LEI is defined herein as the ratio of the lifetime of the catalyst composition to that of the same catalyst composition in the absence of an active metal oxide.
  • Non-limiting examples of preferred molecular sieves particularly for use in converting an oxygenate containing feedstock into olefin(s), include framework types AEL, AEI, BEA, CHA, EDI, FAU, FER, GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW, TAM and TON.
  • the molecular sieve employed in the catalyst composition of the invention has an AEI topology or a CHA topology, or a combination thereof, most preferably a CHA topology.
  • Crystalline molecular sieve materials have a 3 -dimensional, four- connected framework structure of corner-sharing [TO 4 ] tetrahedra, where T is any tetrahedrally coordinated cation, such as [SiO 4 ], [AlO 4 ] and/or [PO 4 ] tetrahedral units.
  • the molecular sieves useful herein conveniently comprise a framework including [AlO 4 ] and [PO 4 ] tetrahedral units, i.e., an aluminophosphate (A1PO) molecular sieve, or [SiO 4 ], [AlO 4 ] and [PO 4 ] ] tetrahedral units, i.e., a silicoaluminophosphate (SAPO) molecular sieve.
  • SAPO silicoaluminophosphate
  • the molecular sieves useful herein is a silicoaluminophosphate (SAPO) molecular sieve or a substituted, preferably a metal substituted, SAPO molecular sieve.
  • suitable metal substituents are an alkali metal of Group 1 of the Periodic Table of Elements, an alkaline earth metal of Group 2 of the Periodic Table of Elements, a rare earth metal of Group 3 of the Periodic Table of Elements, including the Lanthanides lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, erbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; and scandium or yttrium, a transition metal of Groups 4 to 12 of the Periodic Table of Elements, or mixtures of any of these metal species.
  • Non-limiting examples of SAPO and A1PO molecular sieves useful herein include one or a combination of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44 (U.S. Patent No. 6,162,415), SAPO-47, SAPO-56, A1PO-5, AlPO-11, A1PO-18, A1PO-31, A1PO-34, A1PO-36, A1PO-37, A1PO-46, and metal containing molecular sieves thereof.
  • molecular sieves are one or a combination of SAPO-18, SAPO- 34, SAPO-35, SAPO-44, SAPO-56, A1PO-18 and A1PO-34 and metal containing derivatives thereof, such as one or a combination of SAPO-18, SAPO-34, A1PO- 34 and A1PO-18, and metal containing derivatives thereof, and especially one or a combination of SAPO-34 and A1PO-18, and metal containing derivatives thereof.
  • the molecular sieve is an intergrowth material having two or more distinct crystalline phases within one molecular sieve composition.
  • intergrowth molecular sieves are described in the U.S. Patent Application Publication No.
  • SAPO-18, A1PO-18 and RUW-18 have an AEI framework-type
  • SAPO-34 has a CHA framework-type
  • the molecular sieve used herein may comprise at least one intergrowth phase of AEI and CHA framework-types, especially where the ratio of CHA framework-type to AEI framework-type, as determined by the DIFFaX method disclosed in U.S. Patent Application Publication No. 2002-0165089, is greater than 1:1.
  • the molecular sieve is a silicoaluminophosphate
  • the molecular sieve has a Si/Al ratio less than or equal to 0.65, such as from 0.65 to 0.10, preferably from 0.40 to 0.10, more preferably from 0.32 to 0.10, and most preferably from 0.32 to 0.15.
  • the metal oxides useful herein are oxides of Group 3 metals and the
  • Preferred Group 3 metal oxides include oxides of scandium, yttrium and lanthanum, and preferred oxides of the Lanthanide or Actinide series metals include oxides of cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and thorium.
  • the most preferred active metal oxides are scandium oxide, lanthanum oxide, yttrium oxide, cerium oxide, praseodymium oxide, neodymium oxide and mixtures thereof, particularly mixtures of lanthanum oxide and cerium oxide.
  • Enhancement Index as defined by the following equation: ⁇ ⁇ _ Lifetime of Catalyst in Combination with Active Metal Oxide(s) ,
  • Lifetime of Catalyst the lifetime of the catalyst or catalyst composition is measured in the same process under the same conditions, and is the cumulative amount of feedstock processed per gram of catalyst composition until the conversion of feedstock by the catalyst composition falls below some defined level, for example 10%.
  • An inactive metal oxide will have little to no effect on the lifetime of the catalyst composition, or will shorten the lifetime of the catalyst composition, and will therefore have a LEI less than or equal to 1.
  • Active metal oxides of the invention are those Group 3 metal oxides, including oxides of the Lanthanide and Actinide series, that when used in combination with a molecular sieve, provide a molecular sieve catalyst composition that has a LEI greater than 1. By definition, a molecular sieve catalyst composition that has not been combined with an active metal oxide will have a LEI equal to 1.0.
  • a catalyst composition can be produced having an LEI in the range of from greater than 1 to 50, such as from 1.5 to 20.
  • catalyst compositions according to the invention exhibit LEI values greater than 1.1, for example in the range of from 1.2 to 15, and more particularly greater than 1.3, such as greater than 1.5, such as greater than 1.7, such as greater than 2.
  • the active metal o ⁇ ide(s) can be prepared using a variety of methods.
  • Lanthanide or Actinide series is hydrothermally treated under conditions that include a temperature of at least 80°C, preferably at least 100°C.
  • the hydrothermal treatment may take place in a sealed vessel at greater than atmospheric pressure.
  • a preferred mode of treatment involves the use of an open vessel under reflux conditions.
  • Agitation of the Group 3 metal oxide or the oxide of the Lanthanide or Actinide series in a liquid medium for example, by the action of refluxing liquid and/or stirring, promotes the effective interaction of the oxide with the liquid medium.
  • the duration of the contact of the oxide with the liquid medium is preferably at least 1 hour, preferably at least 8 hours.
  • the liquid medium for this treatment preferably has a pH of about 6 or greater, preferably 8 or greater.
  • Non-limiting examples of suitable liquid media include water, hydroxide solutions (including hydroxides of NH 4 + , Na + , K + , Mg + , and Ca 2+ ), carbonate and bicarbonate solutions (including carbonates and bicarbonates of NH 4 + , Na + , K + , Mg 2+ , and Ca 2+ ), pyridine and its derivatives, and alkyl/hydroxyl amines.
