WO2007001934A2 - Molecular sieve ssz-56 composition of matter and synthesis thereof - Google Patents

Molecular sieve ssz-56 composition of matter and synthesis thereof Download PDF

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Publication number
WO2007001934A2
WO2007001934A2 PCT/US2006/023671 US2006023671W WO2007001934A2 WO 2007001934 A2 WO2007001934 A2 WO 2007001934A2 US 2006023671 W US2006023671 W US 2006023671W WO 2007001934 A2 WO2007001934 A2 WO 2007001934A2
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WIPO (PCT)
Prior art keywords
oxide
catalyst
molecular sieve
hydrocarbon
metal
Prior art date
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PCT/US2006/023671
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English (en)
French (fr)
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WO2007001934A3 (en
Inventor
Saleh Elomari
Original Assignee
Chevron U.S.A. Inc.
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Publication date
Application filed by Chevron U.S.A. Inc. filed Critical Chevron U.S.A. Inc.
Priority to KR1020087001726A priority Critical patent/KR101310994B1/ko
Priority to CN2006800304443A priority patent/CN101242887B/zh
Priority to EP06785064A priority patent/EP1909947A4/en
Priority to CA2613399A priority patent/CA2613399C/en
Priority to JP2008518263A priority patent/JP5047169B2/ja
Priority to AU2006262496A priority patent/AU2006262496B2/en
Publication of WO2007001934A2 publication Critical patent/WO2007001934A2/en
Publication of WO2007001934A3 publication Critical patent/WO2007001934A3/en

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    • 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
    • B01J29/86—Borosilicates; Aluminoborosilicates
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • 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
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2300/1081—Alkanes
    • 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
    • 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
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/10—Lubricating oil
    • 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
    • C10G2400/22—Higher 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

Definitions

  • the present invention relates to new crystalline molecular sieve SSZ- 56, a method for preparing SSZ-56 using a trans-fused ring N,N-diethyl-2- methyldecahydroquinolinium cation as a structure directing agent and the use of SSZ-56 in catalysts for, e.g., hydrocarbon conversion reactions.
  • crystalline molecular sieves and zeolites are especially useful in applications such as hydrocarbon conversion, gas drying and separation.
  • New zeolites 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 zeolites can often be formed.
  • the present invention is directed to a family of crystalline molecular sieves with unique properties, referred to herein as "molecular sieve SSZ-56" or simply "SSZ-56".
  • SSZ-56 is in its silicate, aluminosilicate, titanosilicate, 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 and the term “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 2.
  • a molecular sieve having a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, vanadium oxide and mixtures thereof and having, after calcination, the X-ray diffraction lines of Table 2 below.
  • the mole ratio of the first oxide 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.
  • the present invention further provides such a molecular sieve having a composition, as synthesized and in the anhydrous state, in terms of mole ratios as follows:
  • Y is silicon; 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; n is the valence of M (i.e., 1 or 2); and Q is a trans-fused ring N,N-diethyl-2-methyldecahydroquinolinium cation A.
  • a molecular sieve prepared by thermally treating a molecular sieve having a mole ratio of silicon oxide to an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, vanadium oxide and mixtures thereof greater than about 15 at a temperature of from about 200 0 C to about 800°C, the thus-prepared molecular sieve having the X-ray diffraction lines of Table 2.
  • the present invention also includes this thus-prepared molecular sieve which is predominantly in the hydrogen form, which hydrogen form is prepared by ion exchanging with an acid or with a solution of an ammonium salt followed by a second calcination.
  • the molecular sieve is synthesized with a high enough ratio of SDA cation to sodium ion, calcination alone may be sufficient.
  • the SSZ-56 molecular sieve should be predominantly in its hydrogen ion form.
  • "predominantly in the hydrogen form” means that, after calcination, at least 80% of the cation sites are occupied by hydrogen ions and/or rare earth ions.
  • Also provided in accordance with the present invention is a method of preparing a crystalline material comprising (1) a first oxide comprising silicon oxide and (2) a second oxide comprising boron oxide, aluminum oxide, gallium oxide, iron oxide, titanium oxide, vanadium oxide and mixtures thereof and having a mole ratio of the first oxide to the second oxide greater than about 15, said method comprising contacting under crystallization conditions sources of said oxides and a structure directing agent comprising a trans- fused ring N,N-diethyl-2-methyldecahydroquinolinium cation.
  • a process for converting hydrocarbons comprising contacting a hydrocarbonaceous feed at hydrocarbon converting conditions with a catalyst comprising the molecular sieve of this invention.
  • the molecular sieve may be predominantly in the hydrogen form. It may also be substantially free of acidity.
  • the invention includes such a process wherein the molecular sieve has a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, and has, after calcination, the X-ray diffraction lines of Table 2.
  • a hydrocracking process comprising contacting a hydrocarbon feedstock under hydrocracking conditions with a catalyst comprising the molecular sieve of this invention, preferably predominantly in the hydrogen form.
  • This invention also includes a dewaxing process comprising contacting a hydrocarbon feedstock under dewaxing conditions with a catalyst comprising the molecular sieve of this invention, preferably predominantly in the hydrogen form.
  • the present invention also includes a process for improving the viscosity index of a dewaxed product of waxy hydrocarbon feeds comprising contacting the waxy hydrocarbon feed under isomerization dewaxing conditions with a catalyst comprising the molecular sieve of this invention, preferably predominantly in the hydrogen form.
  • the present invention further includes a process for producing a C 2 o+ lube oil from a C 20 + olefin feed comprising isomerizing said olefin feed under isomerization conditions over a catalyst comprising the molecular sieve of this invention.
  • the molecular sieve may be predominantly in the hydrogen form.
  • the catalyst may contain at least one Group VIII metal.
  • a process for catalytically dewaxing a hydrocarbon oil feedstock boiling above about 350°F (177 0 C) and containing straight chain and slightly branched chain hydrocarbons comprising contacting said 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 the molecular sieve of this invention, preferably predominantly in the hydrogen form.
  • the catalyst may contain at least one Group VIII metal.
  • 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 zeolite which is more shape selective than the molecular sieve of said first layer.
  • the first layer may contain at least one Group VIII metal.
  • Also included in the present invention is a process for preparing a lubricating oil which comprises hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent comprising a hydrocracked oil, and catalytically dewaxing said effluent comprising hydrocracked oil at a temperature of at least about 400°F (204 0 C) and at a pressure of from about 15 psig to about 3000 psig (0.103 - 20.7 Mpa gauge)in the presence of added hydrogen gas with a catalyst comprising the molecular sieve of this invention.
  • the molecular sieve may be predominantly in the hydrogen form.
  • the catalyst may contain at least one Group VIII metal.
  • a process for isomerization dewaxing a raffinate comprising contacting said raffinate in the presence of added hydrogen with a catalyst comprising the molecular sieve of this invention.
  • the raffinate may be bright stock, and the molecular sieve may be predominantly in the hydrogen form.
  • the catalyst may contain at least one Group VIII metal.
  • Also included in this invention is a process for increasing the octane of a hydrocarbon feedstock to produce a product having an increased aromatics content
  • a hydrocarbonaceous feedstock which comprises normal and slightly branched hydrocarbons having a boiling range above about 40 0 C and less than about 200°C, under aromatic conversion conditions with a catalyst comprising the molecular sieve of this invention made substantially free of acidity by neutralizing said molecular sieve with a basic metal.
  • a catalyst comprising the molecular sieve of this invention made substantially free of acidity by neutralizing said molecular sieve with a basic metal.
  • the molecular sieve contains a Group VIII metal component.
  • a catalytic cracking process comprising contacting a hydrocarbon feedstock in a reaction zone under catalytic cracking conditions in the absence of added hydrogen with a catalyst comprising the molecular sieve of this invention, preferably predominantly in the hydrogen form. Also included in this invention is such a catalytic cracking process wherein the catalyst additionally comprises a large pore crystalline cracking component.
  • This invention further provides an isomerization process for isomerizing C 4 to C 7 hydrocarbons, comprising contacting a feed having normal and slightly branched C 4 to C 7 hydrocarbons under isomerizing conditions with a catalyst comprising the molecular sieve of this invention, preferably predominantly in the hydrogen form.
  • the molecular sieve may be impregnated with at least one Group VIII metal, preferably platinum.
  • the catalyst may be calcined in a steam/air mixture at an elevated temperature after impregnation of the Group VIII metal.
  • a process for alkylating an aromatic hydrocarbon which comprises contacting under alkylation conditions at least a molar excess of an aromatic hydrocarbon with a C 2 to C2 0 olefin under at least partial liquid phase conditions and in the presence of a catalyst comprising the molecular sieve of this invention, preferably predominantly in the hydrogen form.
