EP1804966A1 - Catalyseur d'isomerisation et procedes associes - Google Patents

Catalyseur d'isomerisation et procedes associes

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Publication number
EP1804966A1
EP1804966A1 EP04796469A EP04796469A EP1804966A1 EP 1804966 A1 EP1804966 A1 EP 1804966A1 EP 04796469 A EP04796469 A EP 04796469A EP 04796469 A EP04796469 A EP 04796469A EP 1804966 A1 EP1804966 A1 EP 1804966A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
component
mass
isomerization
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04796469A
Other languages
German (de)
English (en)
Other versions
EP1804966A4 (fr
Inventor
Ralph D. UOP LLC GILLESPIE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Original Assignee
UOP LLC
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Filing date
Publication date
Application filed by UOP LLC filed Critical UOP LLC
Publication of EP1804966A1 publication Critical patent/EP1804966A1/fr
Publication of EP1804966A4 publication Critical patent/EP1804966A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/14—Inorganic carriers the catalyst containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/06—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing platinum group metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides

Definitions

  • This invention relates to an improved catalytic composite and process for the conversion of hydrocarbons, and more specifically for the selective upgrading of aparaffmic feedstock by isomerization.
  • Refiners are also faced with supplying reformulated gasoline to meet tightened automotive emission standards.
  • Reformulated gasoline differs from the traditional product in having a lower vapor pressure, lower final boiling point, increased content of oxygenates, and lower content of olefins, benzene and aromatics.
  • Benzene content generally is being restricted to 1% or lower, and is limited to 0.8% in U.S. reformulated gasoline.
  • Gasoline aromatics content is likely to be lowered, particularly as distillation end points (usually characterized as the 90% distillation temperature) are lowered, since the high-boiling portion of the gasoline which thereby would be eliminated usually is an aromatics concentrate. Since aromatics ha.
  • US 6,184,430 Bl teaches a method of cracking a feedstock by contacting the feedstock with a metal-promoted anion modified metal oxide catalyst where the metal oxide is one or more of ZrO 2 , HfO 2 , TiO 2 and SnO 2 , the modifier is one or more of SO 4 and WO 3 , and the metal is one or more of Pt, Ni, Pd 5 Rh, Ir, Ru, Mn, and Fe.
  • a catalyst having an oxide of a Group IVB (IUPAC 4) metal modified with an anion or oxyanion of a Group VIB (IUPAC 6) metal and a Group IB (IUPAC 11) metal or metal oxide is disclosed in US 5,902,767.
  • a catalyst having a Group Vm (IUPAC 8, 9, and 10) metal and a zirconia support impregnated with silica and tungsten oxide and a process of isomerization using the catalyst is disclosed.
  • a process for forming a diesel fuel blending component uses an acidic solid catalyst having a Group IVB (IUPAC 4) metal oxide modified with an oxyanion of Group VEB (IUPAC 6) metal and iron or manganese in US 5,780,703 Bl.
  • IUPAC 4 Group IVB
  • VEB oxyanion of Group VEB
  • US 5,310,868 and US 5,214,017 teach catalyst compositions containing sulfated and calcined mixtures of (1) a support containing an oxide or hydroxide of IUPAC 4 (Ti, Zr, Hf), (2) an oxide or hydroxide of IUPAC 6 (Cr, Mo, W); IUPAC 7 (Mn, Tc, Re), or IUPAC 8, 9, and 10 (Group Vm) metal, (3) an oxide or hydroxide of IUPAC 11 (Cu, Ag, Au), IUPAC 12 (Zn, Cd, Hg), IUPAC 3 (Sc, Y) , IUPAC 13 (B, Al, Ga, In, Tl), IUPAC 14 (Ge, Sn, Pb), IUPAC 5 (V, Nb, Ta), or IUPAC 6 (Cr, Mo, W), and (4) a metal of the lanthanide series.
  • IUPAC 4 Ti, Zr, Hf
  • IUPAC 6 Cr, Mo, W
  • IUPAC 7 M
  • the present invention is an improved catalyst and process for hydrocarbon conversion reactions.
