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WO1996013328A1 - Oxydes solides acides - Google Patents

Oxydes solides acides Download PDF

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Publication number
WO1996013328A1
WO1996013328A1 PCT/US1995/014712 US9514712W WO9613328A1 WO 1996013328 A1 WO1996013328 A1 WO 1996013328A1 US 9514712 W US9514712 W US 9514712W WO 9613328 A1 WO9613328 A1 WO 9613328A1
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WO
WIPO (PCT)
Prior art keywords
group
metal
catalyst
oxide
oxyanion
Prior art date
Application number
PCT/US1995/014712
Other languages
English (en)
Inventor
Clarence Dayton Chang
Charles Theodore Kresge
Jose Guadalupe Santiesteban
James Clarke Vartuli
Original Assignee
Mobil Oil Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to AU41558/96A priority Critical patent/AU4155896A/en
Publication of WO1996013328A1 publication Critical patent/WO1996013328A1/fr

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    • 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
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
    • C07C5/226—Catalytic processes not covered by C07C5/23 - C07C5/31 with metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/656—Manganese, technetium or rhenium

Definitions

  • an acidic solid comprising a Group IVB metal oxide modified with an oxyanion of a Group VIB metal.
  • the acidic solid further comprises an oxide of Mn and/or Fe.
  • This modified solid oxide may be used as a catalyst, for example, to isomerize C 4 to C 8 paraffins.
  • the modified solid oxide may be prepared by co-precipitating the Group IVB metal oxide along with the oxyanion of the Group VIB metal.
  • the present catalysts are useful for many hydrocarbon
  • catalysts may be prepared by a complex impregnation procedure involving numerous steps including the precipitation of zirconia precursor,
  • this complex procedure is reduced to just three steps: co-precipitation of tungsten with the zirconia precursor, filtration, and calcination.
  • the co-precipitation method produces a better catalyst at lower manufacturing cost (fewer steps) and is more flexible to address potential environmental concerns.
  • the solid material described herein comprises an oxide of a Group IVB metal, such as zirconia or titania.
  • This Group IVB metal oxide is modified with an oxyanion of a Group VIB metal, such as an oxyanion of tungsten, such as tungstate.
  • the modification of the Group IVB metal oxide with the oxyanion of the Group VIB metal imparts acid functionality to the material.
  • the modification of a Group IVB metal oxide, particularly, zirconia, with a Group VIB metal oxyanion, particularly tungstate, is described in U.S. Patent No. 5,113,034; in Japanese Kokai Patent
  • Group IVB metal oxide modified with an oxyanion of a Group VIB metal is intended to connote a material comprising, by elemental analysis, a Group IVB metal, a Group VIB metal and oxygen, with more acidity than a simple mixture of separately formed Group IVB metal oxide mixed with a separately formed Group VIB metal oxide or oxyanion.
  • the present Group IVB metal e.g., zirconium, oxide
  • a Group VIB metal e.g., tungsten
  • an oxyanion of a Group VIB metal e.g., tungsten
  • solid superacids are formed when sulfates are reacted with hydroxides or oxides of certain metals, e.g., Zr. These superacids are said to have the structure of a bidentate sulfate ion coordinated to the metal, e.g., Zr.
  • a superacid can also be formed when tungstates are reacted with hydroxides or oxides of Zr.
  • the resulting tungstate modified zirconia materials are theorized to have an analogous structure to the aforementioned superacids comprising sulfate and zirconium, wherein tungsten atoms replace sulfur atoms in the bidentate structure.
  • the present catalysts may comprise the bidentate structure suggested in the
  • IVB metal oxide modified with an oxyanion of a Group VIB metal said acidic solid further comprising an oxide of at least one metal selected from the group consisting of iron and manganese.
  • a source of a Group IVB metal oxide comprising co-precipitating a source of a Group IVB metal oxide, a source of an oxyanion of a Group VIB metal, and a source of an oxide of metal selected from the group consisting of Fe and Mn.
