WO2006039213A1 - Tamis moleculaire ssz-65 - Google Patents

Tamis moleculaire ssz-65 Download PDF

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Publication number
WO2006039213A1
WO2006039213A1 PCT/US2005/034250 US2005034250W WO2006039213A1 WO 2006039213 A1 WO2006039213 A1 WO 2006039213A1 US 2005034250 W US2005034250 W US 2005034250W WO 2006039213 A1 WO2006039213 A1 WO 2006039213A1
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WIPO (PCT)
Prior art keywords
catalyst
molecular sieve
oxide
hydrocarbon
conditions
Prior art date
Application number
PCT/US2005/034250
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English (en)
Inventor
Saleh Elomari
Original Assignee
Chevron U.S.A. 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.)
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Publication date
Priority claimed from US10/956,276 external-priority patent/US20050042159A1/en
Priority claimed from US10/956,267 external-priority patent/US7011811B2/en
Priority claimed from US10/956,313 external-priority patent/US7083714B2/en
Application filed by Chevron U.S.A. Inc. filed Critical Chevron U.S.A. Inc.
Priority to JP2007534674A priority Critical patent/JP2008514540A/ja
Priority to CA002582295A priority patent/CA2582295A1/fr
Priority to AU2005292315A priority patent/AU2005292315A1/en
Priority to EP05798730A priority patent/EP1807348A1/fr
Publication of WO2006039213A1 publication Critical patent/WO2006039213A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • 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
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
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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
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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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
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group 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
    • 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
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    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating 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
    • 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
    • C10G45/58—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
    • 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
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C10G2300/1092—C2-C4 olefins
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1096—Aromatics or polyaromatics
    • C—CHEMISTRY; METALLURGY
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil
    • 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
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    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to new crystalline molecular sieve SSZ-65, a method for preparing SSZ-65 using a l-[l-(4-chlorophenyl)-cyclopropylmethyl]-l- ethyl-pyrrolidinium or 1 -ethyl- l-(l-phenyl-cyclopropylmethyl)-pyrrolidinium cation as a structure directing agent and the use of SSZ-65 in catalysts for, e.g., hydrocarbon conversion reactions.
  • crystalline molecular sieves and molecular sieves are especially useful in applications such as hydrocarbon conversion, gas drying and separation. Although many different crystalline molecular sieves have been disclosed, there is a continuing need for new molecular sieves with desirable properties for gas separation and drying, hydrocarbon and chemical conversions, and other applications. New molecular sieves may contain novel internal pore architectures, providing enhanced selectivities in these processes. Crystalline aluminosilicates are usually prepared from aqueous reaction mixtures containing alkali or alkaline earth metal oxides, silica, and alumina.
  • Crystalline borosilicates are usually prepared under similar reaction conditions except that boron is used in place of aluminum. By varying the synthesis conditions and the composition of the reaction mixture, different molecular sieves can often be formed.
  • SSZ-65 a family of crystalline molecular sieves with unique properties, referred to herein as "molecular sieve SSZ-65" or simply "SSZ-65".
  • SSZ-65 is obtained in its silicate, aluminosilicate, titanosilicate, germanosilicate, vanadosilicate or borosilicate form.
  • silicate refers to a molecular sieve having a high mole ratio of silicon oxide relative to aluminum oxide, preferably a mole ratio greater than 100, including molecular sieves comprised entirely of silicon oxide.
  • aluminosilicate refers to a molecular sieve containing both aluminum oxide and silicon oxide
  • borosilicate refers to a molecular sieve containing oxides of both boron and silicon.
  • a molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table II.
  • a molecular sieve having a mole ratio greater than about 15 of (1) an oxide selected from silicon oxide, germanium oxide and mixtures thereof to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereof and having, after calcination, the X-ray diffraction lines of Table II below.
  • the mole ratio of the first oxide or mixture of first oxides to the second oxide can be infinity, i.e., there is no second oxide in the molecular sieve.
  • the molecular sieve is an all-silica molecular sieve or a germanosilicate.
  • the catalyst may be a layered catalyst comprising a first layer comprising the molecular sieve of this invention, and a second layer comprising an aluminosilicate molecular sieve which is more shape selective than the molecular sieve of said first layer.
  • the first layer may contain at least one Group VIII metal.
  • this invention is a process to convert paraffins to aromatics which comprises contacting paraffins under conditions which cause paraffins to convert to aromatics with a catalyst comprising the molecular sieve of this invention, said catalyst comprising gallium, zinc, or a compound of gallium or zinc.
  • a process for isomerizing olefins comprising contacting said olefin under conditions which cause isomerization of the olefin with a catalyst comprising the molecular sieve of this invention.
  • a process for isomerizing an isomerization feed comprising an aromatic C 8 stream of xylene isomers or mixtures of xylene isomers and ethylbenzene, wherein a more nearly equilibrium ratio of ortho-, meta- and para-xylenes is obtained, said process comprising contacting said feed under isomerization conditions with a catalyst comprising the molecular sieve of this invention.