  • the invention also provides improved technology to upgrade naphtha to gasoline and more specifically an improved catalyst and process for the isomerization of full boiling point range naphtha to obtain a high-octane gasoline component.
  • This invention is based on the discovery that a catalyst containing lanthanide series and platinum-group components provides superior performance and stability in the isomerization of full boiling point range naphtha to increase its isoparaffin content.
  • the invention is a catalyst comprising a tungstated support of an oxide or hydroxide of a Group IVB (IUPAC 4) metal, preferably zirconium oxide or hydroxide, at least a first component which is a lanthanide series element and/or yttrium component, and at least a second component being a platinum-group metal component.
  • the first component preferably consists of a single lanthanide-series element or yttrium and the second component preferably consists of a single platinum-group metal.
  • the first component is ytterbium, holmium, yttrium, cerium, europium, or mixtures thereof, and the second component is platinum.
  • the catalyst optionally contains an inorganic-oxide binder, especially alumina.
  • an inorganic-oxide binder especially alumina.
  • One method of preparing the catalyst of the invention is by tungstating or tungstating and the Group IVB (IUPAC 4) metal oxide or hydroxide, incorporating a first component which is at least one lanthanide element, yttrium, or any mixture thereof, and the second component which is a platinum-group metal, and preferably binding the catalyst with a refractory inorganic oxide.
  • IUPAC 4 Group IVB
  • the catalyst of the invention may be used for converting hydrocarbons such as in the isomerization of isomerizable hydrocarbons.
  • Trie hydrocarbons preferably comprise a full boiling point range naphtha which is isomerized to increase its isoparaffin content and octane number as a gasoline blending stock.
  • FIG. 1 is a plot of the conversion of n-heptane achieved by selected catalysts made in
  • FIG. 2 is a plot of the selectivities of the catalysts of FIG. 1 for n-heptane isomerization.
  • FIG. 3 is a plot of the selectivities of the catalysts of FIG. 1 for the isomerization of n- heptane to 2,2-dimethylpentane and 2,4-diniethLylpentane.
  • FIG. 4 is a plot of the yields of the catalysts of FIG. 1 for the isomerization of n- heptane to 2,2-dimethylpentane and 2,4-dimeth.ylpentane.
  • FIG. 5 is a plot of the conversion of n-heptane achieved by selected catalysts made in
  • Example 1 where ytterbium is a modifier.
  • FIG. 6 is a plot of the selectivities of the catalysts of FIG. 5 for n-heptane isomerization.
  • FIG. 7 is a plot of the selectivities of the catalysts of FIG. 5 for the isomerization of n- heptane to 2,2-dimethylpentane and 2,4-dimeth.ylpentane.
  • FIG. 8 is a plot of the yields of the catalysts of FIG. 5 for the isomerization of n- heptane to 2,2-dimethylpentane and 2,4-dimethylpentane.
  • the support material of the catalyst of the present invention comprises an oxide or hydroxide of a Group IVB (IUPAC 4) metal, see Cotton and Wilkinson, Advanced Inorganic Chemistry, John Wiley & Sons (Fifth Edition, 1988) and including zirconium, titanium and hafnium.
  • the metal is selected from zirconium and titanium, with zirconium being especially preferred.
  • the preferred zirconium oxide or hydroxide is converted via calcination to crystalline form. Tungstate is composited on the support material to form, it is believed without so limiting the invention, a mixture of Br ⁇ nsted and Lewis acid sites.
  • a component of at least one lanthanide-series element, yttrium, or mixtures thereof, is incorporated into the composite by any suitable means.
  • a platinum-group metal component is added to the catalytic composite by any means known in the art to effect the catalyst of the invention, e.g., by impregnation.
  • the catalyst is bound with a refractory inorganic oxide.
  • the support, tungstate, metal components, and optional binder may be composited in any order effective to prepare a catalyst useful for the conversion of hydrocarbons, and particularly the isomerization of hydrocarbons.
  • Production of the support of the present catalyst may be based on a hydroxide of a Group rVB (IUPAC 4) metal as raw material.
