Classifications

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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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  • 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
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  • 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
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  • 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
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  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/82—Phosphates
  • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
  • B01J29/85—Silicoaluminophosphates [SAPO compounds]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/19—Catalysts containing parts with different compositions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • 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
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  • 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
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  • 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
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  • 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
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  • 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
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  • 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
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  • 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
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  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
• • 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 olef ⁇ n(s), such as ethylene and/or propylene, from 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.
• oxygenates especially alcohols
• the preferred alcohol for light olefin production is methanol and the preferred process for converting a methanol-containing feedstock into light olefm(s), primarily ethylene and/or propylene, involves contacting the feedstock with a molecular sieve catalyst composition.
• SAPO silicoaluminophosphate
• Silicoaluminophosphate molecular sieves contain a three-dimensional microporous crystalline framework structure of [SiO 2 ], [AlO 2 ] and [PO 2 ] corner sharing tetrahedral units.
• 4,465,889 describes a catalyst composition
• a catalyst composition comprising a silicalite molecular sieve impregnated with a thorium, zirconium, or a titanium metal oxide for use in converting methanol, dimethyl ether, or a mixture thereof into a hydrocarbon product rich in iso-C 4 compounds.
• U.S. Patent No. 6,180,828 discusses the use of a modified molecular sieve to produce methylamines from methanol and ammonia, where for example, a silicoaluminophosphate molecular sieve is combined with one or more modifiers, such as a zirconium oxide, a titanium oxide, a yttrium oxide, montmorillonite or kaolinite.
• 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.
• 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 molecular sieve conveniently comprises a framework including at least [AlO 4 ] and [PO 4 ] tetrahedral units and more particularly a framework including at least [SiO 4 ], [AlO 4 ] and [PO 4 ] tetrahedral units, such as a silicoaluminophosphate.
• the metal oxide includes magnesium oxide.
• the invention resides in a catalyst composition comprising a molecular sieve and at least one oxide of a metal selected from Group 2 of the Periodic Table 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 also comprises at least one oxide of a metal selected from Group 3 of the Periodic Table of Elements, such as yttrium oxide, lanthanum oxide, scandium oxide and mixtures thereof.
• 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 2 of the Periodic Table 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 invention resides in a method for making a catalyst composition, the method comprising combining a silicoaluminophosphate molecular sieve, a binder, a matrix material, and at least one metal oxide that, when saturated with acetone and contacted with said acetone for 1 hour at 25°C, converts more than 25 % of the acetone.
• the invention resides in a method of making a catalyst composition, the method comprising (a) combining a molecular sieve, a binder and a matrix material to produce a catalyst precursor; and (b) adding to the catalyst precursor a metal oxide that has been calcined to a temperature in the range of from 200°C to 700°C.
• the metal oxide is magnesium oxide and is physically mixed with a molecular sieve synthesized from a reaction mixture comprising at least one templating agent and at least two of a silicon source, a phosphorous source and an aluminum source.
• the invention resides in a process for converting a feedstock into one or more olefin(s) in the presence of a molecular sieve catalyst composition comprising a molecular sieve, a binder, a matrix material and an active metal oxide that, when saturated with acetone and contacted with said acetone for 1 hour at 25°C, converts more than 80% of the acetone.
• a molecular sieve catalyst composition comprising a molecular sieve, a binder, a matrix material and an active metal oxide that, when saturated with acetone and contacted with said acetone for 1 hour at 25°C, converts more than 80% of the acetone.
• the invention resides in a process for producing one or more olefin(s), the process comprising contacting a feedstock comprising at least one oxygenate with a catalyst composition comprising a small pore molecular sieve, a binder, a matrix material, a magnesium oxide that has been calcined in the temperature range of from 200°C to 600°C, and a Group 3 metal oxide.
• a catalyst composition comprising a small pore molecular sieve, a binder, a matrix material, a magnesium oxide that has been calcined in the temperature range of from 200°C to 600°C, and a Group 3 metal oxide.
• the invention relates to a catalyst composition, its synthesis and its use in the conversion of hydrocarbon feedstocks, particularly oxygenated feedstocks, into olefin(s). It has been found that combining a molecular sieve with a particular metal oxide results in a catalyst composition with a longer catalyst lifetime when used in the conversion of feedstocks, such as oxygenates, more particularly methanol, into olef ⁇ n(s). In addition, the resultant catalyst composition tends to be more propylene selective and to yield lower amounts of unwanted ethane and propane.