  • the present invention further provides a process for oligomerizing olefins comprising contacting an olefin feed under oligomerization conditions with a catalyst comprising the molecular sieve of this invention.
  • This invention also provides a process for converting oxygenated hydrocarbons comprising contacting said oxygenated hydrocarbon with a catalyst comprising the molecular sieve of this invention under conditions to produce liquid products.
  • the oxygenated hydrocarbon may be a lower alcohol.
  • a process for the production of higher molecular weight hydrocarbons from lower molecular weight hydrocarbons comprising the steps of: (a) introducing into a reaction zone a lower molecular weight hydrocarbon- containing gas and contacting said gas in said zone under C 2+ hydrocarbon synthesis conditions with the catalyst and a metal or metal compound capable of converting the lower molecular weight hydrocarbon to a higher molecular weight hydrocarbon; and (b) withdrawing from said reaction zone a higher molecular weight hydrocarbon-containing stream.
  • a process for the reduction of oxides of nitrogen contained in a gas stream in the presence of oxygen comprises contacting the gas stream with a molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a second tetravalent element different from said first tetravalent element, trivalent element, pentavalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table II.
  • SSZ-65 is prepared by a process comprising: (a) preparing an aqueous solution containing sources of at least one oxide capable of forming a crystalline molecular sieve and a l-[l-(4-chlorophenyl)- cyclopropylmethyl]-l-ethyl-pyrrolidinium or 1 -ethyl- 1 -(I -phenyl- cyclopropylmethyl)-pyrrolidinium cation having an anionic counterion which is not detrimental to the formation of SSZ-65; (b) maintaining the aqueous solution under conditions sufficient to form crystals of SSZ-65; and (c) recovering the crystals of SSZ-65.
  • SSZ-65 may comprise the crystalline material and the SDA in combination with metallic and non-metallic oxides bonded in tetrahedral coordination through shared oxygen atoms to form a cross-linked three dimensional crystal structure.
  • the metallic and non-metallic oxides comprise one or a combination of oxides of a first tetravalent element(s), and one or a combination of a trivalent element(s), pentavalent element(s), second tetravalent element(s) different from the first tetravalent element(s) or mixture thereof.
  • the first tetravalent element(s) is preferably selected from the group consisting of silicon, germanium and combinations thereof. More preferably, the first tetravalent element is silicon.
  • the trivalent element, pentavalent element and second tetravalent element (which is different from the first tetravalent element) is preferably selected from the group consisting of aluminum, gallium, iron, boron, titanium, indium, vanadium and combinations thereof. More preferably, the second trivalent or tetravalent element is aluminum or boron.
  • Typical sources of aluminum oxide for the reaction mixture include aluminates, alumina, aluminum colloids, aluminum oxide coated on silica sol, hydrated alumina gels such as Al(OH) 3 and aluminum compounds such as AlCl 3 and A1 2 (SO 4 ) 3 .
  • Typical sources of silicon oxide include silicates, silica hydrogel, silicic acid, fumed silica, colloidal silica, tetra-alkyl orthosilicates, and silica hydroxides. Boron, as well as gallium, germanium, titanium, indium, vanadium and iron, can be added in forms corresponding to their aluminum and silicon counterparts.
  • a source molecular sieve reagent may provide a source of aluminum or boron. In most cases, the source molecular sieve also provides a source of silica.
  • the source molecular sieve in its dealuminated or deboronated form may also be used as a source of silica, with additional silicon added using, for example, the conventional sources listed above.
  • a source molecular sieve reagent as a source of alumina for the present process is more completely described in U.S. Patent No. 5,225,179, issued July 6, 1993 to Nakagawa entitled “Method of Making Molecular Sieves", the disclosure of which is incorporated herein by reference.
  • an alkali metal hydroxide and/or an alkaline earth metal hydroxide such as the hydroxide of sodium, potassium, lithium, cesium, rubidium, calcium, and magnesium, is used in the reaction mixture; however, this component can be omitted so long as the equivalent basicity is maintained.
  • the SDA may be used to provide hydroxide ion.
  • the molecular sieve is prepared using mild stirring or agitation.
  • the SSZ-65 crystals can be allowed to nucleate spontaneously from the reaction mixture.
  • the use of SSZ-65 crystals as seed material can be advantageous in decreasing the time necessary for complete crystallization to occur.
  • seeding can lead to an increased purity of the product obtained by promoting the nucleation and/or formation of SSZ-65 over any undesired phases.
  • SSZ-65 crystals are added in an amount between 0.1 and 10% of the weight of first tetravalent element oxide, e.g. silica, used in the reaction mixture.
  • SSZ-65 further has a composition, as synthesized (i.e., prior to removal of the SDA from the SSZ-65) and in the anhydrous state, in terms of mole ratios, shown in Table B below.