  • zirconium hydroxide is available from MEI of Flemington, New Jersey.
  • the hydroxide may be prepared by hydrolyzing metal oxy-anion compounds, for example ZrOCl 2 , ZrO(NO 3 ) 2 , ZrO(OH)NO 3 , ZrOSO 4 , TiOCl 2 and the like.
  • metal oxy-anion compounds for example ZrOCl 2 , ZrO(NO 3 ) 2 , ZrO(OH)NO 3 , ZrOSO 4 , TiOCl 2 and the like.
  • commercial ZrO(OH) 2 contains a significant amount of Hf, 1 weight percent.
  • Zirconium alkoxides such as zirconyl acetate and zirconium propoxide may be used as well.
  • the hydrolysis can be effected using a hydrolyzing agent such as ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium sulfate, (NH 4 ) 2 HPO 4 and other such compounds known in the art.
  • the metal oxy-anion component may in turn be prepared from available materials, for example, by treating ZrOCO 3 with nitric acid.
  • the hydroxide as purchased or generated by hydrolysis preferably is dried at a temperature of from. 100 0 C to 300 0 C to vaporize volatile compounds.
  • a tungstated support is prepared by treatment with a suitable tungstating agent to form a solid strong acid.
  • Liquid acids whose strength is greater than sulfuric acid have been termed "superacids".
  • a number of liquid superacids are known in the literature including substituted protic acids, e.g., trifluoromethyl substituted H 2 SO 4 , triflic acid and protic acids activated by Lewis acids (HF plus BF 3 ). While determination of the acid strength of liquid superacids is relatively straightforward, the exact acid strength of a solid strong acid is difficult to directly measure with any precision because of the less defined nature of the surface state of solids relative to the fully solvated molecules found in liquids.
  • solid strong acids are those that have an acid strength greater than sulfonic acid resins such as Amberlyst ® -15. Additionally, since there is disagreement in the literature whether some of these solid, acids are "superacids" only the term solid strong acid as defined above will be used herein.
  • Another way to define a solid strong acid is a solid comprising of interacting protic and Lewis acid sites.
  • solid strong acids can be a combination of a Bronsted (protonic) acid and a Lewis acid component. In other cases, the Bronsted and Lewis acid components are not readily identified or present as distinct species, yet they meet the above criteria.
  • Tungstate ions are incorporated into a catalytic composite, for example, by treatment with ammonium metatungstate in a concentration usually of 0.1 to 20 mass percent tungsten and preferably from 1 to 15 mass percent tungsten.
  • Compounds such as metatungstic acid, sodium tungstate, ammonium tungstate, ammonium paratungstate, which are capable of forming tungstate ions upon calcining, may be employed as alternative sources.
  • ammonium metatungstate is employed to provide tungstate ions and form a solid strong acid catalyst.
  • the tungstate content of the finished catalyst generally is in the range of 0.5 to 25 mass-%, and preferably is from 1 to 25 mass-% on an elemental basis.
  • a first component comprising one or more of the lanthanide-series elements, yttrium, and mixtures thereof, is another essential component of the present catalyst. Included in the lanthanide series are lanthanum, cerium, praseodymium, neodymium, promethiurn, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
  • Preferred lanthanide series elements include ytterbium, cerium, holmium, europium, and mixtures thereof.
  • Ytterbium and holmium are the most preferred first components of the present catalyst, and it is especially preferred that the first component consists essentially of a ytterbium or holmium component.
  • the first component may in general be present in the catalytic compo site in any catalytically available form such as the elemental metal, a compound such as the oxide, hydroxide, halide, oxyhalide, carbonate or nitrate or in chemical combination with one or more of the other ingredients of the catalyst.
  • the first component is preferably an oxide, an intermetallic with platinum, a sulfate, or in the zirconia lattice.