  • the active Group 3 metal oxide or the active oxide of the Lanthanide or Actinide series is prepared by subjecting a liquid solution, such as an aqueous solution, comprising a source of ions of the metal, such as a metal salt, to conditions sufficient to cause precipitation of a hydrated precursor to the solid oxide material, such as by the addition of a precipitating reagent to the solution.
  • a liquid solution such as an aqueous solution
  • a source of ions of the metal such as a metal salt
  • the precipitation is conducted at a pH above 7.
  • the precipitating agent preferably is a base such as sodium hydroxide or ammonium hydroxide.
  • the hydrated precursor to the metal oxide(s) is then recovered, for example by filtration or centrifugation, and washed and dried.
  • the resulting material can then be calcined, such as in an oxidizing atmosphere, at a temperature of at least 400°C, such as at least 500°C, for example from 600°C to 900°C, and particularly from 650°C to 800°C, to form the solid oxide material.
  • the calcination time is typically up to 48 hours, such as for 0.5 to 24 hours, for example for 1.0 to 10 hours. In one embodiment, calcination is carried out at about 700°C for 1 to 3 hours.
  • the catalyst composition of the invention includes any one of the molecular sieves previously described and one or more of the active metal oxides described above, optionally with a binder and/or matrix material different from the active metal oxide(s).
  • the weight ratio of the molecular sieve to the active metal oxide in the catalyst composition is in the range of from 5 weight percent to 800 weight percent, preferably from 10 weight percent to 600 weight percent, more preferably from 20 weight percent to 500 weight percent, and most preferably from 30 weight percent to 400 weight percent.
  • binders that are useful in forming the catalyst composition of the invention.
  • Non-limiting examples of binders that are useful alone or in combination include various types of hydrated alumina, silicas, and/or other inorganic oxide sols.
  • One preferred alumina containing sol is aluminum chlorhydrol.
  • the inorganic oxide sol acts like glue binding the synthesized molecular sieves and other materials such as the matrix together, particularly after thermal treatment.
  • the inorganic oxide sol preferably having a low viscosity, is converted into an inorganic oxide binder component.
  • an alumina sol will convert to an aluminum oxide binder following heat treatment.
  • Aluminum chlorhydrol a hydroxylated aluminum based sol containing a chloride counter ion, has the general formula of Al m O n (OH) 0 Cl p « x(H 2 O) wherein m is 1 to 20, n is 1 to 8, o is 5 to 40, p is 2 to 15, and x is 0 to 30.
  • the binder is Al ⁇ 3 O 4 (OH) 24 Cl 7 » 12(H 2 O) as is described in G.M. Wolterman, et al., Stud. Surf. Sci. and Catal., 76, pages 105- 144 (1993).
  • one or more binders are combined with one or more other alumina materials such as aluminum oxyhydroxide, ⁇ -alumina, boehmite, diaspore, and transitional aluminas such as ⁇ -alumina, ⁇ -alumina, ⁇ - alumina, ⁇ -alumina, ⁇ -alumina, and p-alumina, aluminum trihydroxide, such as gibbsite, bayerite, nordstrandite, doyelite, and mixtures thereof.
  • alumina materials such as aluminum oxyhydroxide, ⁇ -alumina, boehmite, diaspore, and transitional aluminas such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and p-alumina, aluminum trihydroxide, such as gibbsite, bayerite, nordstrandite, doyelite, and mixtures thereof.
  • Non-limiting examples of commercially available colloidal alumina sols include Nalco 8676 available from Nalco Chemical Co., Naperville, Illinois, and Nyacol AL20DW available from Nyacol Nano Technologies, Inc., Ashland, Massachusetts.
  • the catalyst composition contains a matrix material
  • this is preferably different from the active metal oxide and any binder.
  • Matrix materials are typically effective in reducing overall catalyst cost, acting as thermal sinks during regeneration, densifying the catalyst composition, and increasing catalyst physical properties such as crush strength and attrition resistance.
  • Non-limiting examples of matrix materials useful herein include one or more non-active metal oxides including beryllia, quartz, silica or sols, and mixtures thereof, for example silica-magnesia, silica-zirconia, silica-titania, silica- alumina and silica-alumina-thoria.
  • matrix materials are natural clays such as those from the families of montmorillonite and kaolin.
  • the matrix material is a clay or a clay- type composition, particularly having a low iron or titania content, and most preferably is kaolin.
  • Kaolin has been found to form a pumpable, high solids content slurry, to have a low fresh surface area, and to pack together easily due to its platelet structure.
  • a preferred average particle size of the matrix material, most preferably kaolin, is from 0.1 ⁇ m to 0.6 ⁇ m with a D 90 particle size distribution of less than 1 ⁇ m.
  • the catalyst composition typically contains from 1% to 80%, preferably from about 5% to 60%o, and more preferably from 5% to 50%), by weight of the molecular sieve based on the total weight of the catalyst composition.
  • the weight ratio of the binder to the matrix material is typically from 1 :15 to 1:5, such as from 1 :10 to 1 :4, and particularly from 1 :6 to 1 :5.
  • the amount of binder is typically from about 2%> by weight to about 30% by weight, such as from about 5% by weight to about 20%> by weight, and particularly from about 7%> by weight to about 15%> by weight, based on the total weight of the binder, the molecular sieve and matrix material.
  • the catalyst composition typically has a density in the range of from
  • 0.5 g/cc to 5 g/cc such as from from 0.6 g/cc to 5 g/cc, for example from 0.7 g/cc to 4 g/cc, particularly in the range of from 0.8 g/cc to 3 g/cc.
  • the molecular sieve is first synthesized and is then physically mixed with the active metal oxide, preferably in a substantially dry, dried, or calcined state. Most preferably the molecular sieve and active metal oxide are physically mixed in their calcined state. Intimate physical mixing can be achieved by any method known in the art, such as mixing with a mixer muller, drum mixer, ribbon/paddle blender, kneader, or the like. Chemical reaction between the molecular sieve and the metal oxide(s) is unnecessary and, in general, is not preferred.
  • the molecular sieve is conveniently initially formulated into a catalyst precursor with the matrix and/or binder and the active metal oxide is then combined with the formulated precursor.