• the preferred metal oxide is an oxide of a Group 2 metal having an uptake of carbon dioxide at 100°C of at least 0.03 mg/m 2 of the metal oxide and/or a metal oxide that is capable of converting greater than 80% of acetone at room temperature.
• the metal oxide is magnesium oxide which has a surface area greater than 20 m 2 /g and which has been calcined at temperature greater than 200°C. This unexpected result is further enhanced when an oxide of a Group 3 metal (for example scandium, lanthanum, or yttrium) from the Periodic Table of Elements using the IUPAC format described in the CRC Handbook of Chemistry and Physics, 78th Edition, CRC Press, Boca Raton, Florida (1997) is combined with the magnesium oxide.
• Molecular Sieves for example scandium, lanthanum, or yttrium
• Non-limiting examples of preferred molecular sieves particularly for use in converting an oxygenate containing feedstock into olefin(s), include framework types AEL, AFY, 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.
• the molecular sieve used herein has a pore systenm defined by an 8-membered ring of [TO 4 ] tetrahedra and has an average pore size less than 5 A, such as in the range of from 3 A to 5 A, for example from 3 A to 4.5 A, and particularly from 3.5 A to 4.2A.
• 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, AlPO-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, AlPO-18 and A1PO-34 and metal containing derivatives thereof, such as one or a combination of SAPO-18, SAPO-34, A1PO- 34 and AlPO-18, and metal containing derivatives thereof, and especially one or a combination of SAPO-34 and AlPO-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. 2002-0165089 and International Publication No.
• WO 98/15496 published April 16, 1998, both of which are herein fully incorporated by reference.
• SAPO-18, AlPO-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 molecular sieve is SAPO- 18,
• SAPO-34 or an intergrowth thereof in which the framework of the molecular sieves consists essentially of [SiO 4 ], [AlO 4 ] and [PO 4 ] tetrahedral units and hence is free of additional framework elements, such as nickel.
• the metal oxides of the invention are those metal oxides, different from typical binders and/or matrix materials, that, when used in combination with a molecular sieve, provide benefits in catalytic conversion processes.
• the metal oxides useful herein are oxides that, when saturated with acetone and allowed to stand in contact with the acetone for 1 hour at room temperature (about 25°C), convert greater than 80% of the acetone, for example greater than 85%, such as greater than 90%, and in some cases greater than 95%.
• 13 C solid state NMR is the use of 13 C solid state NMR. In this method, the metal oxide is first dehydrated under vacuum while being heated by the use of a stepwise temperature program.
• the highest temperature used in the dehydration procedure is 400°C.
• the metal oxide is then saturated with acetone-2- 13 C at room temperature (ca. 25°C) by the use of conventional vacuum line technique.
• the metal oxide with adsorbed acetone-2- 13 C is transferred into a 7-mm NMR rotor without any contact with air or moisture.
• Quantitative 13 C solid state NMR spectra with Magic Angle Spinning are acquired to determine the conversion of acetone after the sample has been kept at 25 °C for 1 hour.
• Suitable metal oxides are oxides of Group 2 metals, either alone or in combination with Group 3 metal oxides, which have an uptake of carbon dioxide at 100°C of at least 0.03 mg/ m 2 of the metal oxide, such as at least 0.35mg/m 2 of the metal oxide.
• the upper limit on the carbon dioxide uptake of the metal oxide is not critical, in general the metal oxides useful herein will have a carbon dioxide at 100°C of less than 10 mg/m 2 of the metal oxide, such as less than 5 mg/m 2 of the metal oxide.
• the increase in weight of the sample in terms of mg/mg adsorbent based on the adsorbent weight after treatment at 500°C is the amount of adsorbed carbon dioxide.
• the surface area of the sample is measured in accordance with the method of Brunauer, Emmett, and Teller (BET) published as ASTM D 3663 to provide the carbon dioxide uptake in terms of mg carbon dioxide/m 2 of the metal oxide.
• the most preferred Group 2 metal oxide is a magnesium oxide
• Suitable Group 3 metal oxides include yttrium oxide, lanthanum oxide, scandium oxide and mixtures thereof.
• the active metal oxide preferably the MgO, even more preferably the combination of the MgO and a Group 3 metal oxide
• Suitable metal oxides are those metal oxides that have a surface area greater than 20 m 2 /g, that have been calcined to greater than 200°C, and are capable of converting greater than 25%, such as greater than 50%, for example greater than 80% of acetone at room temperature.