  • the materials are generally calcined between 600 0 C and 900 0 C and thus in the oxide form. Although it is not intended to so restrict the present invention, it is believed that best results are obtained when the first component is present in. the composite in a form wherein substantially all of the first component is in an oxidation state above that of the elemental state such as in the form of the oxide, oxyhalide or halide or in a mixture thereof and the subsequently described, oxidation and reduction steps that are preferably used in the preparation of the instant catalytic composite are specifically designed to achieve this end.
  • the first component can be incorporated into the catalyst in any amount which is catalytically effective, suitably from 0.01 to 10 mass-% first component in the finished catalyst on an elemental basis. Best results usually are achieved with 1 to 5 mass-% of the first component, calculated on an elemental basis.
  • the first component is incorporated in the catalytic composite in any suitable manner known to the art, such as by coprecipitation, coextrusion with the porous carrier material, o ⁇ impregnation of the porous carrier material either before, after, or simultaneously with tungstate though not necessarily with equivalent results.
  • the platinum-group metal component last.
  • the lanthanide element(s), yttrium, or mixture thereof and the platinum-group metal the order of addition between the two does not have a significant impact.
  • One method of depositing trie first component involves impregnating the support with a solution (preferably aqueous) of a decomposable compound of the first component.
  • decomposable is meant that upon heating, the compound is converted to element or oxide with the release of byproducts.
  • Illustrative of the decomposable compounds without limitation are complexes or compounds such as, nitrates, halides, sulfates, acetates, organic alkyls, hydroxides, and the like compounds.
  • Conditions for decomposition include temperatures ranging from 200°C to 400°C.
  • the first component can be impregnated onto the carrier either prior to, simultaneously with, or after the platinum-group metal component, although not necessarily with equivalent results. If a sequential technique is used, the composite can be dried or dried and calcined in between impregnations.
  • a second component is an essential ingredient of the catalyst.
  • the second component comprises at least one of platinum, palladium, ruthenium, rhodium, iridium, or osmium; platinum is preferred, and it is especially preferred that the platinum-group metal consists essentially of platinum.
  • the platinum-group metal component may exist within the final catalytic composite as a compound such as an oxide, sulfide, halide, oxyhalide, etc., in chemical combination with one or more of the other ingredients of the composite or as the metal.
  • the second component a platinum-group metal component
  • a platinum-group metal component is deposited on the composite using the same means as for trie first component described above.
  • Illustrative of the decomposable compounds of the platirmm group metals are chloroplatinic acid, ammonium chloroplatinate, bromoplatinic acid, dinitrodiamino platinum, sodium tetrarritroplatinate., rhodium trichoride, hexa-arnminerhodrurn chloride, rhodium carbonylchloride, sodium hexanitrorhodate, chloropalladic acid, palladium chloride, palladium nitrate, diamminepalladium hydroxide, tetraamminepalladium chloride, hexachloroiridate (IV) acid, hexachloroiridate (HI) acid, ammonium hexachloroiridate (IH), ammonium aquohexachloroiridate (IV),
  • the second component a platinum-group component
  • the second component is deposited on the support either before, after, or simultaneously with tungstate and/or the first component though not necessarily with equivalent results. It is preferred that the platiirum-group component is deposited on the support either after or simultaneously with tungstate and/or the first component.
  • the catalyst may optionally further include a third component of iron, cobalt, nickel, rhenium or mixtures thereof.
  • Iron is preferred, and the iron may be present in amounts ranging from 0.1 to 5 mass-% on an. elemental basis.
  • the third component such as iron, may function to lower the amount of the first component, such as ytterbium, needed in the optimal formulation.
  • the third component may be deposited on the composite using the same means as for the first and second components as described above.
  • suitable compounds would include iron nitrate, iron halides, iron sulfate and any other soluble iron compound.
  • the catalytic composite described above can be used as a powder or can be formed into any desired shapes such as pills, cakes, extrudates, powders, granules, spheres, etc., and they may be utilized in any particular size.
  • the composite is formed into the particular shape by means well known in the art. In making trie various shapes, it may be desirable to mix the composite with a binder. However, it must be emphasized that the catalyst may be made and successfully used without a binder.