  • Table B TABLE B As-Svnthesized SSZ-65 Y0 2 /W c 0 d > 15 M 2/n /YO 2 0.01 - 0.03 Q/YO 2 0.02 - 0.05
  • Y is silicon, germanium or a mixture thereof
  • W is aluminum, gallium, iron, boron, titanium, indium, vanadium or mixtures thereof
  • c is 1 or 2
  • d is 2 when c is 1 (i.e., W is tetravalent) or d is 3 or 5 when c is 2 (i.e., d is 3 when W is trivalent or 5 when W is pentavalent)
  • M is an alkali metal cation, alkaline earth metal cation or mixtures thereof
  • SSZ-65 can be made with a mole ratio of YO 2 /W c Od of ⁇ , i.e., there is essentially no W c O d present in the SSZ-65.
  • the SSZ-65 would be an all- silica material or a germanosilicate.
  • SSZ-65 can be made essentially aluminum free, i.e., having a silica to alumina mole ratio of ⁇ .
  • a method of increasing the mole ratio of silica to alumina is by using standard acid leaching or chelating treatments.
  • the X-ray powder diffraction patterns were determined by standard techniques.
  • the radiation was the K-alpha/doublet of copper.
  • the variation in the scattering angle (two theta) measurements, due to instrument error and to differences between individual samples, is estimated at ⁇ 0.1 degrees.
  • the X-ray diffraction pattern of Table I is representative of "as-synthesized" or "as-made” SSZ-65 molecular sieves.
  • cations of metals such as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, and Fe are particularly preferred.
  • the hydrogen, ammonium, and metal components can be ion-exchanged into the SSZ-65.
  • the SSZ-65 can also be impregnated with the metals, or the metals can be physically and intimately admixed with the SSZ-65 using standard methods known to the art. Typical ion-exchange techniques involve contacting the synthetic molecular sieve with a solution containing a salt of the desired replacing cation or cations.
  • SSZ-65 molecular sieves are useful in hydrocarbon conversion reactions. Hydrocarbon conversion reactions are chemical and catalytic processes in which carbon containing compounds are changed to different carbon containing compounds. Examples of hydrocarbon conversion reactions in which SSZ-65 are expected to be useful include hydrocracking, dewaxing, catalytic cracking and olefin and aromatics formation reactions.
  • hydrocracking catalysts contain an effective amount of at least one hydrogenation component of the type commonly employed in hydrocracking catalysts.
  • the hydrogenation component is generally selected from the group of hydrogenation catalysts consisting of one or more metals of Group VIB and Group VIII, including the salts, complexes and solutions containing such.
  • Dewaxing SSZ-65 preferably predominantly in the hydrogen form, can be used to dewax hydrocarbonaceous feeds by selectively removing straight chain paraffins.
  • the viscosity index of the dewax ed product is improved (compared to the waxy feed) when the waxy feed is contacted with SSZ-65 under isomerization dewaxing conditions.
  • the catalytic dewaxing conditions are dependent in large measure on the feed used and upon the desired pour point.
  • Hydrogen is preferably present in the reaction zone during the catalytic dewaxing process.
  • the hydrogen to feed ratio is typically between about 500 and about 30,000 SCF/bbl (standard cubic feet per barrel) (0.089 to 5.34 SCM/liter (standard cubic meters/liter)), preferably about 1000 to about 20,000 SCF/bbl (0.178 to 3.56 SCM/liter).
  • Typical feedstocks include light gas oil, heavy gas oils and reduced crudes boiling above about 350°F (177 0 C).
  • a typical dewaxing process is the catalytic dewaxing of a hydrocarbon oil feedstock boiling above about 350°F (177°C) and containing straight chain and slightly branched chain hydrocarbons by contacting the hydrocarbon oil feedstock in the presence of added hydrogen gas at a hydrogen pressure of about 15-3000 psi (0.103-20.7 MPa) with a catalyst comprising SSZ-65 and at least one Group VIII metal.
  • the SSZ-65 hydrodewaxing catalyst may optionally contain a hydrogenation component of the type commonly employed in dewaxing catalysts. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for examples of these hydrogenation components.
  • the Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium or tin or a mixture thereof may also be used in conjunction with the Group VIII metal compound and preferably a noble metal compound. The most , preferred metal is platinum.
  • the amount of Group VIII metal present in the conversion catalyst should be within the normal range of use in reforming catalysts, from about 0.05 to 2.0 weight percent, preferably 0.2 to 0.8 weight percent. It is critical to the selective production of aromatics in useful quantities that the conversion catalyst be substantially free of acidity, for example, by neutralizing the molecular sieve with a basic metal, e.g., alkali metal, compound. Methods for rendering the catalyst free of acidity are known in the art.
  • the cracking catalysts are typically employed with an inorganic oxide matrix component. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for examples of such matrix components. Isomerization
  • the present catalyst is highly active and highly selective for isomerizing C 4 to C 7 hydrocarbons.