  • tungstate dissolved in water, and said third solution comprising a source of at least one oxide selected from the group consisting of iron and manganese;
  • step (b) maintaining the combined solutions of step (a) under conditions sufficient to form a solid co-precipitate comprising tungstate-modified zirconia and at least one compound comprising Fe and/or Mn;
  • step (c) recovering the solid co-precipitate from step (b) by filtration;
  • step (d) calcining the recovered co-precipitate from step (c).
  • said catalyst comprises an acidic solid comprising a Group IVB metal oxide modified with an oxyanion of a Group VIB metal, said acidic solid further comprising an oxide of at least one metal selected from the group consisting of iron and manganese.
  • a process for isomerizing hydrocarbons comprising contacting a feed comprising C 4 to C 8 hydrocarbons with an isomerization catalyst under sufficient isomerization conditions, said isomerization catalyst comprising (i) a noble metal and (ii) an acidic solid comprising a Group IVB metal oxide modified with an oxyanion of a Group VIB metal, said acidic solid further comprising an oxide of at least one metal selected from the group consisting of iron and manganese.
  • Suitable sources of the Group IVB metal oxide, used for preparing the present catalyst include compounds capable of generating such oxides, such as oxychlorides, chlorides, nitrates, oxynitrates, etc., particularly of zirconium or titanium.
  • Alkoxides of such metals may also be used as precursors or sources of the Group IVB metal oxide. Examples of such alkoxides include zirconium n-propoxide and titanium i-propoxide.
  • These sources of a Group IVB metal oxide, particularly zirconia, may form zirconium hydroxide, i.e., Zr(OH) 4 , or hydrated zirconia as intermediate species upon precipitation from an aqueous medium in the absence of a reactive source of tungstate.
  • zirconium hydroxide i.e., Zr(OH) 4
  • hydrated zirconia is intended to connote materials comprising zirconium atoms covalently linked to other zirconium atoms via bridging oxygen atoms, i.e., Zr-O-Zr, further comprising available surface hydroxy groups.
  • a form of a hydrated zirconia referred to herein as a form of a hydrated zirconia.
  • Suitable sources for the oxyanion of the Group VIB metal, particularly molybdenum or tungsten include, but are not limited to, ammonium metatungstate or
  • metamolybdate tungsten or molybdenum chloride, tungsten or molybdenum carbonyl, tungstic or molybdic acid and sodium tungstate or molybdate.
  • the present modified oxide material may be prepared by combining a first liquid solution comprising a source of a Group IVB metal oxide with a second liquid solution
  • the source of the Group IVB metal oxide and the source of the oxyanion of the Group VIB metal may be combined in a single liquid solution. This solution may then be subjected to conditions sufficient to cause co-precipitation of the solid modified oxide material, such as by the addition of a precipitating reagent to the solution. Water is a preferred solvent for these solutions.
  • maintained during the co-precipitation may be less than about 200oC, e.g., from about 0oC to about 200oC.
  • This liquid medium may be maintained at an ambient temperature (i.e., room temperature) or the liquid may be cooled or heated. A particular range of such temperatures is from about 50oC to about 100°C.
  • the liquid medium from which the present catalyst components are co-precipitated may optionally comprise a solid support material, in which case the present catalyst may be co-precipitated directly onto the solid support material.
  • a solid support material examples include the material designated M41S, which is described in U.S. Patent No. 5,102,643.
  • M41S material designated MCM-41, which is
  • Support materials and/or co-catalyst materials may also, optionally, be co-precipitated from the liquid medium along with the Group IVB metal oxide and the oxyanion of the Group VIB metal.
  • An example of a co-catalyst material is a hydrogenation/dehydrogenation component.
  • a hydrogenation/dehydrogenation component is combined with the material.