  • the olefin may be a O 2 to C 4 olefin, and the aromatic hydrocarbon and olefin may be present in a molar ratio of about 4:1 to about 20:1 , respectively.
  • the aromatic hydrocarbon may be selected from the group consisting of benzene, toluene, ethylbenzene, xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene or mixtures thereof.
  • a process for transalkylating an aromatic hydrocarbon which comprises contacting under transalkylating conditions an aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon under at least partial liquid phase conditions and in the presence of a catalyst comprising the molecular sieve of this invention, preferably predominantly in the hydrogen form.
  • the aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon may be present in a molar ratio of from about 1 :1 to about 25:1 , respectively.
  • the aromatic hydrocarbon may be selected from the group consisting of benzene, toluene, ethylbenzene, xylene, or mixtures thereof, and the polyalkyl aromatic hydrocarbon may be a dialkylbenzene.
  • 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 C2+ 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 catalyst composition for promoting polymerization of 1 -olefins said composition comprising
  • Oxide (1) may be silicon oxide
  • oxide (2) may be an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide.
  • the present invention further provides a for polymerizing 1 -olefins, which process comprises contacting 1 -olefin monomer with a catalytically effective amount of a catalyst composition comprising
  • Oxide (1) may be silicon oxide
  • oxide (2) may be an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide.
  • the present invention further provides a process for hydrogenating a hydrocarbon feed containing unsaturated hydrocarbons, the process comprising contacting the feed and hydrogen under conditions which cause hydrogenation with a catalyst comprising the molecular sieve of this invention.
  • the catalyst can also contain metals, salts or complexes wherein the metal is selected from the group consisting of platinum, palladium, rhodium, iridium or combinations thereof, or the group consisting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, vanadium, rhenium, manganese and combinations thereof.
  • a process for hydrotreating a hydrocarbon feedstock comprising contacting the feedstock with a hydrotreating catalyst and hydrogen under hydrotreating conditions, wherein the catalyst comprises the molecular sieve of this invention.
  • a process for the reduction of oxides of nitrogen contained in a gas stream comprising contacting the gas stream with a molecular sieve, the 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 2.
  • a process for the reduction of oxides of nitrogen contained in a gas stream comprising contacting the gas stream with a molecular sieve, the molecular sieve having a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, and having, after calcination, the X-ray diffraction lines of Table 2.
  • the molecular sieve may contain a metal or metal ions (such as cobalt, copper, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium or mixtures thereof) capable of catalyzing the reduction of the oxides of nitrogen, and the process may be conducted in the presence of a stoichiometric excess of oxygen.
  • a metal or metal ions such as cobalt, copper, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium or mixtures thereof
  • the gas stream is the exhaust stream of an internal combustion engine.
  • the present invention provides a process for treating a cold-start engine exhaust gas stream containing hydrocarbons and other pollutants consisting of flowing said engine exhaust gas stream over a molecular sieve bed which preferentially adsorbs the hydrocarbons over water to provide a first exhaust stream, and flowing the first exhaust gas stream over a catalyst to convert any residual hydrocarbons and other pollutants contained in the first exhaust gas stream to innocuous products and provide a treated exhaust stream and discharging the treated exhaust stream into the atmosphere, the molecular sieve bed characterized in that it comprises 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 which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2.
  • the molecular sieve has a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, and having, after calcination, the X-ray diffraction lines of Table 2.
  • the present invention further provides such a process wherein the engine is an internal combustion engine, including automobile engines, which can be fueled by a hydrocarbonaceous fuel.
  • the molecular sieve has deposited on it a metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, and mixtures thereof.
  • the present invention comprises a family of crystalline molecular sieves designated herein "molecular sieve SSZ-56" or simply “SSZ-56".
  • SSZ-56 a family of crystalline molecular sieves designated herein "molecular sieve SSZ-56” or simply "SSZ-56".
  • SDA structure directing agent
  • the SDA useful for making SSZ-56 has the following structure:
  • the SDA cation is associated with an anion (X " ) which may be any anion that is not detrimental to the formation of the molecular sieve.
  • anion include halogen, e.g., fluoride, chloride, bromide and iodide, hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, and the like. Hydroxide is the most preferred anion.
  • SSZ-56 is prepared from a reaction mixture having the composition shown in Table A below.
  • Y is silicon; W is aluminum, gallium, iron, boron, titanium, indium, vanadium or mixtures thereof; a is 1 or 2, b is 2 when a is 1 (i.e., W is tetravalent); b is 3 when a is 2 (i.e., W is trivalent); M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; n is the valence of M (i.e., 1 or 2); and Q is a trans-fused ring N,N-diethyl-2-methyldecahydroquinolinium cation;.
  • SSZ-56 is prepared by a process comprising: (a) preparing an aqueous solution containing sources of oxides capable of forming a crystalline molecular sieve and a trans-fused ring N,N-diethyl-2 ⁇ methyldecahydroquinolinium cation having an anionic counterion which is not detrimental to the formation of SSZ-56; (b) maintaining the aqueous solution under conditions sufficient to form crystals of SSZ-56; and (c) recovering the crystals of SSZ-56.
  • SSZ-56 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.
  • Typical sources of silicon oxide include silicates, silica hydrogel, silicic acid, fumed silica, colloidal silica, tetra-alkyl orthosilicates, and silica hydroxides. Boron can be added in forms corresponding to its silicon counterpart, such as boric acid.
  • a source zeolite reagent may provide a source of boron. In most cases, the source zeolite also provides a source of silica.
  • the source zeolite in its 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 zeolite reagent 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 alkali metal cation or alkaline earth cation may be part of the as-synthesized crystalline oxide material, in order to balance valence electron charges therein.
  • the reaction mixture is maintained at an elevated temperature until the crystals of the SSZ-56 are formed.
  • the hydrothermal crystallization is usually conducted under autogenous pressure, at a temperature between 100°C and 200°C, preferably between 135°C and 160°C.
  • the crystallization period is typically greater than 1 day and preferably from about 3 days to about 20 days.
  • the molecular sieve is prepared using mild stirring or agitation.
  • the SSZ-56 crystals can be allowed to nucleate spontaneously from the reaction mixture.
  • the use of SSZ-56 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-56 over any undesired phases.
  • SSZ-56 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.
  • the solid product is separated from the reaction mixture by standard mechanical separation techniques such as filtration.
  • the crystals are water-washed and then dried, e.g., at 90 0 C to 150 0 C for from 8 to 24 hours, to obtain the as-synthesized SSZ-56 crystals.
  • the drying step can be performed at atmospheric pressure or under vacuum.
  • SSZ-56 as prepared has a mole ratio of silicon oxide to boron oxide greater than about 15; and has, after calcination, the X-ray diffraction lines of Table 2 below.
  • SSZ-56 further has a composition, as synthesized (i.e., prior to removal of the SDA from the SSZ-56) and in the anhydrous state, in terms of mole ratios, shown in Table B below.
  • Table B TABLE B As-Synthesized SSZ-56 YO 2 /W c Od 15 - infinity M 2 Z n AO 2 0 - 0.03 QAO 2 0.02 - 0.05
  • SSZ-56 can be an all-silica. SSZ-56 is made as a borosilicate and then the boron can be removed, if desired, by treating the borosilicate SSZ-56 with acetic acid at elevated temperature (as described in Jones et al., Chem.
  • SSZ-56 can be made as a borosilicate and then the boron can be removed as described above and replaced with metal atoms by techniques known in the art. Aluminum, gallium, iron, titanium, vanadium and mixtures thereof can be added in this manner. It is believed that SSZ-56 is comprised of a new framework structure or topology which is characterized by its X-ray diffraction pattern. SSZ-56, as-synthesized, has a crystalline structure whose X-ray powder diffraction pattern exhibit the characteristic lines shown in Table 1 and is thereby distinguished from other molecular sieves. TABLE 1
  • the X-ray patterns provided are based on a relative intensity scale in which the strongest line in the X-ray pattern is assigned a value of 100: W(weak) is less than 20; M(medium) is between 20 and 40; S(strong) is between 40 and 60; VS(very strong) is greater than 60.
  • Table 1A below shows the X-ray powder diffraction lines for as- synthesized SSZ-56 including actual relative intensities. TABLE 1A
  • Table 2A shows the X-ray powder diffraction lines for calcined SSZ-56 including actual relative intensities.
  • 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 ⁇ 0.10 degrees.
  • the X-ray diffraction pattern of Table 1 is representative of "as- synthesized" or "as-made” SSZ-56 molecular sieves.
  • the molecular sieve produced by exchanging the metal or other cations present in the molecular sieve with various other cations yields essentially the same diffraction pattern, although again, there may be minor shifts in the interplanar spacing and variations in the relative intensities of the peaks. Notwithstanding these minor perturbations, the basic crystal lattice remains unchanged by these treatments.