  • the active metal oxide can be added as unsupported particles or can be added in combination with a support, such as a binder or matrix material.
  • the resultant catalyst composition can then be formed into useful shaped and sized particles by well-known techniques such as spray drying, pelletizing, extrusion, and the like.
  • the molecular sieve composition and the matrix material are combined with a liquid to form a slurry and then mixed to produce a substantially homogeneous mixture containing the molecular sieve composition.
  • suitable liquids include water, alcohol, ketones, aldehydes, and/or esters. The most preferred liquid is water.
  • the slurry of the molecular sieve composition, binder and matrix material is then fed to a forming unit, such as spray drier, that forms the catalyst composition into the required shape, for example microspheres.
  • a heat treatment such as calcination is usually performed.
  • Typical calcination temperatures are in the range from 400°C to 1,000°C, preferably from 500°C to 800°C and more preferably from 550°C to 700°C.
  • Typical calcination environments are air (which may include a small amount of water vapor), nitrogen, helium, flue gas (combustion product lean in oxygen), or any combination thereof.
  • the catalyst composition is heated in nitrogen at a temperature of from 600°C to 700°C for a period of time typically from 30 minutes to 15 hours, preferably from 1 hour to about 10 hours, more preferably from about 1 hour to about 5 hours, and most preferably from about 2 hours to about 4 hours.
  • the catalyst composition described above is useful in a variety of processes including cracking, of for example a naphtha feed to light olefin(s) (U.S. Patent No. 6,300,537) or higher molecular weight (MW) hydrocarbons to lower MW hydrocarbons; hydrocracking, of for example heavy petroleum and/or cyclic feedstock; isomerization, of for example aromatics such as xylene; polymerization, of for example one or more olefin(s) to produce a polymer product; reforming; hydrogenation; dehydrogenation; dewaxing, of for example hydrocarbons to remove straight chain paraffins; absorption, of for example alkyl aromatic compounds for separating out isomers thereof; alkylation, of for example aromatic hydrocarbons such as benzene and alkylbenzenes; transalkylation, of for example a combination of aromatic and polyalkylaromatic hydrocarbons; dealkylation; hydrodecylization; disproportionation, of for example
  • Preferred processes include processes for converting naphtha to highly aromatic mixtures; converting light olefin(s) to gasoline, distillates and lubricants; converting oxygenates to olefin(s); converting light paraffins to olefins and/or aromatics; and converting unsaturated hydrocarbons (ethylene and/or acetylene) to aldehydes for conversion into alcohols, acids and esters.
  • the most preferred process of the invention is the conversion of a feedstock to one or more olefin(s).
  • the feedstock contains one or more aliphatic-containing compounds, and preferably one or more oxygenates, such that the aliphatic moiety contains from 1 to about 50 carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms, and most preferably from 1 to 4 carbon atoms.
  • Non-limiting examples of suitable aliphatic-containing compounds include alcohols such as methanol and ethanol, alkyl mercaptans such as methyl mercaptan and ethyl mercaptan, alkyl sulfides such as methyl sulfide, alkylamines such as methylamine, alkyl ethers such as dimethyl ether, diethyl ether and methylethyl ether, alkyl halides such as methyl chloride and ethyl chloride, alkyl ketones such as dimethyl ketone, formaldehydes, and various acids such as acetic acid.
  • alcohols such as methanol and ethanol
  • alkyl mercaptans such as methyl mercaptan and ethyl mercaptan
  • alkyl sulfides such as methyl sulfide
  • alkylamines such as methylamine
  • alkyl ethers such as dimethyl ether, diethyl
  • the feedstock comprises methanol, ethanol, dimethyl ether, diethyl ether or a combination thereof, more preferably methanol and/or dimethyl ether, and most preferably methanol.
  • the catalyst composition of the invention is effective to convert the feedstock primarily into one or more olefin(s).
  • the olefin(s) produced typically have from 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbons atoms, and most preferably are ethylene and/or propylene.
  • the catalyst composition of the invention is effective to convert a feedstock containing one or more oxygenates into a product containing greater than 50 weight percent, typically greater than 60 weight percent, such as greater than 70 weight percent, and preferably greater than 80 weight percent of olefin(s) based on the total weight of hydrocarbon in the product.
  • the amount of ethylene and/or propylene produced based on the total weight of hydrocarbon in the product is typically greater than 40 weight percent, for example greater than 50 weight percent, preferably greater than 65 weight percent, and more preferably greater than 78 weight percent.
  • the amount ethylene produced in weight percent based on the total weight of hydrocarbon product produced is greater than 30 weight percent, such as greater than 35 weight percent, for example greater than 40 weight percent.
  • the amount of propylene produced in weight percent based on the total weight of hydrocarbon product produced is greater than 20 weight percent, such as greater than 25 weight percent, for example greater than 30 weight percent, and preferably greater than 35 weight percent.
  • the catalyst composition of the invention for the conversion of a feedstock comprising methanol and dimethylether to ethylene and propylene, it is found that the production of ethane and propane is reduced by greater than 10%, such as greater than 20%, for example greater than 30%>, and particularly in the range of from 30% to 40% compared to a similar catalyst composition at the same conversion conditions but without the active metal oxide component(s).
  • the feedstock may contain one or more diluents, which are generally non-reactive to the feedstock or molecular sieve catalyst composition and are typically used to reduce the concentration of the feedstock.
  • Non-limiting examples of diluents include helium, argon, nitrogen, carbon monoxide, carbon dioxide, water, essentially non-reactive paraffins (especially alkanes such as methane, ethane, and propane), essentially non-reactive aromatic compounds, and mixtures thereof.
  • the most preferred diluents are water and nitrogen, with water being particularly preferred.