  • hydrogenation/dehydrogenation component imparts the ability of the material to catalyze the addition of hydrogen to or the removal of hydrogen from organic compounds, such as hydrocarbons, optionally substituted with one or more heteroatoms, such as oxygen, nitrogen, metals or sulfur, when the organic compounds are contacted with the modified material under sufficient hydrogenation or dehydrogenation conditions.
  • hydrogenation/dehydrogenation components include the oxide, hydroxide or free metal (i.e., zero valent) forms of Group VIII metals (i.e., Pt, Pd, Ir, Rh, Os, Ru, Ni, Co and Fe), Group IVA metals (i.e., Sn and Pb), Group VB metals (i.e., Sb and Bi) and Group VIIB metals (i.e., Mn, Tc and Re).
  • the present catalyst may comprise one or more catalytic forms of one or more noble metals (i.e., Pt, Pd, Ir, Rh, Os or Ru).
  • the valence state of the metal of the hydrogenation/dehydrogenation component may be in a reduced valance state, e.g., when this
  • the reduced valence state of this metal may be attained, in situ, during the course of a reaction, when a reducing agent, such as hydrogen, is included in the feed to the reaction.
  • alkali Group IA
  • alkaline earth Group IIA
  • alkali or alkaline earth compounds may enhance the catalytic properties of components thereof, e.g., Pt or W, in terms of their ability to function as a hydrogenation/dehydrogenation component or an acid
  • the Group IVB metal (i.e., Ti, Zr or Hf) and the Group VIB metal (i.e., Cr, Mo or W) species of the present catalyst are not limited to any particular valence state for these species. These species may be present in this catalyst in any possible positive oxidation value for these species. Subjecting the catalyst, e.g., when the catalyst comprises tungsten, to reducing conditions, e.g., believed to be sufficient to reduce the valence state of the
  • tungsten may enhance the overall catalytic ability of the catalyst to catalyze certain reactions, e.g., the
  • the modified acidic oxide may be contacted with hydrogen at elevated temperatures. These elevated temperatures
  • temperatures may be 100oC or greater, e.g., 250oC or greater, e.g., about 300oC.
  • the duration of this contact may be as short as one hour or even 0.1 hour.
  • extended contact may also be used. This extended contact may take place for a period of 6 hours or greater, e.g., about 18 hours.
  • the modified acidic oxide may be contacted with hydrogen in the presence or absence of a hydrocarbon cofeed.
  • the activity of the catalyst may be increased, in situ, during the course of a reaction, such as hydrocracking, when a hydrocarbon and hydrogen are passed over the catalyst at elevated temperatures.
  • the optional hydrogenation/dehydrogenation component of the present catalyst may be derived from Group VIII metals, such as platinum, iridium, osmium, palladium, rhodium, ruthenium, nickel, cobalt, iron and mixtures of two or more thereof.
  • Optional components of the present catalyst which may be used alone or mixed with the above-mentioned hydrogenation/dehydrogenation components, may be derived from Group IVA metals, particularly Sn, and/or components derived from Group VIIB metals, particularly rhenium and manganese. These components may be added to the catalyst by methods known in the art, such as ion exchange, impregnation or physical admixture.
  • salt solutions of these metals may be contacted with the remaining catalyst components under conditions sufficient to combine the respective components.
  • the metal containing salt may be water soluble.
  • salts include chloroplatinic acid, tetraammineplatinum complexes,
  • platinum chloride platinum chloride, tin sulfate and tin chloride.
  • the optional components may also be co-precipitated along with the other components of the modified oxide material.
  • Suitable iron salts which may be included in this aqueous mixture, include Fe(NO 3 ) 3 and Fe 2 (SO 4 ) 3 .
  • the present modified oxide material may be recovered by filtration from the liquid medium, followed by drying. Calcination of the resulting material may be carried out, particularly in an oxidizing atmosphere, at temperatures from about 500°C to about 900'C, particularly from about 700°C to about 850°C, and more particularly from about 750°C to about 825°C.