  • Crystalline SSZ-56 can be used as-synthesized, but preferably will be thermally treated (calcined). Usually, it is desirable to remove the alkali metal cation by ion exchange and replace it with hydrogen, ammonium, or any desired metal ion.
  • the molecular sieve can be leached with chelating agents, e.g., EDTA or dilute acid solutions, to increase the silica to alumina mole ratio.
  • the molecular sieve can also be steamed; steaming helps stabilize the crystalline lattice to attack from acids.
  • the molecular sieve can be used in intimate combination with hydrogenating components, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as palladium or platinum, for those applications in which a hydrogenation- dehydrogenation function is desired.
  • Metals may also be introduced into the molecular sieve by replacing some of the cations in the molecular sieve with metal cations via standard ion exchange techniques (see, for example, U.S. Patent Nos. 3,140,249 issued July 7, 1964 to Plank et al.; 3,140,251 issued July 7, 1964 to Plank et al.; and 3,140,253 issued July 7, 1964 to Plank et al.).
  • Typical replacing cations can include metal cations, e.g., rare earth, Group IA, Group HA and Group VIII metals, as well as their mixtures.
  • cations of metals such as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, AI, Sn, and Fe are particularly preferred.
  • the hydrogen, ammonium, and metal components can be ion-exchanged into the SSZ-56.
  • the SSZ-56 can also be impregnated with the metals, or the metals can be physically and intimately admixed with the SSZ-56 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.
  • the molecular sieve is typically washed with water and dried at temperatures ranging from 65°C to about 200°C. After washing, the molecular sieve can be calcined in air or inert gas at temperatures ranging from about 200°C to about 800°C for periods of time ranging from 1 to 48 hours, or more, to produce a catalytically active product especially useful in hydrocarbon conversion processes.
  • the spatial arrangement of the atoms which form the basic crystal lattice of the molecular sieve remains essentially unchanged.
  • SSZ-56 can be formed into a wide variety of physical shapes.
  • the molecular sieve can be in the form of a powder, a granule, or a molded product, such as extrudate having a particle size sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) screen, in cases where the catalyst is molded, such as by extrusion with an organic binder, the SSZ-56 can be extruded before drying, or, dried or partially dried and then extruded. SSZ-56 can be composited with other materials resistant to the temperatures and other conditions employed in organic conversion processes. Such matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and metal oxides.
  • SSZ-56 is useful in catalysts for a variety of hydrocarbon conversion reactions such as hydrocracking, dewaxing, isomerization and the like, for the reduction of oxides of nitrogen in a gas stream, and for treating a cold-start engine exhaust stream.
  • Hydrocarbon Conversion Processes SSZ-56 zeolites 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-56 are expected to be useful include hydrocracking, dewaxing, catalytic cracking and olefin and aromatics formation reactions.
  • the catalysts are also expected to be useful in other petroleum refining and hydrocarbon conversion reactions such as isomerizing n-paraffins and naphthenes, polymerizing and oligomerizing olefinic or acetylenic compounds such as isobutylene and butene-1, polymerization of 1 -olefins (e.g., ethylene), reforming, isomerizing polyalkyl substituted aromatics (e.g., m-xylene), and disproportionating aromatics (e.g., toluene) to provide mixtures of benzene, xylenes and higher methylbenzenes and oxidation reactions.
  • 1 -olefins e.g., ethylene
  • reforming isomerizing polyalkyl substituted aromatics (e.g., m-xylene)
  • disproportionating aromatics e.g., toluene
  • the SSZ-56 catalysts may have high selectivity, and under hydrocarbon conversion conditions can provide a high percentage of desired products relative to total products.
  • the SSZ-56 zeolite should be predominantly in its hydrogen ion form.
  • the zeolite is converted to its hydrogen form by ammonium exchange followed by calcination. If the zeolite is synthesized with a high enough ratio of SDA cation to sodium ion, calcination alone may be sufficient.
  • SSZ-56 zeolites can be used in processing hydrocarbonaceous feedstocks.
  • Hydrocarbonaceous feedstocks contain carbon compounds and can be from many different sources, such as virgin petroleum fractions, recycle petroleum fractions, shale oil, liquefied coal, tar sand oil, synthetic paraffins from NAO, recycled plastic feedstocks and, in general, can be any carbon containing feedstock susceptible to zeolitic catalytic reactions.
  • the feed can contain metal or be free of metals, it can also have high or low nitrogen or sulfur impurities. It can be appreciated, however, that in general processing will be more efficient (and the catalyst more active) the lower the metal, nitrogen, and sulfur content of the feedstock.
  • the conversion of hydrocarbonaceous feeds can take place in any convenient mode, for example, in fluidized bed, moving bed, or fixed bed reactors depending on the types of process desired.
  • the formulation of the catalyst particles will vary depending on the conversion process and method of operation.
  • Other reactions which can be performed using the catalyst of this invention containing a metal, e.g., a Group VIII metal such platinum, include hydrogenation-dehydrogenation reactions, denitrogenation and desulfurization reactions.
  • the following table indicates typical reaction conditions which may be employed when using catalysts comprising SSZ-56 in the hydrocarbon conversion reactions of this invention. Preferred conditions are indicated in parentheses.
  • Hvdrocracking Using a catalyst which comprises SSZ-56, preferably predominantly in the hydrogen form, and a hydrogenation promoter, heavy petroleum residual feedstocks, cyclic stocks and other hydrocrackate charge stocks can be hydrocracked using the process conditions and catalyst components disclosed in the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753.
  • the 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.
  • the hydrogenation catalyst is preferably selected from the group of metals, salts and complexes thereof of the group consisting of at least one of platinum, palladium, rhodium, iridium, ruthenium and mixtures thereof or the group consisting of at least one of nickel, molybdenum, cobalt, tungsten, titanium, chromium and mixtures thereof.
  • Reference to the catalytically active metal or metals is intended to encompass such metal or metals in the elemental state or in some form such as an oxide, sulfide, halide, carboxylate and the like.
  • the hydrogenation catalyst is present in an effective amount to provide the hydrogenation function of the hydrocracking catalyst, and preferably in the range of from 0.05 to 25% by weight.
  • Dewaxing SSZ-56 preferably predominantly in the hydrogen form, can be used to dewax hydrocarbonaceous feeds by selectively removing straight chain paraffins.
  • the viscosity index of the dewaxed product is improved (compared to the waxy feed) when the waxy feed is contacted with SSZ-56 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 0 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-56 and at least one Group VIII metal.
  • the SSZ-56 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 hydrogenation component is present in an effective amount to provide an effective hydrodewaxing and hydroisomerization catalyst preferably in the range of from about 0.05 to 5% by weight.
  • the catalyst may be run in such a mode to increase isomerization dewaxing at the expense of cracking reactions.
  • the feed may be hydrocracked, followed by dewaxing. This type of two stage process and typical hydrocracking conditions are described in U.S. Patent No. 4,921 ,594, issued May 1 , 1990 to Miller, which is incorporated herein by reference in its entirety.
  • SSZ-56 may also be utilized as a dewaxing catalyst in the form of a layered catalyst.
  • the catalyst comprises a first layer comprising zeolite SSZ-56 and at least one Group VIII metal, and a second layer comprising an aluminosilicate zeolite which is more shape selective than zeolite SSZ-56.
  • the use of layered catalysts is disclosed in U.S. Patent No. 5,149,421 , issued September 22, 1992 to Miller, which is incorporated by reference herein in its entirety.
  • the layering may also include a bed of SSZ- 56 layered with a non-zeolitic component designed for either hydrocracking or hydrofinishing.
  • SSZ-56 may also be used to dewax raffinates, including bright stock, under conditions such as those disclosed in U. S. Patent No.
  • hydrofinishing mild hydrogenation
  • the hydrofinishing step can be performed either before or after the dewaxing step, and preferably after.
  • Hydrofinishing is typically conducted at temperatures ranging from about 190 0 C to about 340°C at pressures from about 400 psig to about 3000 psig (2.76 to 20.7 Mpa gauge) at space velocities (LHSV) between about 0.1 and 20 and a hydrogen recycle rate of about 400 to 1500 SCF/bbl (0.071 to 0.27 SCM/liter).
  • the hydrogenation catalyst employed must be active enough not only to hydrogenate the olefins, diolefins and color bodies which may be present, but also to reduce the aromatic content. Suitable hydrogenation catalyst are disclosed in U. S. Patent No. 4,921 ,594, issued May 1 , 1990 to Miller, which is incorporated by reference herein in its entirety.
  • the hydrofinishing step is beneficial in preparing an acceptably stable product (e.g., a lubricating oil) since dewaxed products prepared from hydrocracked stocks tend to be unstable to air and light and tend to form sludges spontaneously and quickly.