  • the present process can be conducted over a wide range of pressures including autogenous pressure.
  • the partial pressure of the feedstock exclusive of any diluent therein employed in the process is in the range of from 0.1 kPaa to 5 MPaa, preferably from 5 kPaa to 1 MPaa, and more preferably from 20 kPaa to 500 kPaa.
  • the weight hourly space velocity defined as the total weight of feedstock excluding any diluents per hour per weight of molecular sieve in the catalyst composition, can range from 1 hr “1 to 5000 hr “1 , preferably from 2 hr “1 to 3000 hr “1 , more preferably from 5 hr "1 to 1500 hr "1 , and most preferably from 10 hr "1 to 1000 hr “1 .
  • the WHSN is at least 20 hr "1 and, where the feedstock contains methanol and/or dimethyl ether, is in the range of from 20 hr "1 to 300 hr "1 .
  • the process of the invention is conveniently conducted as a fixed bed process, or more typically as a fluidized bed process (including a turbulent bed process), such as a continuous fluidized bed process, and particularly a continuous high velocity fluidized bed process.
  • the process is conducted as a fluidized bed process utilizing a reactor system, a regeneration system and a recovery system.
  • fresh feedstock optionally with one or more diluent(s)
  • the feedstock is converted in the riser reactor(s) into a gaseous effluent that enters a disengaging vessel in the reactor system along with the coked catalyst composition.
  • the coked catalyst composition is separated from the gaseous effluent within the disengaging vessel, typically with the aid of cyclones, and is then fed to a stripping zone, typically in a lower portion of the disengaging vessel.
  • a gas such steam, methane, carbon dioxide, carbon monoxide, hydrogen, and/or an inert gas such as argon, preferably steam, to recover adsorbed hydrocarbons from the coked catalyst composition that is then introduced into the regeneration system.
  • the coked catalyst composition is contacted with a regeneration medium, preferably a gas containing oxygen, under regeneration conditions capable of burning coke from the coked catalyst composition, preferably to a level less than 0.5 weight percent based on the total weight of the coked molecular sieve catalyst composition entering the regeneration system.
  • a regeneration medium preferably a gas containing oxygen
  • the regeneration conditions may include temperature in the range of from 450°C to 750°C, and preferably from 550°C to 700°C.
  • the regenerated catalyst composition withdrawn from the regeneration system is combined with fresh molecular sieve catalyst composition and/or re-circulated molecular sieve catalyst composition and/or feedstock and/or fresh gas or liquids, and returned to the riser reactor(s).
  • the gaseous effluent is withdrawn from the disengaging system and is passed through a recovery system for separating and purifying the light olefin(s), particularly ethylene and propylene, in the gaseous effluent.
  • the process of the invention forms part of an integrated process for producing light olefin(s) from a hydrocarbon feedstock, particularly methane and/or ethane.
  • the first step in the process is passing the gaseous feedstock, preferably in combination with a water stream, to a syngas production zone to produce a synthesis gas stream, typically comprising carbon dioxide, carbon monoxide and hydrogen.
  • the synthesis gas stream is then converted to an oxygenate containing stream generally by contacting with a heterogeneous catalyst, typically a copper based catalyst, at temperature in the range of from 150°C to 450°C and a pressure in the range of from 5 MPa to 10 MPa.
  • a heterogeneous catalyst typically a copper based catalyst
  • the oxygenate containing stream can be used as a feedstock in a process as described above for producing light olefin(s), such as ethylene and/or propylene.
  • light olefin(s) such as ethylene and/or propylene.
  • the olefm(s) produced are directed to one or more polymerization processes for producing various polyolefins.
  • LEI is defined as the ratio of the lifetime of a molecular sieve catalyst composition containing an active metal oxide(s) compared to that of the same molecular sieve in the absence of a metal oxide, defined as having an LEI of 1.
  • lifetime is defined as the cumulative amount of oxygenate converted, preferably into one or more olefin(s), per gram of molecular sieve, until the conversion rate drops to about 10%) of its initial value. If the conversion has not fallen to 10%> of its initial value by the end of the experiment, lifetime is estimated by linear extrapolation based on the rate of decrease in conversion over the last two data points in the experiment.
  • Principal Olefin is the sum of the selectivity to ethylene and propylene.
  • the ratio "C 2 7C 3 ⁇ ' is the ratio of the ethylene to propylene selectivity weighted over the run.
  • the "C 3 Purity” is calculated by dividing the propylene selectivity by the sum of the propylene and propane selectivities.
  • the selectivities for methane, ethylene, ethane, propylene, propane, C 4 's and C 5 +'s are average selectivities weighted over the run. Note that the C 5 +'s consist only of C 5 's, C 6 's and C 7 's.
  • the selectivity values do not sum to 100% in the Tables because they have been corrected for coke as is well known.
  • SAPO-34 A silicoaluminophosphate molecular sieve, SAPO-34, designated as
  • the reactor located in a furnace to which vaporized methanol was fed.
  • the reactor was maintained at a temperature of 475°C and a pressure of 25 psig (172.4 kPag)
  • the flow rate of the methanol was such that the flow rate of methanol on weight basis per gram of molecular sieve, also known as the weight hourly space velocity (WHSN) was 100 h "1 .
  • Product gases exiting the reactor were collected and analyzed using gas chromatography.
  • the catalyst load was 50 mg and the catalyst bed was diluted with quartz to minimize hot spots in the reactor.
  • La(NO 3 ) 3 -xH 2 O (Aldrich Chemical Company) were dissolved with stirring in 500ml of distilled water. The pH was adjusted to 9 by the addition of concentrated ammonium hydroxide. This slurry was then put in polypropylene bottles and placed in a steambox (100°C) for 72 hours. The product formed was recovered by filtration, washed with excess water, and dried overnight at 85°C. A portion of this catalyst was calcined to 600°C in flowing air for 3 hours to produce lanthanum oxide (La ⁇ ).