• the metal oxide preferably the magnesium oxide, even more preferably the MgO and a Group 3 metal oxide, is calcined at a temperature in the range of from 200 °C to 700°C, such as from about 250°C to 650°C, for example in the range of from 300°C to 600°C, and typically from 350°C to 550°C.
• the magnesium metal oxide has a surface area of about 250 m 2 /g, and/or the magnesium oxide is calcined to about 550 °C.
• the active metal oxides can be prepared using a variety of methods.
• the active metal oxides can be made from active metal oxide precursors, such as metal salts, preferably Group 2 or Group 3 metal salt precursors.
• suitable sources of the Group 2 metal oxide include compounds that form these metal oxides during calcination, such as oxychlorides and nitrates.
• a further suitable source of the Group 2 or Group 3 metal oxides include salts containing the cation of the Group 2 or Group 3 metals, such as halides, nitrates, and acetates. Alkoxides are also sources of the Group 2 or Group 3 metal oxides.
• the active metal oxide is prepared by the thermal decomposition of metal-containing compounds, such as magnesium oxalate and barium oxalate, at high temperatures, such as 600°C, in flowing air.
• metal-containing compounds such as magnesium oxalate and barium oxalate
• prepared metal oxides usually have low BET surface area, e.g., less than 30 m 2 /g.
• the active metal oxide is prepared by the hydrolysis of metal-containing compounds followed by dehydration and calcination.
• MgO is hydroxylated by mixing the oxide with deionized water, forming a white slurry. The slurry is slowly heated to dryness on a heating plate to form white powder.
• the white powder is further dried in a vacuum oven at 100°C for at least 4 hrs, such as for 12 hrs.
• the dried white powder is then calcined in air at a temperature of at least 400°C, such as at least 500°C, and typically at least 550°C.
• the active metal oxide is prepared by the so-called aerogel method (Koper, O. B., Lagadic, I., Nolodin, A. and Klabunde, K. J. Chem. Mater. 1997, 9, 2468-2480).
• Mg powder is reacted under nitrogen purge with anhydrous methanol to form Mg(OCH 3 ) 2 solution in methanol.
• the resultant Mg(OCH 3 ) 2 solution is added to toluene.
• Water is then added dropwise to the Mg(OH) 2 solution in methanol-toluene under vigorous stirring.
• the resultant colloidial suspension of Mg(OH) 2 is placed in an autoclave, pressurized to 100 psig (690 kPag) with dry nitrogen, and heated slowly to a final pressure of about 1000 psig (6895 kPag).
• the supercritical solvent is vented to produce a fine white powder of Mg(OH) 2 .
• ⁇ anocrystalline MgO is obtained by heating the fine white powder at 400 °C under vacuum.
• Such prepared active metal oxides have the highest BET surface area, generally greater than 300 m 2 /g.
• Various methods exist for making mixed metal oxides from Group 2 and Group 3 metal oxide precursors e.g., wet impregnation, incipient wetness and co-precipitation.
• mixed metal oxides are prepared by impregnating a Group 3 metal oxide precursor onto a Group 2 metal oxide.
• a Group 3 metal oxide precursor such as La(acetylacetonate) 3 is dissolved in an organic solvent such as toluene. The amount of solvent used is enough to fill the mesoporous and macroporous volume of the Group 2 metal oxide.
• the Group 3 metal oxide precursor solution is added dropwise to the Group 2 metal oxide.
• the wet mixture is dried in a vacuum oven for 1 to 12 hours to remove the solvent.
• the resulting solid mixture is then calcined at a temperature, e.g., 400°C, high enough to decompose the Group 3 metal oxide precursor into an oxide.
• a mixed oxide is prepared by the incipient wetness technique.
• a Group 3 metal oxide precursor such as lanthanum acetate is dissolved in deionized water. The solution is added dropwise to a Group 2 metal oxide. The mixture is dried in a vacuum oven at 50°C for 1 to 12 hours. The dried mixture is broken up and calcined at 550 °C in air for 3 hours.
• a mixed metal oxide is prepared by co- precipitation. An aqueous solution comprising Group 2 and Group 3 metal oxide precursors is subject to conditions sufficient to cause precipitation of a hydrated precursor of the solid oxide materials, such as by the addition of sodium hydroxide or ammonium hydroxide.