  • Lube oil may be prepared using SSZ-56.
  • a C 20+ lube oil may be made by isomerizing a C 20 + olefin feed over a catalyst comprising SSZ-56 in the hydrogen form and at least one Group VIII metal.
  • the lubricating oil may be made by hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent comprising a hydrocracked oil, and catalytically dewaxing the effluent at a temperature of at least about 400 0 F (204 0 C) and at a pressure of from about 15 psig to about 3000 psig (0.103-20.7 Mpa gauge) in the presence of added hydrogen gas with a catalyst comprising SSZ-56 in the hydrogen form and at least one Group VIII metal.
  • Aromatics Formation SSZ-56 can be used to convert light straight run naphthas and similar mixtures to highly aromatic mixtures.
  • normal and slightly branched chained hydrocarbons preferably having a boiling range above about 40°C and less than about 200°C, can be converted to products having a substantial higher octane aromatics content by contacting the hydrocarbon feed with a catalyst comprising SSZ-56.
  • the conversion catalyst preferably contains a Group VIII metal compound to have sufficient activity for commercial use.
  • 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 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 zeolite with a basic metal, e.g., alkali metal, compound. Methods for rendering the catalyst free of acidity are known in the art. See the aforementioned U.S.
  • Catalytic Cracking Hydrocarbon cracking stocks can be catalytically cracked in the absence of hydrogen using SSZ-56, preferably predominantly in the hydrogen form.
  • SSZ-56 When SSZ-56 is used as a catalytic cracking catalyst in the absence of hydrogen, the catalyst may be employed in conjunction with traditional cracking catalysts, e.g., any aluminosilicate heretofore employed as a component in cracking catalysts.
  • the relative weight ratio of the TC to the SSZ-56 is generally between about 1 : 10 and about 500: 1 , desirably between about 1 : 10 and about 200: 1 , preferably between about 1 :2 and about 50: 1 , and most preferably is between about 1:1 and about 20:1.
  • the novel zeolite and/or the traditional cracking component may be further ion exchanged with rare earth ions to modify selectivity.
  • 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.
  • the present process comprises contacting the isomerization catalyst, i.e., a catalyst comprising SSZ-56 in the hydrogen form, with a hydrocarbon feed under isomerization conditions.
  • the feed is preferably a light straight run fraction, boiling within the range of 3O 0 F to 250 0 F (-1 0 C to 121 0 C) and preferably from 60°F to 200 0 F (16 0 C to 93 0 C).
  • the hydrocarbon feed for the process comprises a substantial amount of C 4 to C 7 normal and slightly branched low octane hydrocarbons, more preferably C 5 and Ce hydrocarbons. It is preferable to carry out the isomerization reaction in the presence of hydrogen.
  • 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 iridium, 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-56 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 Ci 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-56.
  • SSZ-56 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-56 zeolite 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 0 F (38 0 C to 315 0 C), preferably 25O 0 F to 450 0 F (121 0 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 reaction temperature may range from about 100 0 F to 600 0 F (38 0 C to 315 0 C), but it is preferably about 250 0 F to 450°F (121 0 C to 232 0 C).
  • the reaction pressure should be sufficient to maintain at least a partial liquid phase, typically in the range of about 50 psig to 1000 psig (0.345 to 6.89 Mpa gauge), preferably 300 psig to 600 psig (2.07 to 4.14 Mpa gauge).
  • the weight hourly space velocity will range from about 0.1 to 10.
  • Aromatics SSZ-56 can be used to convert light gas C 2 -C 6 paraffins to higher molecular weight hydrocarbons including aromatic compounds.
  • the zeolite will contain a catalyst metal or metal oxide wherein said metal is selected from the group consisting of Groups IB, HB, VIII and INA 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-56 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 feed stream typically may be the effluent from a fluid catalytic cracking unit or a methyl-tert-butyl ether unit.
  • a fluid catalytic cracking unit effluent typically contains about 40-60 weight percent normal butenes.
  • a methyl-tert-butyl ether unit effluent typically contains 40-100 weight percent normal butene.
  • the feed stream preferably contains at least about 40 weight percent normal butene, more preferably at least about 65 weight percent normal butene.
  • iso-olefin and methyl branched iso-olefin may be used interchangeably in this specification.
  • the process is carried out under isomerization conditions.
  • the hydrocarbon feed is contacted in a vapor phase with a catalyst comprising the SSZ-56.
  • the process may be carried out generally at a temperature from about 625 0 F to about 950°F (329-51O 0 C), for butenes, preferably from about 700 0 F to about 900 0 F (371 -482 0 C) 1 and about 350 0 F to about 650 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 liquid hourly space velocity during contacting is generally from about 0.1 to about 50 hr '1 , based on the hydrocarbon feed, preferably from about 0.1 to about 20 hr '1 , more preferably from about 0.2 to about 10 hr "1 , most preferably from about 1 to about 5 hr "1 .
  • a hydrogen/hydrocarbon molar ratio is maintained from about 0 to about 30 or higher.
  • the hydrogen can be added directly to the feed stream or directly to the isomerization zone.
  • the reaction is preferably substantially free of water, typically less than about two weight percent based on the feed.
  • the process can be carried out in a packed bed reactor, a fixed bed, fluidized bed reactor, or a moving bed reactor. The bed of the catalyst can move upward or downward.
  • 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-56 may also be useful in a process for isomerizing one or more xylene isomers in a Cs 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 Cs aromatics stream may be recovered by crystallization and centrifugation.
  • the mother liquor from the crystallizer is then reacted under xylene isomerization conditions to restore ortho-, meta- and para-xylenes to a near equilibrium ratio.
  • part of the ethylbenzene in the mother liquor is converted to xylenes or to products which are easily separated by filtration.
  • the isomerate is blended with fresh feed and the combined stream is distilled to remove heavy and light by-products.
  • the resultant C 8 aromatics stream is then sent to the crystallizer to repeat the cycle.
  • isomerization in the vapor phase is conducted in the presence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene (e.g., ethylbenzene).
  • 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-56 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-56.
  • the zeolite 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.
  • zeolite 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 zeolite 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 zeolites 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-56 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-56 and a metal or metal compound capable of converting the lower molecular weight hydrocarbon to a higher molecular weight hydrocarbon.
  • a catalyst comprising SSZ-56 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.
  • the molecular sieve of the present invention may be used in a catalyst for the polymerization of 1 -olefins, e.g., the polymerization of ethylene.
  • a catalyst for the polymerization of 1 -olefins e.g., the polymerization of ethylene.
  • the molecular sieve as hereinbefore described is reacted with a particular type of organometallic compound.
  • Organometallic compounds useful in forming the polymerization catalyst include trivalent and tetravalent organotitanium and organochromium compounds having alkyl moieties and, optionally, halo moieties.
  • alkyl includes both straight and branched chain alkyl, cycloalkyl and alkaryl groups such as benzyl.
  • organochromium and organotitanium compounds are disclosed in U. S. Patent No. 4,376,722, issued March 15, 1983 to Chester et al., U. S. Patent No. 4,377,497, issued March 22, 1983 to Chester et al., U. S. Patent No. 4,446,243, issued May 1 , 1984 to Chester et al., and U. S. Patent No. 4,526,942, issued July 2, 1985 to Chester et al.
  • the disclosure of the aforementioned patents are incorporated herein by reference in their entirety.
  • organometallic compounds used to form the polymerization catalyst include, but are not limited to, compounds corresponding to the general formula:
  • M is a metal selected from titanium and chromium; Y is alkyl; X is halogen (e.g., Cl or Br); n is 1-4; and m is greater than or equal to n and is 3 or 4.
  • organotitanium and organochromium compounds encompassed by such a formula include compounds of the formula CrY 4 , CrY 3 , CrY 3 X, CrY 2 X, CrY 2 X 2 , CrYX 2 , CrYX 3 , TiY 4 , TiY 3 , TiY 3 X, TiY 2 X, TiY 2 X 2 , TiYX 2 , TiYX 3 , wherein X can be Cl or Br and Y can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, is
  • Y include C- I-5 alkyl, especially butyl.
  • the organotitanium and organochromium materials employed in the catalyst can be prepared by techniques well known in the art. See, for example the aforementioned Chester et al. patents.
  • the organotitanium or organochromium compounds can be with the molecular sieve of the present invention, such as by reacting the organometallic compound and the molecular sieve, in order to form the olefin polymerization catalyst. Generally, such a reaction takes place in the same reaction medium used to prepare the organometallic compound under conditions which promote formation of such a reaction product.
  • the molecular sieve can simply be added to the reaction mixture after formation of the organometallic compound has been completed.