  • the binder when employed, usually comprises from 0.1 to 50 ⁇ nass-%, preferably from 5 to 20 mass-%, of the finished catalyst. Refractory inorganic oxide are suitable binders.
  • binders without limitation are silica, aluminas, silica-alumina, magnesia, zirconium and mixtures thereof.
  • a preferred binder material is alumina, with eta- and/or especially gamma-alumina being favored.
  • the composite and optional binder are mixed along with a peptizing agent such as HCl, HNO 3 , KOH, etc. to form a homogeneous mixture which is formed into a desired shape by forming means well known in the art. These forming means include extrusion, spray drying, oil dropping, marumarizing, conical screw mixing, etc. Extrusion means include screw extruders and extrusion presses.
  • the forming means will determine how much water, if any, is added to the mixture. Thus, if extrusion is used, then the mixture should be in the form of a dough, whereas if spray drying or oil dropping is ⁇ sed, then enough water needs to be present in order to form a slurry. These particles are calcined at a temperature of 26O 0 C to 65O 0 C for a period of 0.5 to 2 hours.
  • the catalytic composites of the present invention either as synthesized or after calcination can be used as catalysts in hydrocarbon conversion processes. Calcination is required, for example, to form zirconium oxide from zirconium hydroxide.
  • Hydrocarbon conversion processes are well known in the art and include cracking, hydrocracking, alkylation of both aromatics and isoparaffms, isomerization, polymerization, reforniiag, dewaxing, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanation, ring opening, and syngas shift processes.
  • Specific reaction conditions and the types of feeds, which can be used in these processes, are set forth in US 4,310,440 and US 4,440,871, which are hereby incorporated by reference.
  • a preferred hydrocarbon conversion process is the isomerization of paraffins.
  • feedstocks boiling within the gasoline range contain paraffins, naphthenes, and aromatics, and may comprise small amounts of olefins.
  • Feedstocks which may be utilized include straight-run naphthas, natural gasoline, synthetic naphthas, thermal gasoline, catalytically cracked gasoline, partially reformed naphthas or raffmates from extraction of aromatics.
  • the feedstock essentially is encompassed- by the range of a full-range naphtha, or within the boiling point range of O 0 C to 23O 0 C.
  • the principal components of the preferred feedstock are alkanes and cycloalkanes having from 4 to 10 carbon atoms per molecule, especially those having from 7 to 8 carbon atoms per molecule. Smaller amounts of aromatic and olefinic hydrocarbons also may be present. Usually, the concentration of C 7 and heavier components is more than 10 mass-% of the feedstock. Although there are no specific limits to the total content in the feedstock of cyclic hydrocarbons, the feedstock generally contains between 2 and 40 mass-% of cyclics comprising naphthenes and aromatics.
  • the aromatics contained in the naphtha feedstock may comprise from 0 to 20 mass-% and more usually from 0 to 10 mass-% of the total.
  • Benzene usually comprises the principal aromatics constituent of the preferred feedstock, optionally along with smaller amounts of toluene and higher-boiling aromatics within the boiling ranges described above.
  • the reactants may be contacted with the bed of catalyst particles in either upward, downward, or radial-flow fashion.
  • the reactants may be in the liquid phase, a mixed liquid-vapor phase, or a vapor phase when contacted with the catalyst particles, with excellent results being obtained by application of the present invention to a primarily liquid-phase operation.
  • the isomerization zone maybe in a single reactor or in two or more separate reactors with suitable means therebetween to ensure that the desired isomerization temperature is maintained at the entrance to each zone. Two or more reactors in sequence are preferred to enable improved isomerization thro " ugh control of individual reactor temperatures and for partial catalyst replacement without a process shutdown.
  • Isomerization conditions in the isomerization zone include reactor temperatures usually ranging from 25 0 C to 300 0 C. Lower reaction temperatures are generally preferred in order to favor equilibrium mixtures having the highest concentration of high-octane highly branched isoalkanes and to minimize cracking of the feed to lighter hydrocarbons. Temperatures in the range of 100 0 C to 25O 0 C are preferred in the process of the present invention. Reactor operating pressures generally range from 100 kPa to 10 MPa absolute, preferably between 0.3 and 4 MPa.