  • the activity means that the catalyst can operate at relatively low temperature which thermodynamically favors highly branched paraffins. Consequently, the catalyst can produce a high octane product.
  • the high selectivity means that a relatively high liquid yield can be achieved when the catalyst is run at a high octane.
  • hydrogen is added to give a hydrogen to hydrocarbon ratio (H 2 /HC) of between 0.5 and 10 H 2 /HC, more preferably between 1 and 8 H 2 /HC.
  • H 2 /HC hydrogen to hydrocarbon ratio
  • a low sulfur feed is especially preferred in the present process.
  • the feed preferably contains less than 10 ppm, more preferably less than 1 ppm, and most preferably less than 0.1 ppm sulfur.
  • acceptable levels can be reached by hydrogenating the feed in a presaturation zone with a hydrogenating catalyst which is resistant to sulfur poisoning. See the aforementioned U.S.
  • Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for a further discussion of this hydrodesulfurization process. It is preferable to limit the nitrogen level and the water content of the feed. Catalysts and processes which are suitable for these purposes are known to those skilled in the art. After a period of operation, the catalyst can become deactivated by sulfur or coke. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for a further discussion of methods of removing this sulfur and coke, and of regenerating the catalyst.
  • the conversion catalyst preferably contains a Group VIII metal compound to have sufficient activity for commercial use. By Group VIII metal compound as used herein is meant the metal itself or a compound thereof.
  • the Group VIII noble metals and their compounds, platinum, palladium, and indium, or combinations thereof can be used. Rhenium and tin may also be used in conjunction with the noble metal. The most preferred metal is platinum.
  • the amount of Group VIII metal present in the conversion catalyst should be within the normal range of use in isomerizing catalysts, from about 0.05 to 2.0 weight percent, preferably 0.2 to 0.8 weight percent.
  • Alkylation and Transalkylation SSZ-65 can be used in a process for the alkylation or transalkylation of an aromatic hydrocarbon.
  • the process comprises contacting the aromatic hydrocarbon with a C 2 to Cj 6 olefin alkylating agent or a polyalkyl aromatic hydrocarbon transalkylating agent, under at least partial liquid phase conditions, and in the presence of a catalyst comprising SSZ-65.
  • SSZ-65 can also be used for removing benzene from gasoline by alkylating the benzene as described above and removing the alkylated product from the gasoline.
  • the SSZ-65 molecular sieve should be predominantly in its hydrogen ion form. It is preferred that, after calcination, at least 80% of the cation sites are occupied by hydrogen ions and/or rare earth ions.
  • suitable aromatic hydrocarbon feedstocks which may be alkylated or transalkylated by the process of the invention include aromatic compounds such as benzene, toluene and xylene.
  • the preferred aromatic hydrocarbon is benzene.
  • naphthalene or naphthalene derivatives such as dimethylnaphthalene may be desirable.
  • Mixtures of aromatic hydrocarbons may also be employed.
  • Suitable olefins for the alkylation of the aromatic hydrocarbon are those containing 2 to 20, preferably 2 to 4, carbon atoms, such as ethylene, propylene, butene-1, trans-butene-2 and cis-butene-2, or mixtures thereof. There may be instances where pentenes are desirable.
  • the preferred olefins are ethylene and propylene. Longer chain alpha olefins may be used as well.
  • the transalkylating agent is a polyalkyl aromatic hydrocarbon containing two or more alkyl groups that each may have from 2 to about 4 carbon atoms.
  • suitable polyalkyl aromatic hydrocarbons include di-, tri- and tetra-alkyl aromatic hydrocarbons, such as diethylbenzene, triethylbenzene, diethylmethylbenzene (diethyltoluene), di-isopropylbenzene, di-isopropyltoluene, dibutylbenzene, and the like.
  • Preferred polyalkyl aromatic hydrocarbons are the dialkyl benzenes.
  • a particularly preferred polyalkyl aromatic hydrocarbon is di-isopropylbenzene.
  • reaction conditions are as follows.
  • the aromatic hydrocarbon feed should be present in stoichiometric excess. It is preferred that molar ratio of aromatics to olefins be greater than four-to-one to prevent rapid catalyst fouling.
  • the reaction temperature may range from 100°F to 600°F (38°C to 315°C), preferably 250°F to 45O 0 F (121°C to 232 0 C).
  • the reaction pressure should be sufficient to maintain at least a partial liquid phase in order to retard catalyst fouling.
  • WHSV weight hourly space velocity
  • the molar ratio of aromatic hydrocarbon will generally range from about 1 :1 to 25 : 1 , and preferably from about 2: 1 to 20: 1.
  • SSZ-65 can be used to convert light gas C 2 -C 6 paraffins to higher molecular weight hydrocarbons including aromatic compounds.
  • the molecular sieve will contain a catalyst metal or metal oxide wherein said metal is selected from the group consisting of Groups IB, HB, VIII and IIIA of the Periodic Table.