  • Pr(NO 3 ) 3 -6H 2 O Fifty grams of Pr(NO 3 ) 3 -6H 2 O were dissolved with stirring in 500ml of distilled water. The pH was adjusted to 8 by the addition of concentrated ammonium hydroxide. This slurry was then put in polypropylene bottles and placed in a steambox (100°C) for 72 hours. The product formed was recovered by filtration, washed with excess water, and dried overnight at 85°C. A portion of this catalyst was calcined to 600°C in flowing air for 3 hours to produce praseodymium oxide (Pr 2 O 3 ).
  • La(NO 3 ) 3 -6H 2 O were dissolved with stirring in 500ml of distilled water.
  • Another solution containing 20 grams of concentrated ammonium hydroxide and 500ml of distilled water was prepared. These two solutions were combined at the rate of 50ml/min using a nozzle mixer. The pH of the final composite was adjusted to approximately 9 by the addition of concentrated ammonium hydroxide.
  • This slurry was then put in polypropylene bottles and placed in a steambox (100°C) for 72 hours. The product formed was recovered by filtration, washed with excess water, and dried overnight at 85°C. A portion of this catalyst was calcined to 700°C in flowing air for 3 hours to produce a mixed metal oxide containing a nominal 5 weight percent lanthanum based on the final weight of the mixed metal oxide.
  • the carbon dioxide uptake of the oxides of Examples 1 through 9 were measured using a Mettler TGA/SDTA 851 thermogravimetric analysis system under ambient pressure.
  • the metal oxide samples were first dehydrated in flowing air to about 500°C for one hour after which the uptake of carbon dioxide was measured at 100°C.
  • the surface area of the samples were measured in accordance with the method of Brunauer, Emmett, and Teller (BET) to provide the carbon dioxide uptake in terms of mg carbon dioxide/m 2 of the metal oxide presented in Table 1.
  • BET Brunauer, Emmett, and Teller
  • Example 2 the molecular sieve catalyst composition produced in Example A was tested in the process of Example B using 40 mg of the molecular sieve catalyst composition with 10 mg of La 2 O 3 produced via precipitation in Example 2. The components were well mixed and then diluted with sand to form the reactor bed. The results of this experiment are shown in Tables 2 and 3 illustrating that the addition of La 2 O 3 produced via precipitation, an active Group 3 metal oxide, increased lifetime by 340%. Selectivity to ethane decreased by 55%> and selectivity to propane decreased by 44%, suggesting a significant reduction in hydrogen transfer reactions.
  • Example 14 the molecular sieve catalyst composition produced in Example A was tested in the process of Example B using 40 mg of the molecular sieve catalyst composition with 10 mg of Y 2 O 3 produced in Example 3. The components were well mixed and then diluted with sand to form the reactor bed. The results of this experiment are shown in Tables 2 and 3 illustrating that the addition of Y 2 O 3 , an active Group 3 metal oxide, increased lifetime by 1090%. Selectivity to ethane decreased by 45% and selectivity to propane decreased by 28%, suggesting a significant reduction in hydrogen transfer reactions.
  • Example 15 the molecular sieve catalyst composition produced in Example A was tested in the process of Example B using 40 mg of the molecular sieve catalyst composition with 10 mg of Y 2 O 3 produced in Example 3. The components were well mixed and then diluted with sand to form the reactor bed. The results of this experiment are shown in Tables 2 and 3 illustrating that the addition of Y 2 O 3 , an active Group 3 metal oxide, increased lifetime by 1090%. Selectivity to ethane decreased by
  • Example 15 the molecular sieve catalyst composition produced in Example A was tested in the process of Example B using 40 mg of the molecular sieve catalyst composition with 10 mg of Sc 2 O 3 produced in Example 4. The components were well mixed and then diluted with sand to form the reactor bed. The results of this experiment are shown in Tables 2 and 3 illustrating that the addition of Sc 2 O 3 , an active Group 3 metal oxide, increased lifetime by 167%. Selectivity to ethane decreased by 27% and selectivity to propane decreased by 21%, suggesting a significant reduction in hydrogen transfer reactions.
  • Example 16 the molecular sieve catalyst composition produced in Example A was tested in the process of Example B using 40 mg of the molecular sieve catalyst composition with 10 mg of Ce 2 O 3 produced in Example 5. The components were well mixed and then diluted with sand to form the reactor bed. The results of this experiment are shown in Tables 2 and 3 illustrating that the addition of Ce 2 O 3 , an active Lanthanide metal oxide, increased lifetime by 630%). Selectivity to ethane decreased by 50% and selectivity to propane decreased by 34%, suggesting a significant reduction in hydrogen transfer reactions.
  • Example 17 the molecular sieve catalyst composition produced in Example A was tested in the process of Example B using 40 mg of the molecular sieve catalyst composition with 10 mg of Pr 2 O 3 produced in Example 6. The components were well mixed and then diluted with sand to form the reactor bed. The results of this experiment are shown in Tables 2 and 3 illustrating that the addition of Pr 2 O 3 , an active Lanthanide metal oxide, increased lifetime by 640%>. Selectivity to ethane decreased by 51%» and selectivity to propane decreased by 38%, suggesting a significant reduction in hydrogen transfer reactions.
  • Example 18 the molecular sieve catalyst composition produced in Example A was tested in the process of Example B using 40 mg of the molecular sieve catalyst composition with 10 mg of Nd 2 O 3 produced in Example 7. The components were well mixed and then diluted with sand to form the reactor bed. The results of this experiment are shown in Tables 2 and 3 illustrating that the addition of Nd 2 O 3 , an active Lanthanide metal oxide, increased lifetime by 340%. Selectivity to ethane decreased by 49%> and selectivity to propane decreased by 34%, suggesting a significant reduction in hydrogen transfer reactions.
  • Example 19 the molecular sieve catalyst composition produced in Example A was tested in the process of Example B using 40 mg of the molecular sieve catalyst composition with 10 mg of the mixed metal oxide produped in Example 8. The components were well mixed and then diluted with sand to form the reactor bed. The results of this experiment are shown in Tables 2 and 3 illustrating that the addition of 5% LaO x /Ce 2 O 3 , an active Lanthanide metal oxide modified by a Group 3 oxide, increased lifetime by 450%). Selectivity to ethane decreased by 47%> and selectivity to propane decreased by 37%, suggesting a significant reduction in hydrogen transfer reactions.