  • the calcination time may be up to 48 hours, particularly for about 0.1-24 hours, and more particularly for about 1.0-10 hours. In an important embodiment, calcination is carried out at about 800°C for about 1 to about 3 hours.
  • the optional components of the catalyst may be added after or before the calcination step by techniques known in the art, such as impregnation, co-impregnation, co-precipitation, physical admixture, etc.
  • the optional components e.g., the
  • hydrogenation/dehydrogenation component may also be combined with the remaining catalyst components before or after these remaining components are combined with a binder or matrix material as described hereinafter.
  • zirconium oxide is important; of the Group VIB anions, tungstate is important; and of the optional
  • platinum and/or platinum-tin are important.
  • elemental analysis of the present acidic solid will reveal the presence of Group IVB metal, Group VIB metal and oxygen.
  • the amount of oxygen measured in such an analysis will depend on a number of factors, such as the valence state of the Group IVB and Group VIB metals, the form of the optional hydrogenation/ dehydrogenation component, moisture content, etc.
  • the amount of Group VIB oxyanion in the present catalyst may be expressed as that amount which increases the acidity of the Group IVB oxide. This amount is referred to herein as an acidity increasing amount. Elemental analysis of the present catalyst may be used to determine the relative amounts of Group IVB metal and Group VIB metal in the catalyst. From these amounts, mole ratios in the form of XO 2 /YO 3 may be calculated, where X is said Group IVB metal, assumed to be in the form XO 2 , and Y is said Group VIB metal, assumed to be in the form of YO 3 .
  • the present catalysts may have calculated mole ratios, expressed in the form of XO 2 /YO 3 , where X is at least one Group IVB metal (i.e., Ti, Zr, and Hf) and Y is at least one Group VIB metal (i.e., Cr, Mo, or W), of up to 1000, e.g., up to 300, e.g., from 2 to 100, e.g., from 4 to 30.
  • Group IVB metal i.e., Ti, Zr, and Hf
  • Y is at least one Group VIB metal (i.e., Cr, Mo, or W)
  • incorporated into the present acidic solid may also be expressed in terms of calculated mole ratios of oxides, based upon the elemental analysis of the solid for the Group IVB metal, X, along with Mn and Fe. More
  • this acidic solid may have a calculated mole ratio, expressed in terms of XO 2 /(MnO 2 + Fe 2 O 3 ) , of, for example, from 10 to 500. It will be appreciated, however, that Mn need not necessarily be in the form of MnO 2 , and Fe need not be in the form of Fe 2 O 3 . More particularly, at least a portion of these components may be in the form of free metals or other combined forms than MnO 2 or Fe 2 O 3 e.g., as salts with elements other than oxygen, in any possible valence state for X, Mn, or Fe.
  • XO 2 /(MnO 2 + Fe 2 O 3 ) is given merely for the purposes of expressing calculated quantities of X, Mn, and Fe, and is not to be construed as being limitive of the actual form of these elements in the present acidic solid material.
  • the amount of optional hydrogenation/dehydrogenation component may be that amount which imparts or increases the catalytic ability of the overall material to catalytically hydrogenate or dehydrogenate a hydrogenatable or
  • This amount is referred to herein as a catalytic amount.
  • the present catalyst may comprise, for example, from about 0.001 to about 5 wt%, e.g., from about 0.1 to about 2 wt %, of the optional
  • this catalyst may also comprise up to about five weight percent of Fe and/or Mn, as measured by elemental analysis of the catalyst.
  • the present catalyst is acidic and may be observed as being highly acidic, even to the extent of being a
  • Superacids are a known class of acidic acids
  • this catalyst whether analyzed in the presence or absence of optional components (e.g., hydrogenation/ dehydrogenation components) and/or binder materials, may have an acid strength of a superacid as measured by the color change of an appropriate
  • the Ho acid strength of the present catalyst may have a value of less than -13, i.e., an "acid strength" of greater than -13.
  • an "acid strength" of greater than -13.