  • the metal is gallium, niobium, indium or zinc in the range of from about 0.05 to 5% by weight.
  • Isomerization of Olefins SSZ-65 can be used to isomerize olefins.
  • the feed stream is a hydrocarbon stream containing at least one C 4-6 olefin, preferably a C 4-6 normal olefin, more preferably normal butene.
  • Normal butene as used in this specification means all forms of normal butene, e.g., 1-butene, cis-2-butene, and trans-2-butene.
  • hydrocarbons other than normal butene or other C 4-6 normal olefins will be present in the feed stream. These other hydrocarbons may include, e.g., alkanes, other olefins, aromatics, hydrogen, and inert gases.
  • the process may be carried out generally at a temperature from about 625°F to about 95O°F (329-510 0 C), for butenes, preferably from about 700°F to about 900 0 F (371- 482°C), and about 35O 0 F to about 65O 0 F (177-343 0 C) for pentenes and hexenes.
  • the pressure ranges from subatmospheric to about 200 psig (1.38 MPa gauge), preferably from about 15 psig to about 200 psig (0.103 to 1.38 MPa gauge), and more preferably from about 1 psig to about 150 psig (0.00689 to 1.03 MPa gauge).
  • the mole percent conversion of, e.g., normal butene to iso-butene is at least 10, preferably at least 25, and more preferably at least 35.
  • Xylene Isomerization SSZ-65 may also be useful in a process for isomerizing one or more xylene isomers in a C 8 aromatic feed to obtain ortho-, meta-, and para-xylene in a ratio approaching the equilibrium value.
  • xylene isomerization is used in conjunction with a separate process to manufacture para-xylene. For example, a portion of the para-xylene in a mixed C 8 aromatics stream may be recovered by crystallization and centrifugation.
  • the catalyst should comprise about 0.1 to 2.0 wt.% of a hydrogenation/dehydrogenation component selected from Group VIII (of the Periodic Table) metal component, especially platinum or nickel.
  • Group VIII metal component is meant the metals and their compounds such as oxides and sulfides.
  • the isomerization feed may contain 10 to 90 wt. of a diluent such as toluene, trimethylbenzene, naphthenes or paraffins.
  • Oligomerization It is expected that SSZ-65 can also be used to oligomerize straight and branched chain olefins having from about 2 to 21 and preferably 2-5 carbon atoms.
  • the oligomers which are the products of the process are medium to heavy olefins which are useful for both fuels, i.e., gasoline or a gasoline blending stock and chemicals.
  • the oligomerization process comprises contacting the olefin feedstock in the gaseous or liquid phase with a catalyst comprising SSZ-65.
  • the molecular sieve can have the original cations associated therewith replaced by a wide variety of other cations according to techniques well known in the art. Typical cations would include hydrogen, ammonium and metal cations including mixtures of the same.
  • the molecular sieve have a fairly low aromatization activity, i.e., in which the amount of aromatics produced is not more than about 20% by weight. This is accomplished by using a molecular sieve with controlled acid activity [alpha value] of from about 0.1 to about 120, preferably from about 0.1 to about 100, as measured by its ability to crack n-hexane.
  • Alpha values are defined by a standard test known in the art, e.g., as shown in U.S. Patent No. 3,960,978 issued on June 1, 1976 to Givens et al. which is incorporated totally herein by reference. If required, such molecular sieves may be obtained by steaming, by use in a conversion process or by any other method which may occur to one skilled in this art.
  • Condensation of Alcohols SSZ-65 can be used to condense lower aliphatic alcohols having 1 to 10 carbon atoms to a gasoline boiling point hydrocarbon product comprising mixed aliphatic and aromatic hydrocarbon. The process disclosed in U.S. Patent No.
  • the catalyst may be in the hydrogen form or may be base exchanged or impregnated to contain ammonium or a metal cation complement, preferably in the range of from about 0.05 to 5% by weight.
  • the metal cations that may be present include any of the metals of the Groups I through VIII of the Periodic Table. However, in the case of Group IA metals, the cation content should in no case be so large as to effectively inactivate the catalyst, nor should the exchange be such as to eliminate all acidity. There may be other processes involving treatment of oxygenated substrates where a basic catalyst is desired.
  • Methane Upgrading Higher molecular weight hydrocarbons can be formed from lower molecular weight hydrocarbons by contacting the lower molecular weight hydrocarbon with a catalyst comprising SSZ-65 and a metal or metal compound capable of converting the lower molecular weight hydrocarbon to a higher molecular weight hydrocarbon.
  • a catalyst comprising SSZ-65 and a metal or metal compound capable of converting the lower molecular weight hydrocarbon to a higher molecular weight hydrocarbon.
  • Examples of such reactions include the conversion of methane to C 2+ hydrocarbons such as ethylene or benzene or both.
  • useful metals and metal compounds include lanthanide and or actinide metals or metal compounds.
  • SSZ-65 may be used for the catalytic reduction of the oxides of nitrogen in a gas stream.