  • Molecular sieve is added in an amount sufficient to provide from about 0.1 to 10 parts by weight, preferably from about 0.5 to 5 parts by weight, of organometallic compound in the reaction medium per 100 parts by weight of molecular sieve. Temperature of the reaction medium during reaction of organometallic compound with molecular sieve is also maintained at a level which is low enough to ensure the stability of the organometallic reactant. Thus, temperatures in the range of from about -150° C. to 50° C, preferably from about -80° C. to 0° C. can be usefully employed. Reaction times of from about 0.01 to 10 hours, more preferably from about 0.1 to 1 hour, can be employed in reacting the organotitanium or organochromium compound with the molecular sieve.
  • the catalyst material so formed may be recovered and dried by evaporating the reaction medium solvent under a nitrogen atmosphere.
  • olefin polymerization reactions can be conducted in this same solvent based reaction medium used to form the catalyst.
  • the polymerization catalyst can be used to catalyze polymerization of 1 -olefins.
  • the polymers produced using the catalysts of this invention are normally solid polymers of at least one mono-1 -olefin containing from 2 to 8 carbon atoms per molecule. These polymers are normally solid homopolymers of ethylene or copolymers of ethylene with another mono-1 - olefin containing 3 to 8 carbon atoms per molecule.
  • Exemplary copolymers include those of ethylene/propylene, ethylene/1 -butene, ethylene/1 -hexane, and ethylene/1 -octene and the like.
  • the major portion of such copolymers is derived from ethylene and generally consists of about 80-99, preferably 95-99 mole percent of ethylene. These polymers are well suited for extrusion, blow molding, injection molding and the like.
  • the polymerization reaction can be conducted by contacting monomer or monomers, e.g., ethylene, alone or with one or more other olefins, and in the substantial absence of catalyst poisons such as moisture and air, with a catalytic amount of the supported organometallic catalyst at a temperature and at a pressure sufficient to initiate the polymerization reaction.
  • monomer or monomers e.g., ethylene, alone or with one or more other olefins, and in the substantial absence of catalyst poisons such as moisture and air
  • catalyst poisons such as moisture and air
  • an inert organic solvent may be used as a diluent and to facilitate materials handling if the polymerization reaction is conducted with the reactants in the liquid phase, e.g. in a particle form (slurry) or solution process.
  • the reaction may also be conducted with reactants in the vapor phase, e.g., in a fluidized bed arrangement in the absence of a solvent but, if desired, in the presence of an inert gas such as nitrogen.
  • the polymerization reaction is carried out at temperatures of from about 30° C. or less, up to about 200° C. or more, depending to a great extent on the operating pressure, the pressure of the olefin monomers, and the particular catalyst being used and its concentration.
  • the selected operating temperature is also dependent upon the desired polymer melt index since temperature is definitely a factor in adjusting the molecular weight of the polymer.
  • the temperature used is from about 30° C. to about 100° C.
  • the pressure to be used in the polymerization reactions can be any pressure sufficient to initiate the polymerization of the monomer(s) to high molecular weight polymer.
  • the pressure therefore, can range from subatmospheric pressures, using an inert gas as diluent, to superatmospheric pressures of up to about 30,000 psig or more.
  • the preferred pressure is from atmospheric (0 psig) up to about 1000 psig. As a general rule, a pressure of 20 to 800 psig is most preferred.
  • an inert organic solvent medium to be employed in the solution or slurry process embodiments of this invention is not too critical, but the solvent should be inert to the supported organometallic catalyst and olefin polymer produced, and be stable at the reaction temperature used. It is not necessary, however, that the inert organic solvent medium also serve as a solvent for the polymer to be produced.
  • saturated aliphatic hydrocarbons having from about 3 to 12 carbon atoms per molecule such as hexane, heptane, pentane, isooctane, purified kerosene and the like
  • saturated cycloaliphatic hydrocarbons having from about 5 to 12 carbon atoms per molecule such as cyclohexane, cyclopentane, dimethylcyclopentane and methylcyclohexane and the like
  • aromatic hydrocarbons having from about 6 to 12 carbon atoms per molecule such as benzene, toluene, xylene, and the like.
  • Particularly preferred solvent media are cyclohexane, pentane, hexane and heptane.
  • Hydrogen can be introduced into the polymerization reaction zone in order to decrease the molecular weight of the polymers produced (i.e., give a much higher Melt Index, Ml). Partial pressure of hydrogen when hydrogen is used can be within the range of 5 to 100 psig, preferably 25 to 75 psig.
  • the melt indices of the polymers produced in accordance with the instant invention can range from about 0.1 to about 70 or even higher. More detailed description of suitable polymerization conditions including examples of particle form, solution and fluidized bed polymerization arrangements are found in Karapinka; U.S. Pat. No. 3,709,853; Issued Jan.
  • Hvdrotreating SSZ-56 is useful in a hydrotreating catalyst.
  • oxygen, sulfur and nitrogen present in the hydrocarbonaceous feed is reduced to low levels.
  • Aromatics and olefins, if present in the feed, may also have their double bonds saturated.
  • the hydrotreating catalyst and hydrotreating conditions are selected to minimize cracking reactions, which can reduce the yield of the most desulfided product (typically useful as a fuel).
  • Hydrotreating conditions typically include a reaction temperature between 400-900 0 F (204-482 0 C), preferably 650-850 0 F (343-454 0 C); a pressure between 500 and 5000 psig (3.5-34.6 Mpa), preferably 1000 to 3000 psig (7.0-20.8 MPa); a feed rate (LHSV) of 0.5 hr "1 to 20 hr “1 (v/v); and overall hydrogen consumption 300 to 2000 scf per barrel of liquid hydrocarbon feed (53.4-356 m 3 H 2 /1TI 3 feed).
  • the hydrotreating catalyst will typically be a composite of a Group Vl metal or compound thereof, and a Group VIII metal or compound thereof supported on the molecular sieve of this invention..
  • Such hydrotreating catalyst are presulfided.
  • Catalysts useful for hydrotreating hydrocarbon feeds are disclosed in U. S. Patents No. 4,347,121 , issued August 31 ,1982 to Mayer et al, and 4,810,357, issued March 7, 1989 to Chester et al, both of which are incorporated herein by reference in their entirety.
  • Suitable catalysts include noble metals from Group VIII, such as Fe, Co, Ni, Pt or Pd, and/or Group Vl metals, such as Cr, Mo, Sn or W. Examples of combinations of Group VIII and Group Vl metals include Ni-Mo or Ni-Sn.
  • Other suitable catalysts are described in U. S. Patents No.
  • the amount of hydrogenation component(s) in the catalyst suitably range from about 0.5% to about 10% by weight of Group VIII component(s) and from 5% to about 25% by weight of Group Vl metal component(s), calculated as metal oxide(s) per 100 parts by weight of total catalyst., where the percentages by weight are based on the weight of the catalyst before sulfiding.
  • the hydrogenation component(s) in the catalyst may be in the oxidic and/or sulfidic form.
  • Hvdrogenation SSZ-56 can be used in a catalyst to catalyze hydrogenation of a hydrocarbon feed containing unsaturated hydrocarbons.
  • the unsaturated hydrocarbons can comprise olefins, dienes, polyenes, aromatic compounds and the like.
  • Hydrogenation is accomplished by contacting the hydrocarbon feed containing unsaturated hydrocarbons with hydrogen in the presence of a catalyst comprising SSZ-56.
  • the catalyst can also contain one or more metals of Group VIB and Group VIII, including salts, complexes and solutions thereof.
  • references to these catalytically active metals is intended to encompass such metals or metals in the elemental state or in some form such as an oxide, sulfide, halide, carboxylate and the like.
  • metals include metals, salts or complexes wherein the metal is selected from the group consisting of platinum, palladium, rhodium, iridium or combinations thereof, or the group consisting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, vanadium, rhenium, manganese and combinations thereof.
  • the hydrogenation component of the catalyst i.e., the aforementioned metal
  • Hydrogenation conditions such as temperature, pressure, space velocities, contact time and the like are well known in the art.
  • SSZ-56 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-56 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 cobalt, copper, 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 zeolite 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 zeolite 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 zeolite.
  • the process is conducted in an excess of oxidant, e.g., oxygen.
  • hydrocarbonaceous fuels such as gasoline and fuel oils
  • gaseous waste products resulting from the combustion of hydrocarbonaceous fuels, such as gasoline and fuel oils comprise carbon monoxide, hydrocarbons and nitrogen oxides as products of combustion or incomplete combustion, and pose a serious health problem with respect to pollution of the atmosphere.
  • exhaust gases from other carbonaceous fuel-burning sources such as stationary engines, industrial furnaces, etc.
  • the exhaust gases from automotive engines are a principal source of pollution.
  • the Environmental Protection Agency EPA has promulgated strict controls on the amounts of carbon monoxide, hydrocarbons and nitrogen oxides which automobiles can emit. The implementation of these controls has resulted in the use of catalytic converters to reduce the amount of pollutants emitted from automobiles.