  • Liquid hourly space velocities range from 0.2 to 25 hr "1 , with a range of 0.5 to 10 hr "1 being preferred.
  • Hydrogen is admixed with or remains with the parafflnic feedstock to the isomerization zone to provide a mole ratio of hydrogen to hydrocarbon feed of from 0.01 to 20, preferably from 0.05 to 5.
  • the hydrogen may be supplied totally from outside the process or supplemented by hydrogen recycled to the feed after separation from the reactor effluent.
  • Light hydrocarbons and small amounts of inerts such as nitrogen and argon maybe present in the hydrogen.
  • Water should be removed from hydrogen supplied from outside the process, preferably by an adsorption system as is known in the art.
  • the hydrogen to hydrocarbon mol ratio in the reactor effluent is equal to or less than 0.05, generally obviating the need to recycle hydrogen from the reactor effluent to the feed.
  • the catalyst of the present invention provides the advantages of high activity and improved stability.
  • the isomerization zone generally also contains a separation section, optimally comprising one or more fractional distillation columns having associated appurtenances and separating lighter components from an isoparaffin-rich product.
  • a fract ⁇ onator may separate an isoparaffin concentrate from a cyclics concentrate with the latter being recycled to a ring-cleavage zone.
  • the isoparaffin-rich product and/or the isoparafifin concentrate are blended into finished gasoline along with other gasoline components from refinery processing including, but not limited to, one or more of butanes, butenes, pentanes, naphtha, catalytic reformate, isomerate, alkylate, polymer, aromatic extract, heavy aromatics, gasoline from catalytic cracking, hydrocracking, thermal cracking, thermal reforming, steam pyrolysis and coking, oxygenates such as methanol, ethanol, propanol, isopropanol, tert-butyl alcohol, sec-butyl alcohol, methyl tertiary butyl ether, ethyl tertiary butyl ether, methyl tertiary amyl ether and higher alcohols and ethers, and.
  • refinery processing including, but not limited to, one or more of butanes, butenes, pentanes, naphtha, catalytic reformate, isomerate, alky
  • Catalyst samples of Table 1 were prepared starting with zirconium hydroxide that had been prepared by precipitating zirconyl nitrate with ammonium hydroxide at 65°C.
  • the zirconium hydroxide was dried at 120 0 C, ground to 40-60 mesh. Multiple discrete portions of the zirconium hydroxide were prepared. Solutions of either ammonium metatungstate or a metal salt (component 1) were prepared and added to the portions of zirconium hydroxide. The materials were agitated briefly and then dried with 8O 0 C to 100°C air while rotating. The impregnated samples were then dried in a muffle oven at 150°C for 2 hours under air.
  • a metal salt (component 2, where component 2 is not the same as component 1) were prepared and added to the dried materials. The samples were briefly agitated and dried while rotating. The samples were then calcined at 600 0 C to 850°C for 5 hours. The final impregnation solutions of chloroplatinic acid were prepared and added to the solids. The samples were agitated and dried while rotating as before. The samples were finally calcined at 525°C in air for 2 hours.
  • the catalysts were made at modifier levels of 2.5 rnass-% and 5 mass-%; tungstate levels of 5 mass-%, IO mass-%, and 15 mass-%; and calcination temperatures of 65O 0 C, 700 0 C, 75O 0 C, 800 0 C, and 85O 0 C (with the exception of Gd, which was only prepared at 65O 0 C, 700 0 C, and 75O 0 C calcination temperatures).