  • the gas stream also contains oxygen, often a stoichiometric excess thereof.
  • the SSZ-65 may contain a metal or metal ions within or on it which are capable of catalyzing the reduction of the nitrogen oxides. Examples of such metals or metal ions include copper, cobalt, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium and mixtures thereof.
  • One example of such a process for the catalytic reduction of oxides of nitrogen in the presence of a molecular sieve is disclosed in U.S. Patent No.
  • the catalytic process is the combustion of carbon monoxide and hydrocarbons and the catalytic reduction of the oxides of nitrogen contained in a gas stream, such as the exhaust gas from an internal combustion engine.
  • the molecular sieve used is metal ion-exchanged, doped or loaded sufficiently so as to provide an effective amount of catalytic copper metal or copper ions within or on the molecular sieve.
  • the process is conducted in an excess of oxidant, e.g., oxygen.
  • oxidant e.g., oxygen.
  • l-[l-(4-Chloro-phenyl)- cyclopropylmethyl]- 1-ethyl-pyrrolidinium The structure directing agent is synthesized according to the synthetic scheme shown below (Scheme 1). l-[l-(4-chloro-phenyl)-cyclopropylmethyl]-l-ethyl-pyrrolidinium iodide is , prepared from the reaction of the parent amine l-[l-(4-chloro-phenyl)- cyclopropylmethyl] -pyrrolidine with ethyl iodide.
  • the reaction mixture is cooled down and excess ethyl iodide and the solvent are removed at reduced pressure on a rotary evaporator.
  • the obtained dark tan-colored solids (162 gm) are further purified by dissolving in acetone (500 ml) followed by precipitation by adding diethyl ether. Filtration and air-drying the obtained solids gives 153 gm (93% yield) of the desired l-[l-(4-chloro-phenyl)- cyclopropylmethyl] -1-ethyl-pyrrolidinium iodide as a white powder.
  • the product is pure by 1 H and 13 C-NMR analysis.
  • the hydroxide form of 1 - [ 1 -(4-chloro-phenyl)-cyclopropylmethyl] - 1 -ethyl- pyrrolidinium cation is obtained by an ion exchange treatment of the iodide salt with Ion-Exchange Resin-OH (BIO RAD ® AHl -X8).
  • Ion-Exchange Resin-OH BIO RAD ® AHl -X8
  • 100 gm (255 mmol) of l-[l-(4-chloro-phenyl)-cyclopropylmethyl]-l-ethyl- pyrrolidinium iodide is dissolved in 300 ml de-ionized water.
  • the parent amine l-[l-(4-chloro-phenyl)-cyclopropylmethyl]-pyrrolidine is obtained from the LiAlH 4 -reduction of the precursor amide [ 1 -(4-chloro-phenyl)- cyclopropylj-pyrrolidin-l-yl-methanone.
  • 45.5 gm (1.2 mol.) Of LiAlH 4 is suspended in 750 ml anhydrous tetrahydrofuran (THF).
  • the suspension is cooled down to O 0 C (ice-bath), and 120 gm (0.48 mole) of [l-(4-chloro-phenyl)- cyclopropyl]-pyrrolidin-l-yl-methanone dissolved in 250 ml THF is added (to the suspension) drop-wise via an addition funnel. Once all the amide solution is added, the ice-bath is replaced with a heating mantle and the reaction mixture is heated at reflux overnight. Then, the reaction solution is cooled down to O 0 C (the heating mantle was replaced with an ice-bath), and the mixture is diluted with 500 ml diethyl ether. The reaction is worked up by adding 160 ml of 15% wt.
  • the parent amide [l-(4-chloro-phenyl)-cyclopropyl]-pyrrolidin-l-yl- methanone is prepared by reacting pyrrolidine with l-(4-chloro-phenyl)- cyclopropanecarbonyl chloride.
  • a 2-Liter reaction flask equipped with a mechanical stirrer is charged with 1000 ml of dry benzene, 53.5 gm (0.75 mol.) of pyrrolidine and 76 gm (0.75 mol.) of triethyl amine.
  • the organic layer is washed twice with 500 ml water and once with brine. Then, the organic layer is dried over anhydrous sodium sulfate, filtered and concentrated on a rotary evaporator at reduced pressure to give 122 gm (0.49 mol, 97% yield) of the amide as a tan-colored solid substance.
  • the l-(4-chloro-phenyl)-cyclopropanecarbonyl chloride used in the synthesis of the amide is synthesized by treatment of the parent acid l-(4-chloro-phenyl)- cyclopropanecarboxylic acid with thionyl chloride (SOCl 2 ) as described below.
  • SDA 1 -ethyl- l-(l-phenyl-cyclopropylmethyl)-pyrro Ii dinium cation is synthesized using the synthesis procedure of Example 1, except that the synthesis starts from 1 -phenyl-cyclopropanecarbonyl chloride and pyrrolidine.