  • the use of Hammett indicators to measure the acidity of solid superacids is discussed in the Soled et al. U.S. Patent No. 5,157,199. This Soled et al. patent also describes the Ho acid strength for certain sulfated transition metal superacids.
  • the catalyst described herein may be used as a
  • Suitable feeds contain substantial amounts of normal and/or singly
  • the feed may also contain appreciable amounts of C 6 and C 7 cyclic
  • the present isomerization process may be carried out by contacting the hydrocarbon feed in either liquid or gas phase with the solid catalyst at temperatures less than 500oC, particularly less than 350oC, particularly less than 300oC, and at pressure in the range from 1 to 200
  • atmospheres particularly from 1 to 100 atmospheres, more particularly 5 to 50 atmospheres.
  • the isomerization process may be carried out either in the presence or absence of hydrogen, especially in the presence of
  • the mole ratio of hydrogen to hydrocarbon is particularly in the range of 0.01:1 to 10:1.
  • Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica, and/or metal oxides.
  • the latter may be either naturally occurring or in the form of gelatinous precipitates, sols, or gels
  • the present catalyst need not contain any sulfate ion (U.S. Patent No. 4,918,041). It is noted that the present catalyst need not contain any sulfate ion (U.S. Patent No. 4,918,041). It is noted that the present catalyst need not contain any sulfate ion (U.S. Patent No. 4,918,041). It is noted that the present catalyst need not contain any sulfate ion (U.S. Patent No. 4,918,041). It is
  • the present catalyst is more stable and also much easier to regenerate than sulfated catalysts, such as the superacid sulfated catalysts referred to in the
  • the feedstock for the present process may be one which contains significant amounts of C 5 + normal and/or slightly branched paraffins.
  • the feedstock may contain monocyclic aromatic compounds and/or cyclic paraffins, such as cyclohexane.
  • the hydrocarbons having 6 or less carbon atoms in the feedstock at least 1 wt.%, e.g., at least 5 wt.%, e.g., at least 10 wt.%, e.g., at least 20 wt.%, e.g., at least 30 wt.%, of these hydrocarbons may be cyclic hydrocarbons, e.g., aromatics or cyclic paraffins.
  • the present catalyst may be used to isomerize C 4 -C 8 paraffin hydrocarbons, either as pure compounds or
  • the paraffins will normally be present in mixtures and, in addition to the C 4 -C 8 materials, may contain hydrocarbons boiling outside this range; cycloparaffins and aromatics may also be present.
  • the feed will comprise C 4 -C 8 paraffins such as butane, pentane, hexane and these may be present in refinery streams such as raffinate cuts from solvent extraction units, reformer feedstock or pyrolysis gasoline from ethylene crackers.
  • the feeds may also contain cyclic hydrocarbons, e.g., in the form of C 6 + naphthas; the cyclic materials in such feeds may undergo ring opening reactions in the presence of the catalyst with its associated metal component, to form paraffins which then undergo
  • the isomerization is carried out in the presence of the catalyst, particularly in the presence of hydrogen.
  • Reaction temperatures are suitably in the range of 200 to 800°F (93 to 425oC); temperatures outside this range may be utilized although they are normally less typical;
  • temperatures from 300 to 700oF are typical. Pressures will normally be up to 1000 psig (7,000 kPa abs.) although there is no reason why higher pressures should not be utilized. Lower pressures, in the range of 50 to 600 psig (445 to 790 kPa abs.) may readily be employed and the use of relatively low pressures within this range will generally be preferred in order to permit the use of low pressure equipment.
  • the isomerization is usually carried out in the presence of hydrogen, typically at a molar ratio relative to the feed from 0.01 to 10:1 and usually from 0.5:1 to 2:1. Space velocities are typically from 0.1 to
  • the optional noble metal component of the present catalyst provides a hydrogenation-dehydrogenation component to the catalyst.