  • the instant invention can also be used to treat exhaust streams from alcohol fueled engines.
  • the adsorbent bed is typically placed immediately before the catalyst.
  • the exhaust stream is first flowed through the adsorbent bed and then through the catalyst.
  • the adsorbent bed preferentially adsorbs hydrocarbons over water under the conditions present in the exhaust stream.
  • the adsorbent bed has reached a temperature (typically about 150° C.) at which the bed is no longer able to remove hydrocarbons from the exhaust stream. That is, hydrocarbons are actually desorbed from the adsorbent bed instead of being adsorbed.
  • Examples of the molecular sieve include faujasites, clinoptilolites, mordenites, chabazite, silicalite, zeolite Y, ultrastable zeolite Y, and ZSM-5.
  • Canadian Patent No. 1,205,980 discloses a method of reducing exhaust emissions from an alcohol fueled automotive vehicle. This method consists of directing the cool engine startup exhaust gas through a bed of zeolite particles and then over an oxidation catalyst and then the gas is discharged to the atmosphere. As the exhaust gas stream warms up it is continuously passed over the adsorption bed and then over the oxidation bed.
  • this invention generally relates to a process for treating an engine exhaust stream and in particular to a process for minimizing emissions during the cold start operation of an engine.
  • the engine consists of any internal or external combustion engine which generates an exhaust gas stream containing noxious components or pollutants including unburned or thermally degraded hydrocarbons or similar organics. Other noxious components usually present in the exhaust gas include nitrogen oxides and carbon monoxide.
  • the engine may be fueled by a hydrocarbonaceous fuel.
  • hydrocarbonaceous fuel includes hydrocarbons, alcohols and mixtures thereof. Examples of hydrocarbons which can be used to fuel the engine are the mixtures of hydrocarbons which make up gasoline or diesel fuel.
  • the alcohols which may be used to fuel engines include ethanol and methanol. Mixtures of alcohols and mixtures of alcohols and hydrocarbons can also be used.
  • the engine may be a jet engine, gas turbine, internal combustion engine, such as an automobile, truck or bus engine, a diesel engine or the like.
  • the process of this invention is particularly suited for hydrocarbon, alcohol, or hydrocarbon-alcohol mixture, internal combustion engine mounted in an automobile.
  • hydrocarbon for convenience the description will use hydrocarbon as the fuel to exemplify the invention.
  • the use of hydrocarbon in the subsequent description is not to be construed as limiting the invention to hydrocarbon fueled engines.
  • Pollutants will be used herein to collectively refer to any unbumed fuel components and combustion byproducts found in the exhaust stream.
  • the fuel is a hydrocarbon fuel
  • hydrocarbons, nitrogen oxides, carbon monoxide and other combustion byproducts will be found in the engine exhaust gas stream.
  • the temperature of this engine exhaust stream is relatively cool, generally below 500° C. and typically in the range of 200° to 400° C.
  • This engine exhaust stream has the above characteristics during the initial period of engine operation, typically for the first 30 to 120 seconds after startup of a cold engine.
  • the engine exhaust stream will typically contain, by volume, about 500 to 1000 ppm hydrocarbons.
  • the engine exhaust gas stream which is to be treated is flowed over a molecular sieve bed comprising molecular sieve SSZ-56 a first exhaust stream.
  • molecular sieve SSZ-56 is described below.
  • the first exhaust stream which is discharged from the molecular sieve bed is now flowed over a catalyst to convert the pollutants contained in the first exhaust stream to innocuous components and provide a treated exhaust stream which is discharged into the atmosphere. It is understood that prior to discharge into the atmosphere, the treated exhaust stream may be flowed through a muffler or other sound reduction apparatus well known in the art.
  • the catalyst which is used to convert the pollutants to innocuous components is usually referred to in the art as a three-component control catalyst because it can simultaneously oxidize any residual hydrocarbons present in the first exhaust stream to carbon dioxide and water, oxidize any residual carbon monoxide to carbon dioxide and reduce any residual nitric oxide to nitrogen and oxygen.
  • the catalyst may not be required to convert nitric oxide to nitrogen and oxygen, e.g., when an alcohol is used as the fuel.
  • the catalyst is called an oxidation catalyst. Because of the relatively low temperature of the engine exhaust stream and the first exhaust stream, this catalyst does not function at a very high efficiency, thereby necessitating the molecular sieve bed.
  • the adsorbent bed used in the instant invention can be conveniently employed in particulate form or the adsorbent can be deposited onto a solid monolithic carrier. When particulate form is desired, the adsorbent can be formed into shapes such as pills, pellets, granules, rings, spheres, etc.
  • the adsorbent In the employment of a monolithic form, it is usually most convenient to employ the adsorbent as a thin film or coating deposited on an inert carrier material which provides the structural support for the adsorbent.
  • the inert carrier material can be any refractory material such as ceramic or metallic materials. It is desirable that the carrier material be unreactive with the adsorbent and not be degraded by the gas to which it is exposed. Examples of suitable ceramic materials include sillimanite, petalite, cordierite, mullite, zircon, zircon mullite, spondumene, alumina-titanate, etc. Additionally, metallic materials which are within the scope of this invention include metals and alloys as disclosed in U.S. Pat. No.
  • the carrier material can best be utilized in any rigid unitary configuration which provides a plurality of pores or channels extending in the direction of gas flow. It is preferred that the configuration be a honeycomb configuration.
  • the honeycomb structure can be used advantageously in either unitary form, or as an arrangement of multiple modules.
  • the honeycomb structure is usually oriented such that gas flow is generally in the same direction as the cells or channels of the honeycomb structure.
  • monolithic structures refer to U.S. Pat. Nos. 3,785,998 and 3,767,453.
  • the molecular sieve is deposited onto the carrier by any convenient . way well known in the art.
  • a preferred method involves preparing a slurry using the molecular sieve and coating the monolithic honeycomb carrier with the slurry.
  • the slurry can be prepared by means known in the art such as combining the appropriate amount of the molecular sieve and a binder with water. This mixture is then blended by using means such as sonification, milling, etc. This slurry is used to coat a monolithic honeycomb by dipping the honeycomb into the slurry, removing the excess slurry by draining or blowing out the channels, and heating to about 100° C. If the desired loading of molecular sieve is not achieved, the above process may be repeated as many times as required to achieve the desired loading.
  • the adsorbent may optionally contain one or more catalytic metals dispersed thereon.
  • the metals which can be dispersed on the adsorbent are the noble metals which consist of platinum, palladium, rhodium, ruthenium, and mixtures thereof.
  • the desired noble metal may be deposited onto the adsorbent, which acts as a support, in any suitable manner well known in the art.
  • One example of a method of dispersing the noble metal onto the adsorbent support involves impregnating the adsorbent support with an aqueous solution of a decomposable compound of the desired noble metal or metals, drying the adsorbent which has the noble metal compound dispersed on it and then calcining in air at a temperature of about 400° to about 500° C. for a time of about 1 to about 4 hours.
  • decomposable compound is meant a compound which upon heating in air gives the metal or metal oxide. Examples of the decomposable compounds which can be used are set forth in U.S. Pat. No. 4,791 ,091 which is incorporated by reference.
  • Preferred decomposable compounds are chloroplatinic acid, rhodium trichloride, chloropalladic acid, hexachloroiridate (IV) acid and hexachlororuthenate. It is preferable that the noble metal be present in an amount ranging from about 0.01 to about 4 weight percent of the adsorbent support. Specifically, in the case of platinum and palladium the range is 0.1 to 4 weight percent, while in the case of rhodium and ruthenium the range is from about 0.01 to 2 weight percent. These catalytic metals are capable of oxidizing the hydrocarbon and carbon monoxide and reducing the nitric oxide components to innocuous products.
  • the adsorbent bed can act both as an adsorbent and as a catalyst.
  • the catalyst which is used in this invention is selected from any three component control or oxidation catalyst well known in the art. Examples of catalysts are those described in U.S. Pat. Nos. 4,528,279; 4,791 ,091 ; 4,760,044; 4,868,148; and 4,868,149, which are all incorporated by reference.
  • Preferred catalysts well known in the art are those that contain platinum and rhodium and optionally palladium, while oxidation catalysts usually do not contain rhodium. Oxidation catalysts usually contain platinum and/or palladium metal.
  • These catalysts may also contain promoters and stabilizers such as barium, cerium, lanthanum, nickel, and iron.
  • the noble metals promoters and stabilizers are usually deposited on a support such as alumina, silica, titania, zirconia, alumino silicates, and mixtures thereof with alumina being preferred.
  • the catalyst can be conveniently employed in particulate form or the catalytic composite can be deposited on a solid monolithic carrier with a monolithic carrier being preferred.