  • a 23 cc Teflon liner is charged with 5.4 gm of 0.6M aqueous solution of 1- ethyl-l-(l-phenyl-cyclopropylmethyl)-pyrrolidinium hydroxide (3 mmol SDA), 1.2 gm of IM aqueous solution of NaOH (1.2 mmol NaOH) and 5.4 gm of de-ionized water.
  • 0.06 gm of sodium borate decahydrate (0.157 mmol of Na 2 B 4 O 7 -IOH 2 O; -0.315 mmol B 2 O 3 ) is added and stirred until completely dissolved.
  • the reaction is monitored by checking the gel's pH (increase in the pH usually results from condensation of the silicate species during crystallization, and decrease in pH often indicates decomposition of the SDA), and by checking for crystal formation by scanning electron microscopy.
  • the reaction is usually complete after heating for 12 days at the conditions described above.
  • the starting reaction gel turns to a mixture comprised of a liquid and powdery precipitate.
  • the mixture is filtered through a fritted-glass funnel.
  • the collected solids are thoroughly washed with water and, then, rinsed with acetone (10 ml) to remove any organic residues.
  • the solids are allowed to air-dry overnight and, then, dried in an oven at 120° C for lhour.
  • SSZ-65 as synthesized in Example 3 is calcined to remove the structure directing agent (SDA) as described below.
  • SDA structure directing agent
  • a thin bed of SSZ-65 in a calcination dish is heated in a muffle furnace from room temperature to 12O 0 C at a rate of l°CZminute and held for 2 hours. Then, the temperature is ramped up to 54O 0 C at a rate of l°C/minute and held for 5 hours. The temperature is ramped up again at l°C/minute to 595 0 C and held there for 5 hours.
  • a 50/50 mixture of air and nitrogen passes through the muffle furnace at a rate of 20 standard cubic feet (0.57 standard cubic meters) per minute during the calcination process.
  • Example 17 Conversion of Borosilicate-SSZ-65 to Aluminosilicate SSZ-6S
  • the calcined version of borosilicate SSZ-65 (as synthesized in Example 3 and calcined in Example 16) is easily converted to the aluminosilicate SSZ-65 version by suspending borosilicate SSZ-65 in IM solution of aluminum nitrate nonahydrate (15 ml of IM A1(NO 3 ) 3 .9H 2 O soln./l gm SSZ-65). The suspension is heated at reflux overnight. The resulting mixture is then filtered and the collected solids are thoroughly rinsed with de-ionized water and air-dried overnight.
  • Example 18 Ammonium- Ion Exchange of SSZ-65
  • the Na + form of SSZ-65 (prepared as in Example 3 or as in Example 5 and calcined as in Example 16) is converted to NH 4 + -SSZ-65 form by heating the material in an aqueous solution OfNH 4 NO 3 (typically lgm NH 4 NO 3 /1 gm SSZ-65 in 20 ml H 2 O) at 9O 0 C for 2-3 hours. The mixture is then filtered and the obtained NH 4 - exchanged-product is washed with de-ionized water and dried.
  • aqueous solution OfNH 4 NO 3 typically lgm NH 4 NO 3 /1 gm SSZ-65 in 20 ml H 2 O
  • SSZ-65 has a micropore volume of 0.16 cc/gm based on argon adsorption isotherm at 87.5° K (-186°C) recorded on ASAP 2010 equipment from Micromerities.
  • the sample is first degassed at 400 0 C for 16 hours prior to argon adsorption.
  • the low- pressure dose is 6.00 cm 3 /g (STP).
  • a maximum of one hour equilibration time per dose is used and the total run time is 35 hours.
  • Example 20 Constraint Index
  • the hydrogen form of SSZ-65 of Example 3 (after treatment according to Examples 16, 17 and 18) is pelletized at 3 KPSI, crushed and granulated to 20-40 mesh.
  • a 0.6 gram sample of the granulated material is calcined in air at 54O 0 C for 4 hours and cooled in a desiccator to ensure dryness. Then, 0.5 gram is packed into a 3/8 inch stainless steel tube with alundum on both sides of the molecular sieve bed.
  • a Lindburg furnace is used to heat the reactor tube. Helium is introduced into the reactor tube at 10 cc/min. and at atmospheric pressure. The reactor is heated to about 315°C, and a 50/50 feed of n-hexane and 3-methylpentane is introduced into the reactor at a rate of 8 ⁇ l/min. The feed is delivered by a Brownlee pump. Direct sampling into a GC begins after 10 minutes of feed introduction.
  • the Constraint hid ex (CI) value is calculated from the GC data using methods known in the art.
  • SSZ-65 has a CI of 0.67 and a conversion of 92% after 20 minutes on stream. The material fouls rapidly and at 218 minutes the CI is 0.3 and the conversion is 15.7%. The data suggests a large pore molecular sieve with perhaps large cavities.