  • Metals having a strong hydrogenation function are preferred, especially platinum and the other noble metals such as palladium, rhodium, iridium, rhenium, although other metals capable of acting as a hydrogenation component may also be used, for example, nickel, tungsten or other metals of Group VIII, either singly, in mixtures or in combination with other metals.
  • the amount of the noble metal component may be in the range 0.001 to 5 wt.% of the total catalyst, e.g., from 0.1 to 2 wt. %.
  • Base metal hydrogenation components may be added in somewhat greater amounts. The hydrogenation component can be exchanged onto the support material, impregnated into it or physically admixed with it. If the metal is to be
  • platinum compounds include chloroplatinic acid, platinous chloride and various platinum compounds
  • the metal compounds may be either compounds in which the metal is present in the cation or anion of the compound; both types of compounds can be used.
  • Platinum compounds in which the metal is in the form of a cation of cationic complex, e.g., Pt(NH 3 ) 4 Cl 2 are particularly useful, as are anionic complexes such as the vanadate and metatungstate ions.
  • Cationic forms of other metals are also useful since they may be exchanged onto the support or impregnated into it.
  • the catalyst may be subjected to a final calcination under conventional conditions in order to dehydrate the catalyst and to confer the required mechanical strength on the catalyst. Prior to use the catalyst may be subjected to presulfiding.
  • a source of hydrogenation metal such as H 2 PtCl 6
  • H 2 PtCl 6 it may be desirable to subject the present catalyst to extended reducing
  • Higher isomerization activity may be provided by the inclusion of an additional material having Lewis or
  • Br ⁇ nsted acid activity in the catalyst especially when the catalyst comprises a porous binder material.
  • both liquid and solid acid materials may be used.
  • suitable additional acidic materials include aluminum trichloride, boron trifluoride and complexes of boron trifluoride, for example, with water, lower alcohols or esters.
  • the maximum amount which may be added is set by the ability of the support material, especially the binder material, to sorb the added component and is readily determined by experiment.
  • the present catalyst may be used as the exclusive isomerization catalyst in single or multiple catalyst beds or it may be used in combination with other isomerization catalysts.
  • a feed may be first contacted with a catalyst bed comprising the present catalyst followed by contact with a second catalyst bed comprising a different catalyst, such as Pt on mordenite, Pt on zeolite beta or a chlorided platinum-alumina catalyst, as described in U.S. Patent Nos. 4,783,575 and 4,834,866.
  • the temperature of the first catalyst bed may be higher than the temperature of the second catalyst bed.
  • relatively high temperatures e.g., as high as 500oC
  • relatively high pressures e.g., as high as 200 atmospheres
  • the present catalyst can be shaped into a wide variety of particle sizes.
  • the particles can be in the form of a powder, a granule, or a molded product, such as an extrudate having particle size sufficient to pass through a 2 mesh (Tyler) screen and be retained on a 400 mesh (Tyler) screen.
  • the catalyst can be extruded before drying or partially dried and then extruded.
  • the present catalyst may be composited with a matrix material to form the finished form of the catalyst and for this purpose conventional matrix materials such as alumina, silica-alumina and silica are suitable with preference given to silica when a non-acidic binder is desired.
  • binder materials may be used, for example, titania, zirconia and other metal oxides or clays.
  • the active catalyst may be composited with the matrix in amounts from 80:20 to 20:80 by weight, e.g., from 80:20 to 50:50 active catalyst:matrix. Compositing may be done by conventional means including mulling the materials together followed by extrusion of pelletizing into the desired finished catalyst particles.
  • the catalyst may be treated by conventional pre-sulfiding treatments, e.g., by heating in the presence of hydrogen sulfide, to convert oxide forms of the metal components to their corresponding sulfides.
  • hydrogenation/dehydrogenation component it may be used in reactions requiring the use of a dual-functional (1) acidic and (2) hydrogenation/dehydrogenation catalyst.