• the temperature at which the liquid medium is maintained during the co-precipitation is typically from 20°C to 100°C.
• the resulting gel is then hydrothermally treated at temperatures between 50 and 100 °C for several days.
• the hydrothermal treatment typically takes place at greater than atmospheric pressure.
• the resulting material is then recovered, for example by filtration or centrifugation, and washed and dried.
• the resulting material is then calcined at a temperature of greater than 200°C, preferably greater than 300°C, and more preferably greater 400°C, and most preferably greater than 450°C.
• the catalyst composition of the invention includes any one of the molecular sieves previously described and one or more active metal oxides described above, optionally together with a binder and/or matrix material different from the active metal oxide(s).
• the weight ratio of the active metal oxide(s) to the molecular sieve in the catalyst composition is in the range of from 1 weight percent to 800 weight percent, such as from 5 weight percent to 200 weight percent, particularly from 10 weight percent to 100 weight percent.
• binders that are useful in forming catalyst compositions.
• 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 13 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), which is herein incorporated by reference.
• one or more binders are combined with one or more other non-limiting examples of alumina materials such as aluminum oxyhydroxide, ⁇ -alumina, boehmite, diaspore, and transitional aluminas such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and p-alumina, aluminum trihydroxide, such as gibbsite, bayerite, nordstrandite, doyelite, and mixtures thereof.
• the binder is an alumina sol, predominantly comprising aluminum oxide, optionally including some silicon.
• the binder is peptized alumina made by treating an alumina hydrate, such as pseudobohemite, with an acid, preferably an acid that does not contain a halogen, to prepare a sol or aluminum ion solution.
• an alumina hydrate such as pseudobohemite
• an acid preferably an acid that does not contain a halogen
• sol or aluminum ion solution 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 to assist in shielding heat from the catalyst composition for example during regeneration, densifying the catalyst composition, and increasing catalyst strength such as crush strength and attrition resistance.
• Non-limiting examples of matrix materials 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. These natural clays include subbentonites and those kaolins known as, for example, Dixie, McNamee, Georgia and Florida clays.
• Non-limiting examples of other matrix materials include haloysite, kaolinite, dickite, nacrite, or anauxite.
• the matrix material such as a clay
• the matrix material is a clay or a clay- type composition, particularly a clay or clay-type composition having a low iron or titania content, and most preferably the matrix material 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 about 0.1 ⁇ m to about 0.6 ⁇ m with a D 90 particle size distribution of less than about 1 ⁇ m.
• the catalyst composition contains a binder or matrix material
• the catalyst composition typically contains from 1% to 80%, such as from 5% to 60%, and particularly 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 l:10 to 1 :4, and particularly from 1:6 to 1:5.
• the amount of binder is typically from 2% by weight to 30% by weight, such as from 5% by weight to 20% by weight, and particularly from 7% by weight to 15% by weight, based.on the total weight of the binder, the molecular sieve and matrix material. It has been found that a higher sieve content and lower matrix content increases the molecular sieve catalyst composition performance, whereas a lower sieve content and higher matrix content improves the attrition resistance of the composition.
• 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 0J 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 formed and is then physically mixed with the Group 2 metal oxide described above, or with a mixture of Group 2 and Group 3 metal oxides, preferably in a substantially dry, dried, or calcined state. Most preferably the molecular sieve and active metal oxides are physically mixed in their calcined state.
• intimate mixing of the molecular sieve and one or more active metal oxides improves conversion processes using the molecular sieve composition and catalyst composition of the invention. Intimate 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, at an elevated temperature is usually performed.
• Typical calcination temperatures are in the range from 400°C to 1,000°C, such as from 500°C to 800°C, for example 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. Heating is carried out for a period of time typically from 30 minutes to 15 hours, such as from 1 hour to 10 hours, for example from 1 hour to 5 hours, and particularly from 2 hours to 4 hours.
• the catalyst compositions described above are useful in a variety of processes including cracking, of for example a naphtha feed to light olefin(s) (U.S. Patent No.
• MW hydrocarbons 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 alkyl benzene, optionally with propylene to produce cumene or with long chain olefins; transalkylation, of for example a combination of aromatic and polyalkylaromatic hydrocarbons; dealkylation; hydrodecylization; disproportionation, of for example toluene to make benzene and paraxylene; oligomer
• 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.