  • Example 21 Hvdrocracking of n-Hexadecane A 1 gm sample of SSZ-65 (prepared as in Example 3 and treated as in Examples 16, 17 and 18) is suspended in 10 gm de-ionized water. To this suspension, a solution of Pd(NH 3 ) 4 (NO 3 ) 2 at a concentration which would provide 0.5 wt.
  • % Pd with respect to the dry weight of the molecular sieve sample is added.
  • the pH of the solution is adjusted to pH of ⁇ 9 by a drop- wise addition of dilute ammonium hydroxide solution.
  • the mixture is then heated in an oven at 75 0 C for 48 hours.
  • the mixture is then filtered through a glass frit, washed with de-ionized water, and air- dried.
  • the collected Pd-SSZ-65 sample is slowly calcined up to 482°C in air and held there for three hours.
  • the calcined Pd/SSZ-65 catalyst is pelletized in a Carver Press and granulated to yield particles with a 20/40 mesh size.
  • Sized catalyst (0.5 g) is packed into a 1 A inch OD tubing reactor in a micro unit for n-hexadecane hydroconversion.
  • the table below gives the run conditions and the products data for the hydrocracking test on n- hexadecane.
  • SSZ-65 is synthesized in a manner similar to that of Example 3 using a 1-[1- (4-chlorophenyl)-cyclopropylmethyl]-l-ethyl-pyrrolidinium cation as the SDA.

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Abstract

L'invention concerne un tamis moléculaire cristallin SSZ-65 synthétisé au moyen de cations de 1-[1-(4-chlorophényl)-cyclopropylméthyl]-1-éthyl-pyrrolidinium ou 1 éthyl-1-(1-phényl-cyclopropylméthyl)-pyrrolidinium en tant qu'agents structurels. L'invention concerne également des procédés de synthèse de SSZ-65 et des procédés faisant intervenir SSZ-65 dans un catalyseur.
PCT/US2005/034250 2004-09-30 2005-09-26 Tamis moleculaire ssz-65 WO2006039213A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2007534674A JP2008514540A (ja) 2004-09-30 2005-09-26 モレキュラーシーブｓｓｚ−６５
CA002582295A CA2582295A1 (fr) 2004-09-30 2005-09-26 Tamis moleculaire ssz-65
AU2005292315A AU2005292315A1 (en) 2004-09-30 2005-09-26 Molecular sieve SSZ-65
EP05798730A EP1807348A1 (fr) 2004-09-30 2005-09-26 Tamis moleculaire ssz-65

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US10/956,276 US20050042159A1 (en) 2003-03-26 2004-09-30 Using molecular sieve SSZ-65 for reduction of oxides of nitrogen in a gas stream
US10/956,276 2004-09-30
US10/956,267 US7011811B2 (en) 2003-03-26 2004-09-30 Molecular sieve SSZ-65 composition of matter and synthesis thereof
US10/956,313 US7083714B2 (en) 2003-03-26 2004-09-30 Hydrocarbon conversion using molecular sieve SSZ-65
US10/956,267 2004-09-30
US10/956,313 2004-09-30

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US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
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US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
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US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US8815050B2 (en) 2011-03-22 2014-08-26 Marathon Gtf Technology, Ltd. Processes and systems for drying liquid bromine
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
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CN109071245A (zh) * 2016-02-01 2018-12-21 优美科股份公司及两合公司 用于直接合成含铁的aei-沸石催化剂的方法
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CN114210363A (zh) * 2022-01-18 2022-03-22 天津派森新材料技术有限责任公司 一种ssz-16含铜催化剂的制备方法

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Cited By (31)

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US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US8415512B2 (en) 2001-06-20 2013-04-09 Grt, Inc. Hydrocarbon conversion process improvements
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
US8232441B2 (en) 2004-04-16 2012-07-31 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US7880041B2 (en) 2004-04-16 2011-02-01 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US7883568B2 (en) 2006-02-03 2011-02-08 Grt, Inc. Separation of light gases from halogens
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8415517B2 (en) 2008-07-18 2013-04-09 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8367884B2 (en) 2010-03-02 2013-02-05 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8815050B2 (en) 2011-03-22 2014-08-26 Marathon Gtf Technology, Ltd. Processes and systems for drying liquid bromine
US8436220B2 (en) 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
CN109071245A (zh) * 2016-02-01 2018-12-21 优美科股份公司及两合公司 用于直接合成含铁的aei-沸石催化剂的方法
CN112390699A (zh) * 2019-08-16 2021-02-23 中国石油化工股份有限公司 一种降烯烃的方法
CN112390699B (zh) * 2019-08-16 2023-01-24 中国石油化工股份有限公司 一种降烯烃的方法
CN114210363A (zh) * 2022-01-18 2022-03-22 天津派森新材料技术有限责任公司 一种ssz-16含铜催化剂的制备方法
WO2023138204A1 (fr) * 2022-01-18 2023-07-27 天津派森新材料技术有限责任公司 Procédé de préparation d'un catalyseur contenant du cuivre ssz-16

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