Abstract

L'nvention concerne une composition catalytique, un procédé de préparation de celle-ci et son utilisation dans la conversion d'une charge, de préférence une charge oxygénée, en une ou plusieurs oléfine(s), de préférence de l'éthylène et/ou du propylène. Cette composition catalytique comprend un tamis moléculaire et au moins un oxyde d'un métal choisi dans le Groupe 3 du tableau périodique des éléments, à savoir les lanthanides et les actinides.
EP03743673A 2002-02-28 2003-02-10 Compositions de tamis moleculaires, catalyseur de celles-ci, leur preparation et utilisation dans des procedes de conversion Withdrawn EP1478464A2 (fr)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
US36096302P 2002-02-28 2002-02-28
US360963P 2002-02-28
US36601202P 2002-03-20 2002-03-20
US366012P 2002-03-20
US37469702P 2002-04-22 2002-04-22
US374697P 2002-04-22
US215511 2002-08-09
US10/215,511 US6906232B2 (en) 2002-08-09 2002-08-09 Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
PCT/US2003/004169 WO2003074177A2 (fr) 2002-02-28 2003-02-10 Compositions de tamis moleculaires, catalyseur de celles-ci, leur preparation et utilisation dans des procedes de conversion

Publications (1)

Publication Number Publication Date
EP1478464A2 true EP1478464A2 (fr) 2004-11-24

Family

ID=27792286

Family Applications (3)

Application Number Title Priority Date Filing Date
EP03743671A Withdrawn EP1478462A2 (fr) 2002-02-28 2003-02-10 Compositions de tamis moleculaire, catalyseur de ces compositions, leur fabrication et leur utilisation dans des procedes de conversion
EP03743673A Withdrawn EP1478464A2 (fr) 2002-02-28 2003-02-10 Compositions de tamis moleculaires, catalyseur de celles-ci, leur preparation et utilisation dans des procedes de conversion
EP03709038A Withdrawn EP1478461A2 (fr) 2002-02-28 2003-02-10 Compostions de tamis moleculaires, catalyseur associe et fabrication et utilisation dans des procedes de conversion

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP03743671A Withdrawn EP1478462A2 (fr) 2002-02-28 2003-02-10 Compositions de tamis moleculaire, catalyseur de ces compositions, leur fabrication et leur utilisation dans des procedes de conversion

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP03709038A Withdrawn EP1478461A2 (fr) 2002-02-28 2003-02-10 Compostions de tamis moleculaires, catalyseur associe et fabrication et utilisation dans des procedes de conversion

Country Status (11)

Country Link
EP (3) EP1478462A2 (fr)
JP (3) JP2005518929A (fr)
KR (3) KR20040089679A (fr)
CN (3) CN100335172C (fr)
AU (3) AU2003216248B2 (fr)
BR (1) BR0308011A (fr)
CA (2) CA2477432A1 (fr)
EA (3) EA007871B1 (fr)
MY (2) MY139847A (fr)
TW (3) TWI265825B (fr)
WO (3) WO2003074177A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7595275B2 (en) 2006-08-15 2009-09-29 Exxonmobil Chemical Patents Inc. Catalyst compositions and their synthesis