• 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 20 weight percent, such as greater than 30 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 temperatures, such as in the range of from 200°C to 1000°C, for example from 250°C to 800°C, including from 250°C to 750 °C, conveniently from 300°C to 650°C, preferably from 350°C to 600°C and more preferably from 350°C to 550°C.
• 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.
• the coked catalyst composition is contacted with 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.
• 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 olefin(s) produced are directed to one or more polymerization processes for producing various poly olefins.
• the following examples are offered.
• SAPO-34 A silicoaluminophosphate molecular sieve, SAPO-34, designated as
• MSA was crystallized in the presence of tetraethyl ammonium hydroxide (Rl) and dipropylamine (R2) as the organic structure directing agents or templating agents.
• Rl tetraethyl ammonium hydroxide
• R2 dipropylamine
• C 4 's, C 5 +, etc. refer to the number of carbons in the hydrocarbon.
• selectivity consist of the sum of C 5 's, C 6 's and C 7 's.
• the weighed averages (selectivity) were calculated based on the following formula, *y + (x 2 -X ⁇ )*(Y ⁇ + y 2 )/2+ (x 3 -x 2 )*(y 2 + y 3 )/2 + ..., where X; and y ; are yield and g methanol fed/g molecular sieve, respectively. Lifetime of catalysts (g methanol/g molecular sieve) reported is methanol that was cumulatively converted.
• Example 1 the catalyst composition consisted of a molecular sieve, designated as MSA as described in Example A.
• the catalyst was diluted with quartz to form the reactor bed.
• Table 2 The results of this experiment in the reactor and conditions discussed above in Example B are shown in Table 2.
• Example 2 Preparation of MgO and Acetone Conversion Measurement
• the MgO was prepared as follows. 5.0 g of MgO (98%, ACS reagent grade from Aldrich) was mixed with 150 ml of deionized water to form a white slurry. The white slurry was slowly heated to dryness on a heating plate. The dried cake was broken into pieces and was ground to a fine powder. The powder was further dried in an oven at 120°C for 12 hrs. The white powder was then calcined at 550°C in air for 3 hrs.
• the prepared active metal oxide, MgO has a relatively high surface area (BET area of about 250 m 2 /g).
• the MgO powders were sieved to get particles of various sizes. Particle sizes between 75 to 150 micron were used in a conversion process as described in Example B.
• 0.25 g of this prepared MgO was loaded into a glass tube, and the tube was connected to a vacuum line via a 9-mm O-ring joint. The MgO was then heated to 450°C and kept at 450°C for 2 hrs under vacuum to remove water from the oxide. After cooling down to room temperature, 25°C, the MgO was saturated with acetone-2- 13 C. The MgO with adsorbed acetone-2- 13 C was then loaded into a 7-mm NMR rotor without any contact with air or moisture.
• the molecular sieve catalyst composition consisted of 33.6 wt% of MSA, 50.4 wt% of binder and 16 wt% MgO as described in Example 2 above.
• the catalyst composition was well mixed, and then diluted with quartz to form the reactor bed.
• the results of this experiment in the reactor and conditions discussed above in Example B are shown in Table 3.
• the data in Table 2 and Table 3 illustrate that by constituting 16 wt% of the catalyst composition loading with the MgO, the lifetime of the SAPO-34 molecular sieve has increased to 31.66 g/g molecular sieve from 16.34 g/g molecular sieve, an increase of 94%.
• Example 4 Mixing MgO with a Group 3 Metal Oxide ( 5 wt% La 2 O 3 )
• the loading of a Group 3 metal oxide where the metal is La onto the high surface area MgO was achieved via incipient wetness.
• 0.2261 g of Lanthanum acetate was dissolved in ca. 1.9 ml of deionized water.
• the solution was added drop-wise to 2.0146 g of MgO.
• the mixture was dried in a vacuum oven at 50 °C for 1 hr.
• the dried mixture was broken up and calcined at 550 °C in air for 3 hrs.
• the wt% of La ⁇ is about 5 %.
• the metal oxides powders were sieved to get particles of various sizes. Particle sizes between 75 to 150 micron were used in a conversion process.
• Example 5 - Molecular Sieve and a Mixed Metal Oxide: La ⁇ O ⁇ wt%)/MgO [0092]
• the catalyst composition consisted of 33.6 wt% of
• the lowest conversion measured was 30.69 wt% with a lifetime of 57.57 g methanol/g sieve at that conversion.
• the reported lifetime was estimated by extrapolating the conversion from 30.69 wt% to 10 wt%.

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