  • the first row of Table 1 indicates that a total of 30 different catalysts were made, a catalyst having 2.5 mass-% Ce and 5 mass-% WO 4 and calcined at 65O 0 C, a catalyst having 5 mass-% Ce and 5 mass-% WO 4 and calcined at 65O 0 C, a catalyst having 2.5 mass-% Ce and 10 mass-% WO 4 and calcined at 65O 0 C, a catalyst having 5 mass-% Ce and 10 mass-% WO 4 and calcined at 65O 0 C, a catalyst having 2.5 mass-% Ce and 15 mass-% WO 4 and calcined at 65O 0 C, a catalyst having 5 mass-% Ce and 15 mass-% WO 4 and calcined at 65O 0 C; a catalyst having 2.5 mass-% Ce and 5 mass-% WO 4 and calcined at 700 0 C, a catalyst having 5 mass-% Ce and 5 mass-% WO 4 and calcined at 700 0 C
  • Example 1 The catalysts of Example 1 were prepared as described above in Example 1. Also, reference catalysts were prepared as described in Example 1 but with trie addition of the modifier step being omitted from the preparation. Approximately 95 nig of each sample was loaded into a multi-unit reactor assay. The catalysts were pretreated in air at 450°C for 6 hours and reduced at 200 0 C in H 2 for 1 hour. n-Heptane, 8 mol-%, in hydrogen was then passed over the samples at 120 0 C, 15O 0 C 3 and 180 0 C, approximately 1 atm, and 0.3, 0.6, and 1.2 hr "1 WHSV (based on heptane only). The products were analyzed using online gas chromatographs.
  • FIGs. 1 - 4 selected results are shown in FIGs. 1 - 4 for experiments at 18O 0 C, 1.2 hr "1 WHSV, and using catalysts comprising 15 mass-% W 5 O.5 mass-% Pt.
  • the identity of the modifier (or first component), the amount of modifier, and the calcination temperature are identified along the x-axis of the plots of FIGs. 1 - 4.
  • FIG. 1 is a plot of the conversion of heptane achieved by each of the catalysts.
  • FIG. 2 shows the selectivity of the catalysts for C 7 isomerization. This plot demonstrates that even though some cracking is occurring, selectivities to C 7 isomerization remain high.
  • FIG. 3 shows the selectivity of the catalysts for Cy isomerization to produce two of the desired dimethyl-branched isomers, 2,2-dimethylpentane and 2,4-dimethylpentane.
  • Fig. 4 shows the yield of the catalysts for C 7 isomerization to produce two desired dimethyl-branched isomers, 2,2-dimethylpentane and 2,4-dimethylpentane.
  • FIGs. 5-8 present further selected results of the experiment where ytterbium was the modifier. On each of FIGs.
  • the amount of tungsten on the catalyst, the amount of modifier on the catalyst, the calcination temperature of the catalyst, and the weight hourly space velocity of the run is found on the x-axis.
  • the y-axis is the conversion of the n-heptane feed.
  • the plot demonstrates that conversion increases as the amount of tungsten increases, but conversion decreases as the weight hourly space velocity increases.
  • increasing the amount of modifier from 2.5 mass-% to 5 mass-% does not have a dramatic effect on the conversion.
  • FIG. 6 demonstrates that the selectivity for C 7 isomerization increases with increasing space velocity.
  • FIG. 8 shows the yield of two of the desired dimethyl-branched isomers, 2,2-dimethylpentane and 2,4-dimethylpentane.
  • the results in FIG. 8 indicate that the yield to the specific dimethylpentane isomers (1) decreases as the space velocity is increased; (2) is highest with a calcination temperature of 800 0 C; and (3) is greater at the lower levels of modifiers.

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Abstract

L'invention concerne un catalyseur et un procédé permettant d'améliorer sélectivement une charge paraffinique en vue d'obtenir un produit riche en isoparaffine à mélanger dans l'essence. Ledit catalyseur comprend un support d'un oxyde ou hydroxyde tungstaté d'un métal du groupe IVB (IUPAC 4), un premier composant d'au moins un élément lanthanide, d'yttrium ou des mélanges de ceux-ci, de préférence de l'ytterbium ou de l'holmium, et au moins un composant métallique du groupe du platine, de préférence du platine.
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KR20070084551A (ko) 2007-08-24
EP1804966A4 (fr) 2011-05-18
AU2004324481B2 (en) 2010-02-04
CA2584795C (fr) 2010-07-20
CA2584795A1 (fr) 2006-05-04
CN101052465A (zh) 2007-10-10

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