  • the particulate form and monolithic form of the catalyst are prepared as described for the adsorbent above. EXAMPLES The following examples demonstrate but do not limit the present invention.
  • the parent amine 2-Methyldecahydroquinoline was obtained by hydrogenation of 2-methylquinoline (quinaldine) as described below.
  • a 1000- ml stainless steel hydrogenation vessel was charged with 200 gm (1.4 mol) of 2-methylquinoline (quinaldine), purchased from Aldrich Chemical Company, and 300 ml glacial acetic acid, 10 gm of PtO 2 and 15 ml concentrated H 2 SO 4 .
  • the mixture was purged twice with nitrogen (the vessel was pressurized with nitrogen to 1000 psi and evacuated). Then, the reaction vessel was pressurized to 1500-psi of hydrogen gas and allowed to stir at 5O 0 C overnight.
  • N-Ethyl-2-methyldecahydroquinolinium hydroiodide was prepared according to the method described below. To a solution 100 gm (0.65 mol) of 2-methyldecahydroquinoline (trans and cis) in 350 ml acetonitrile, 111 gm (0.72 mole) of ethyl iodide was added. The mixture was stirred (using an overhead stirrer) at room temperature for 96 hours. Then, an additional 1/2 mole equivalent of ethyl iodide was added and the mixture was heated at reflux for 6 hours.
  • reaction mixture was concentrated on a rotary evaporator at reduced pressure and the obtained solids were rinsed with 500 ml ethyl ether to remove any unreactive amines and excess iodide.
  • the reaction afforded a mixture of two N-ethyl-2-methyl-decahydroquinolinium hydroiodide salts (mono-ethyl derivatives) and a small mixture of the quaternized derivatives.
  • N,N-Diethy!-2-methyldecahydroquinolinium iodide was prepared according to the procedure shown below. The procedure below is typical for making the N,N-diethyl-2-methyl-decahydro-quinolinium iodide.
  • the obtained transfused ring N-ethyl-2-methyl-decahydroquinolinium hydroiodide (28 gm, 0.09 mol) was added to an acetonitrile (150 ml) and KHCO 3 (14 gm, 0.14 mol) solution.
  • acetonitrile 150 ml
  • KHCO 3 14 gm, 0.14 mol
  • 30 gm (0.19 mol) of ethyl iodide was added and the resulting mixture was stirred (with an overhead stirrer) at room temperature for 72 hours.
  • one more mole equivalent of ethyl iodide was added and the reaction was heated to reflux and allowed to stir at the reflux temperature for 6 hours. Heating was stopped and the reaction was allowed to further stir at room temperature overnight.
  • the reaction was worked up by removing the excess ethyl iodide and the solvent at reduced pressure on a rotary evaporator.
  • the resulting solids were suspended in 500 ml chloroform, which dissolves the desired product and leaves behind the unwanted KHCO 3 and its salt by-products.
  • the solution was filtered, and the filtrate was dried over anhydrous MgSO 4 . Filtration followed by concentration at reduced pressure on a rotary evaporator, gave the desired N,N-diethyl-2-methyl- decahydroquinolinium iodide as a pale tan-colored solid.
  • the solid was further purified by recrystallization in isopropyl alcohol. The reaction afforded 26.8 gm (87% yield).
  • the N,N-diethyl-2-methyl-decahydro-quinolinium iodide of the cis-fused ring isomer was made according to the procedure described above.
  • the trans-fused ring derivative A (see the scheme 1 below) is the templating agent (SDA) useful for making SSZ-56.
  • SDA templating agent
  • N,N-Diethyl-2-methyldecahydroquinolinium hydroxide The hydroxide version of N,N-diethyl-2-methyldecahydro-quinolinium cation was prepared by ion exchange as described in the procedure below.
  • the reaction progress was checked by monitoring the gel's pH and by looking for crystal formation using Scanning Electron Microscopy (SEM) at 3-6 days intervals.
  • SEM Scanning Electron Microscopy
  • the reaction was usually completed after heating for 18-24 days (shorter crystallization periods were achieved at 160 0 C).
  • the final pH at the end of the reaction ranged from 10.8- 11.6.
  • the reaction mixture usually a white fine powdery precipitate with clear liquid
  • the collected solids were rinsed a few times with de-ionized water ( ⁇ 1000 ml), and then let to air-dry overnight followed by drying in an oven at 120 0 C for 15- 20 minutes.
  • the reaction yielded about 0.55 -0.6 gm of pure boron-SSZ-56 as determined by XRD analysis.
  • Borosilicate SSZ-56 In a 23 cc Teflon liner, 3 gm of 0.5M solution (1.5 mmol) of N,N-diethyl- 2-methyldecahydroquinolinium hydroxide (the trans-fused ring isomer), 0.5 gm of 1.0N solution of aqueous NaOH (0.5 mmol), 4.5 gm of de-ionized water, 0.65 gm of calcined boron-BETA zeolite and 0.03 gm of SSZ-56 (made as described above) were mixed.
  • the Teflon liner was capped and placed in a Parr reactor and heated in an oven at 150 0 C while tumbling at about 43 rpm.
  • the reaction progress was checked by monitoring the gel's pH and by looking for crystal formation using Scanning Electron Microscopy (SEM) at 3 day intervals. The crystallization was complete (SEM analysis) after heating for 6 days.
  • the final pH at the end of the reaction was usually 11.2.
  • the reaction mixture was filtered, and the collected solids were rinsed with de-ionized water ( ⁇ 1000 ml), and then let to air-dry overnight followed by drying in an oven at 120 0 C for 15-20 minutes.
  • Borosilicate SSZ-56 from Sodium Borate Decahvdrate as the Boron Sources and CAB-O-SIL M-5 as the Silicon Source
  • the resulting gel was capped and placed in a Parr reactor and heated in an oven at 160 0 C while tumbling at about 43 rpm.
  • the reaction progress was checked by monitoring the gel's pH and by looking for crystal formation using Scanning Electron Microscopy (SEM) at 6 days intervals.
  • SEM Scanning Electron Microscopy
  • the reaction was usually completed after heating for 18-24 days.
  • the final pH at the end of the reaction ranged from 11.5-12.3.
  • the reaction mixture a white fine powdery precipitate with clear liquid, was filtered.
  • the collected solids were rinsed few times with de-ionized water ( ⁇ 1000 ml), and then air-dried overnight followed by drying in an oven at 120 0 C for 15 minutes.
  • the reaction usually yields about 0.75-0.9 gm of pure boron-SSZ-56.
  • Borosilicate SSZ-56 from Sodium Borate Decahvdrate as the Boron Source and CAB-O-SIL M-5 as the Silicon Source
  • the resulting gel was capped and placed in a Parr reactor and heated in an oven at 16O 0 C while tumbling at about 43 rpm.
  • the reaction progress was checked by monitoring the gel's pH and by looking for crystal formation using Scanning Electron Microscopy (SEM) at 3-5 days intervals. The reaction was completed after heating for 7 days. The final pH at the end of the reaction was about 12.2.
  • SEM Scanning Electron Microscopy
  • Calcination of SSZ-56 Removing the templating agent molecules (structure-directing agents: SDAs) from zeolite SSZ-56 to free its channels and cavities was accomplished by the calcination method described below.
  • a sample of the as-made SSZ-56 synthesized according to the procedures of Examples 2, 3, 4 or 5 discussed above is calcined by preparing a thin bed of SSZ-56 in a calcination dish which was heated in a muffle furnace from room temperature to 595 0 C in three stages. The sample was heated to120°C at a rate of 1°C/minute and held for 2 hours. Then, the temperature was ramped up to 54O 0 C at a rate of 1 °C/minute and held for 5 hours.
  • the temperature was then ramped up again at 1°C/minute to 595 0 C and held there for 5 hours.
  • a nitrogen stream with a slight bleed of air was passed over the zeolite at a rate of 20 standard cubic feet (0.57 standard cubic meters) per minute during heating the calcination process.
  • the Na + form of SSZ-56 prepared as in Examples 2, 3, 4 or 5 and calcined as in Example 6 was converted to NH/-SSZ-56 form by heating the material in an aqueous solution of NH 4 NO 3 (typically 1gm NH 4 NO 3 /1 gm SSZ- 56 in 20 ml H 2 O) at 9O 0 C for 2-3 hours. The mixture was then filtered and the step was repeated as many times as desired (usually done 2-3 times). After filtration, the obtained NH 4 -exchanged-product was washed with de-ionized water and air dried.
  • the NH 4 + form of SSZ-56 can be converted to the H + form by calcination to 54O 0 C (as described in Example 6 above stopping at the end of the second stage).
  • the aluminosilicate version of SSZ-56 was prepared by way of exchanging borosilicate SSZ-56 with aluminum nitrate according to the procedure described below.