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2477432A1 (fr) * 2002-02-28 2003-09-12 Exxonmobil Chemical Patents Inc. Compositions de tamis moleculaire, catalyseur de ces compositions, leur fabrication et leur utilisation dans des procedes de conversion
US7074739B2 (en) 2002-11-19 2006-07-11 Exxonmobil Chemical Patents Inc. Multi-component molecular sieve catalyst compositions and their use in aromatics reactions
US6951830B2 (en) 2003-08-05 2005-10-04 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst compositions, their production and use in conversion processes
US7404891B2 (en) * 2004-03-29 2008-07-29 Exxonmobil Chemical Patents Inc. Heat recovery technique for catalyst regenerator flue gas
US7166757B2 (en) 2004-07-30 2007-01-23 Exxonmobil Chemical Patents Inc. Conversion of oxygenates to olefins
WO2007021394A2 (fr) * 2005-08-18 2007-02-22 Exxonmobil Chemical Patents Inc. Conversion catalytique d'oxygenates en olefines
CN101003018A (zh) * 2006-01-20 2007-07-25 中国石油天然气股份有限公司 一种多相催化固体碱催化剂及其制备方法和应用
US7335621B2 (en) 2006-04-19 2008-02-26 Exxonmobil Chemical Patents Inc. Catalyst compositions and preparation thereof
JP4710744B2 (ja) 2006-07-18 2011-06-29 トヨタ自動車株式会社 複合金属酸化物の製造方法
CN101239878B (zh) * 2007-02-07 2010-05-19 中国石油化工股份有限公司 碳四及其以上烯烃增产乙烯、丙烯的方法
CN101239866B (zh) * 2007-02-07 2010-12-01 中国石油化工股份有限公司 含氧化合物生产乙烯、丙烯的方法
CA2578494A1 (fr) * 2007-02-14 2008-08-14 Nova Chemicals Corporation Craquage catalytique d'ethers en 1-olefines
EP2022565A1 (fr) * 2007-07-06 2009-02-11 Casale Chemicals S.A. Procédé pour la préparation de tamis moléculaires en silicoaluminoposphate (SAPO), catalyseurs contenant lesdits tamis et procédés de déshydratation catalytique utilisant lesdits catalyseurs
JP5543347B2 (ja) * 2007-08-13 2014-07-09 サウディ ベーシック インダストリーズ コーポレイション 脂肪族燃料促進物質を芳香族化合物に転化するプロセス
DE102007059129A1 (de) * 2007-12-07 2009-06-10 Süd-Chemie AG Katalysator mit erhöhter Olefinselektivität zur Umsetzung von Oxygenaten zu Olefinen
RU2493909C2 (ru) * 2008-04-04 2013-09-27 Петр ВАСИЛЬЕВ Цеолитовый катализатор с цеолитовой вторичной структурой
JP5818133B2 (ja) * 2011-05-20 2015-11-18 国立大学法人東京工業大学 オレフィン製造用触媒及びオレフィンの製造方法
CN102344328B (zh) * 2011-07-25 2014-03-12 浙江大学 一种使用移动床技术将甲醇转化为丙烯的半连续方法
EP2907571B1 (fr) * 2012-10-15 2017-12-13 Mitsubishi Gas Chemical Company, Inc. Procédé de production d'un catalyseur pouvant être utilisé dans la production d'un composé de méthylamine, et procédé de production dudit composé de méthylamine
JP6105810B2 (ja) 2013-05-07 2017-03-29 シントス エス．アー．Ｓｙｎｔｈｏｓ Ｓ．Ａ． １，３−ブタジエンを生産するためのプロセス、及び１，３−ブタジエンを生産するための触媒におけるランタンの使用
CN107661774B (zh) * 2016-07-27 2020-11-03 中国科学院大连化学物理研究所 一种催化剂及合成气直接转化制低碳烯烃的方法
CN107661773B (zh) * 2016-07-29 2020-08-04 中国科学院大连化学物理研究所 一种催化剂及合成气直接转化制液体燃料联产低碳烯烃的方法
CN108568311B (zh) * 2017-03-07 2021-03-23 中国科学院大连化学物理研究所 一种催化剂及合成气直接转化制乙烯的方法
JP6894530B2 (ja) * 2017-04-27 2021-06-30 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ トルエン、ｐ−キシレン及び軽質オレフィンのうちの少なくとも１種を製造するための触媒のインサイチュ製造方法及び反応プロセス
CN109939667B (zh) * 2018-01-26 2021-01-05 中国科学院大连化学物理研究所 一种催化剂及合成气直接转化制低碳烯烃的方法
CN109939722B (zh) * 2018-01-26 2021-05-25 中国科学院大连化学物理研究所 一种有机碱修饰的复合催化剂及一氧化碳加氢制乙烯的方法
WO2020091969A1 (fr) * 2018-10-30 2020-05-07 Exxonmobil Chemical Patents Inc. Teneur en ions métalliques du groupe 1 de catalyseurs à tamis moléculaire microporeux
CN111346664B (zh) * 2018-12-24 2022-11-15 中国石油化工股份有限公司 改性钒硅分子筛及其制备方法以及硫醚氧化方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003074176A2 (fr) * 2002-02-28 2003-09-12 Exxonmobil Chemical Patents Inc. Compositions de tamis moleculaire, catalyseur de ces compositions, leur fabrication et leur utilisation dans des procedes de conversion

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465889A (en) * 1982-07-02 1984-08-14 Summit Gas Systems Pte. Ltd. Catalytic conversion of methanol, dimethyl ether and mixtures thereof to a hydrocarbon product rich in iso-C4 compounds and new catalysts therefor
US4781816A (en) 1987-10-19 1988-11-01 Phillips Petroleum Company Cracking process
US6040264A (en) * 1996-04-04 2000-03-21 Exxon Chemical Patents Inc. Use of alkaline earth metal containing small pore non-zeolitic molecular sieve catalysts in oxygenate conversion
TW412510B (en) * 1996-12-31 2000-11-21 Exxon Chemical Patents Inc Oxygenate conversions using small pore non-zeolitic molecular sieve catalysts
US6423879B1 (en) * 1997-10-02 2002-07-23 Exxonmobil Oil Corporation Selective para-xylene production by toluene methylation
JP4221532B2 (ja) * 1998-06-26 2009-02-12 三菱瓦斯化学株式会社 メチルアミン製造用触媒及び該触媒を用いたメチルアミン類の製造方法
US6388156B1 (en) * 1999-05-14 2002-05-14 Exxonmobil Chemical Patents Inc. Direct selective synthesis of para-xylene by reacting an aromatic compound with a methylating agent formed from CO, Co2 and H2
WO2001064340A1 (fr) * 2000-03-01 2001-09-07 Exxonmobil Chemical Patents Inc. Tamis moleculaire de silico-aluminophosphates contenant du thorium destine a la production d'olefines
US6448197B1 (en) * 2000-07-13 2002-09-10 Exxonmobil Chemical Patents Inc. Method for making a metal containing small pore molecular sieve catalyst
WO2002005952A2 (fr) * 2000-07-13 2002-01-24 Uop Llc Catalyseur resistant a l'attrition pour production d'olefines legeres
CA2369318A1 (fr) * 2002-01-28 2003-07-28 Universite Concordia Catalyseurs hybrides utilises pour le craquage catalytique avance d'essences lourdes et d'autres matieres premieres a base d'hydrocarbures dans la production selective d'olefines legeres

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003074176A2 (fr) * 2002-02-28 2003-09-12 Exxonmobil Chemical Patents Inc. Compositions de tamis moleculaire, catalyseur de ces compositions, leur fabrication et leur utilisation dans des procedes de conversion

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7595275B2 (en) 2006-08-15 2009-09-29 Exxonmobil Chemical Patents Inc. Catalyst compositions and their synthesis

Also Published As

Publication number Publication date
AU2003225560A1 (en) 2003-09-16
TWI306780B (en) 2009-03-01
CN1646221A (zh) 2005-07-27
WO2003074177A3 (fr) 2003-12-31
CN1638865A (zh) 2005-07-13
CA2477428A1 (fr) 2003-09-12
AU2003225560B2 (en) 2008-05-08
WO2003074177A2 (fr) 2003-09-12
CN1298427C (zh) 2007-02-07
KR20040089680A (ko) 2004-10-21
MY139847A (en) 2009-11-30
WO2003074175A2 (fr) 2003-09-12
WO2003074176A2 (fr) 2003-09-12
EA200401101A1 (ru) 2005-04-28
CN100335172C (zh) 2007-09-05
TWI265825B (en) 2006-11-11
EA200401102A1 (ru) 2005-04-28
EA007873B1 (ru) 2007-02-27
AU2003212993A1 (en) 2003-09-16
TWI265824B (en) 2006-11-11
KR20040091080A (ko) 2004-10-27
CA2477428C (fr) 2011-03-22
AU2003216248A1 (en) 2003-09-16
BR0308011A (pt) 2005-01-04
CA2477432A1 (fr) 2003-09-12
CN1642648A (zh) 2005-07-20
EA007872B1 (ru) 2007-02-27
TW200303237A (en) 2003-09-01
KR20040089679A (ko) 2004-10-21
AU2003212993A8 (en) 2003-09-16
JP2005518930A (ja) 2005-06-30
EA007871B1 (ru) 2007-02-27
MY140018A (en) 2009-11-30
WO2003074176A3 (fr) 2003-12-18
WO2003074175A3 (fr) 2003-12-04
TW200303238A (en) 2003-09-01
CN1327964C (zh) 2007-07-25
EP1478461A2 (fr) 2004-11-24
EP1478462A2 (fr) 2004-11-24
JP2005518929A (ja) 2005-06-30
JP2005518928A (ja) 2005-06-30
EA200401061A1 (ru) 2005-04-28
TW200306890A (en) 2003-12-01
AU2003216248B2 (en) 2008-12-11

Similar Documents

Publication Publication Date Title
AU2003216248B2 (en) Catalyst compositions comprising molecular sieves, their preparation and use in conversion processes
US6844291B2 (en) Molecular sieve compositions, catalyst thereof, their making and use in conversion processes
US7411106B2 (en) Molecular sieve compositions, catalyst thereof, their making and use in conversion processes
US7319178B2 (en) Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
US6995111B2 (en) Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
AU2002350150B2 (en) Molecular sieve catalyst composition, its making and use in conversion processes
US7166757B2 (en) Conversion of oxygenates to olefins
US7378563B2 (en) Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
WO2006023095A1 (fr) Conversion de composes oxygenes en olefines
US7307196B2 (en) Molecular sieve compositions, catalyst thereof, their making and use in conversion processes
US7199277B2 (en) Pretreating a catalyst containing molecular sieve and active metal oxide
US7186875B2 (en) Conversion of oxygenates to olefins
ZA200406712B (en) Catalyst composition comprising molecular sieves, their preparation and use in conversion processes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040827

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO

17Q First examination report despatched

Effective date: 20091002

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140902