  • the H + version of calcined borosilicate SSZ-56 (prepared as in Examples 2, 3, 4 or 5 and treated with ammonium nitrate and calcined as Example 6) was easily converted to the aluminosilicate SSZ-56 by suspending the zeolite (H + /borosilicate SSZ-56) in 1 M solution of aluminum nitrate nonahydrate (10 ml of 1 M AI(NO 3 ) 3 .9H 2 O soln./1 gm SSZ-56). The suspension was heated at reflux overnight.
  • the resulting mixture was then filtered and the collected solids were thoroughly rinsed with de-ionized water and air-dried overnight. The solids were further dried in an oven at 12O 0 C for 2 hours.
  • the exchange can also be done on the Na + version of SSZ-56 (as prepared in Examples 2, 3, 4 or 5 and calcined as in Example 6).
  • a calcined sample of Na + version of borosilicate SSZ-56 (synthesized as in Example 2 and calcined as in Example 6) had a micropore volume of 0.16 cc/gm based on argon adsorption isotherm at 87.5° K (-186 0 C) recorded on ASAP 2010 equipment from Micromerities.
  • the sample was first degassed at 400 0 C for 16 hours prior to argon adsorption.
  • the low-pressure dose was 2.00 cm3/g (STP).
  • a maximum of one hour equilibration time per dose was used and the total run time was 37 hours.
  • the argon adsorption isotherm was analyzed using the density function theory (DFT) formalism and parameters developed for activated carbon slits by Olivier (Porous Mater. 1995, 2, 9) using the Saito Foley adaptation of the Horvarth-Kawazoe formalism (Microporous Materials, 1995, 3, 531) and the conventional t-plot method (J. Catalysis, 1965, 4, 319).
  • DFT density function theory
  • the hydrogen form of SSZ-56 synthesized as in Example 2 was calcined and ammonium exchanged as in Examples 6 and 7 was aluminum exchanged as in Example 8.
  • the obtained aluminum-exchanged sample of SSZ-56 was then ammonium exchanged as in Example 7 followed by calcination to 540 0 C as in Example 6.
  • the H-AI-SSZ-56 was pelletized at 4 KPSI, crushed and granulated to 20-40 mesh.
  • a 0.6 gram sample of the granulated material was calcined in air at 54O 0 C for 4 hours and cooled in a desiccator to ensure dryness. Then, 0.5 gram was packed into a 3/8 inch stainless steel tube with alundum on both sides of the molecular sieve bed.
  • a Lindburg furnace was used to heat the reactor tube. Helium was introduced into the reactor tube at 10 cc/min. and at atmospheric pressure. The reactor was 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 was delivered by a Brownlee pump. Direct sampling into a GC began after 10 minutes of feed introduction. The Constraint Index (Cl) value was calculated from the GC data using methods known in the art. SSZ-56 had a Cl of 0.76 and a conversion of 79% after 15 minutes on stream. The material fouled rapidly and at 105 minutes the Cl was 0.35 and the conversion was 25.2%. The Cl test showed the material was very active catalytic material.
  • a 1 gm sample of SSZ-56 (prepared as described for the Constraint Index test in Example 11) was 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 was added. The pH of the solution was adjusted to pH of 9.2 by a drop-wise addition of 0.15N solution of ammonium hydroxide. The mixture was then heated in an oven at 75 0 C for 48 hours. The mixture was then filtered through a glass frit, washed with de-ionized water, and air-dried. The collected Pd-SSZ-56 sample was slowly calcined up to 482°C in air and held there for three hours.
  • the calcined Pd/SSZ-56 catalyst was pelletized in a Carver Press and granulated to yield particles with a 20/40 mesh size. Sized catalyst (0.5 g) was packed into a % inch OD tubing reactor in a micro unit for n-hexadecane hyd reconversion.
  • the table below gives the run conditions and the products data for the hydrocracking test on n-hexadecane.
  • SSZ-56 is a very active and isomerisation selective catalyst at 96.5% n-C-

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Publication number Priority date Publication date Assignee Title
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
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
US7880041B2 (en) 2004-04-16 2011-02-01 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US7883568B2 (en) 2006-02-03 2011-02-08 Grt, Inc. Separation of light gases from halogens
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
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
US8367884B2 (en) 2010-03-02 2013-02-05 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8436220B2 (en) 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
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
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
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
EP2958855A4 (en) * 2013-02-22 2016-09-07 Chevron Usa Inc NEW ZEOLITIC MATERIALS WITH HETERO-TEROME SUBSTITUTIONS ON THE EXTERNAL SURFACE OF THE RETICULAR SKELETON
WO2017151246A1 (en) * 2016-03-04 2017-09-08 Chevron U.S.A. Inc. Molecular sieve ssz-106, its synthesis and use
WO2020263724A1 (en) * 2019-06-28 2020-12-30 Uop Llc Process for transalkylating benzene
CN114516641A (zh) * 2020-11-18 2022-05-20 中国科学院大连化学物理研究所 一种丝光沸石分子筛及其制备方法、应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8697018B2 (en) * 2011-08-05 2014-04-15 Chevron U.S.A. Inc. Reduction of oxides of nitrogen in a gas stream using molecular sieve SSZ-25
US8647602B2 (en) * 2012-06-08 2014-02-11 Chevron U.S.A. Inc. Method for making aluminosilicate zeolite SSZ-56
CN112041268B (zh) * 2018-08-27 2023-04-04 雪佛龙美国公司 分子筛ssz-56的合成

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6049018A (en) * 1999-01-21 2000-04-11 Mobil Corporation Synthetic porous crystalline MCM-68, its synthesis and use
US6080382A (en) * 1996-12-31 2000-06-27 Chevron U. S. A. Inc. Zeolite SSZ-48
US6569401B1 (en) * 2002-08-01 2003-05-27 Chevron U.S.A. Inc. Zeolite SSZ-64 composition of matter and synthesis thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1099512B (de) * 1957-12-05 1961-02-16 Union Carbide Corp Verfahren zur Herstellung eines kristallinen Zeoliths (Zeolith H)
US5965104A (en) * 1996-12-31 1999-10-12 Chevron U.S.A. Inc. Zeolite SSZ-43
KR100893537B1 (ko) 2001-07-13 2009-04-17 셰브런 유.에스.에이.인크. 제올라이트 에스에스제트-57
JP4977318B2 (ja) * 2002-08-01 2012-07-18 シェブロン ユー．エス．エー． インコーポレイテッド 分子篩ｓｓｚ−６４
US6827843B2 (en) * 2002-12-26 2004-12-07 Chevron U.S.A., Inc. Hydrocarbon conversion using molecular sieve SSZ-63
AU2003300993A1 (en) * 2002-12-26 2004-07-29 Chevron U.S.A. Inc. Molecular sieve ssz-63
WO2004094347A2 (en) * 2003-03-26 2004-11-04 Chevron U.S.A. Inc. Molecular sieve ssz-65
US6929789B2 (en) * 2003-08-28 2005-08-16 Chevron U.S.A. Inc. Zeolite SSZ-61 composition of matter and synthesis thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6080382A (en) * 1996-12-31 2000-06-27 Chevron U. S. A. Inc. Zeolite SSZ-48
US6049018A (en) * 1999-01-21 2000-04-11 Mobil Corporation Synthetic porous crystalline MCM-68, its synthesis and use
US6569401B1 (en) * 2002-08-01 2003-05-27 Chevron U.S.A. Inc. Zeolite SSZ-64 composition of matter and synthesis thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1909947A2 *

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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
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
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
US8415517B2 (en) 2008-07-18 2013-04-09 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8273929B2 (en) 2008-07-18 2012-09-25 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
US8198495B2 (en) 2010-03-02 2012-06-12 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
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
EP2958855A4 (en) * 2013-02-22 2016-09-07 Chevron Usa Inc NEW ZEOLITIC MATERIALS WITH HETERO-TEROME SUBSTITUTIONS ON THE EXTERNAL SURFACE OF THE RETICULAR SKELETON
WO2017151246A1 (en) * 2016-03-04 2017-09-08 Chevron U.S.A. Inc. Molecular sieve ssz-106, its synthesis and use
US9890049B2 (en) 2016-03-04 2018-02-13 Chevron U.S.A. Inc. Molecular sieve SSZ-106, its synthesis and use
WO2020263724A1 (en) * 2019-06-28 2020-12-30 Uop Llc Process for transalkylating benzene
CN114516641A (zh) * 2020-11-18 2022-05-20 中国科学院大连化学物理研究所 一种丝光沸石分子筛及其制备方法、应用
CN114516641B (zh) * 2020-11-18 2023-06-06 中国科学院大连化学物理研究所 一种丝光沸石分子筛及其制备方法、应用

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