  • Such conversion processes include, as non-limiting examples, hydrocracking hydrocarbons with reaction conditions
  • dehydrogenating hydrocarbon compounds with reaction conditions including a temperature of from 100°C to 700oC, a pressure of from 0.1 atmosphere (bar) (10 KPa) to 30 atmospheres (3040 KPa), a weight hourly space velocity of from 0.1 to 20, and a hydrogen/ hydrocarbon mole ratio of from 0 to 20; dehydrogenating hydrocarbon compounds with reaction conditions including a temperature of from 300oC to 700oC, a pressure of from 0.1 atmosphere (10 KPa) to 10
  • atmospheres (1013 KPa) and a weight hourly space velocity of from 0.1 to 20 converting paraffins to aromatics with reaction conditions including a temperature of from 100oC to 700°C, a pressure of from 0.1 atmosphere (10 KPa) to 60 atmospheres (6080 KPa), a weight hourly space velocity of from 0.5 to 400 and a hydrogen/hydrocarbon mole ratio of from 0 to 20; converting olefins to aromatics, e.g., benzene, toluene and xylenes, with reaction conditions including a temperature of from 100oC to 700oC, a pressure of from 0.1 atmosphere (10 KPa) to 60 atmospheres (6080 KPa), a weight hourly space velocity of from 0.5 to 400 and a hydrogen/ hydrocarbon mole ratio of from 0 to 20;
  • transalkylating aromatic hydrocarbons in the presence of polyalkylaromatic hydrocarbons with reaction conditions including a temperature of from 100oC to 500oC, a pressure of from atmospheric (101 KPa) to 200 atmospheres (20265
  • KPa a weight hourly space velocity of from 10 to 1000 and an aromatic hydrocarbon/polyalkylaromatic hydrocarbon mole ratio of from 0.3/1 to 20/1, and a hydrogen/hydrocarbon mole ratio of from 0 to 20; and transferring hydrogen from paraffins to olefins with reaction conditions including a temperature from -25oC to 400oC, e.g., from 75oC to 200oC, a pressure from below atmospheric (101 KPa) to 5000 psig (34566 KPa), e.g., from atmospheric (101 KPa) to 1000 psig (6994 KPa), a mole ratio of total paraffin to total olefin of from 1:2 to 500:1, e.g., from 5:1 to 100:1; and a weight hourly space velocity based on olefin of from 0.01 to 100, e.g., from 0.05 to 5.
  • reaction conditions including a temperature from -25oC to 400oC, e.g.,
  • the present catalyst may also be used in an
  • the isoparaffin may be isobutane and the olefin may be ethylene, propylene and/or butene(s), e.g., 2-butene.
  • the isoparaffin/olefin alkylation reaction may take place in the presence or absence of a hydrogenation/ dehydrogenation component, in the presence or absence of cofed hydrogen, at a temperature of from -25oC to 400oC with 75oC being a more useful upper limit, at a pressure from below atmospheric (101 KPa) to 5000 psig (34566 KPa), at a weight hourly space velocity based on olefin of from 0.01 to 100 hr -1 , and at a mole ratio of total isoparaffin to total olefin of from 1:2 to 500:1.
  • the present catalyst may also be used in various hydroprocessing reactions, such as the removal of metals, nitrogen and/or sulfur from feedstocks, such as resids, including such elements, particularly in the form of heteroatoms.
  • hydroprocessing reactions comprise contacting the feedstock along with a sufficient amount of hydrogen with the present catalyst under conditions
  • This Example describes the preparation of a tungstate-modified zirconia (WO x /ZrO 2 ).
  • Five hundred grams of ZrOCl 2 • 8H 2 O were dissolved with stirring in 7.0 liters of distilled H 2 O.
  • a solution containing 263 ml of cone. NH 4 OH, 500 mL of distilled H 2 O, and 54 grams of (NH 4 ) 6 H 2 W 12 O 40 • ⁇ H 2 O was added dropwise over a 30-45 minute period.
  • the pH of the solution was adjusted to approximately 9 (if needed) by adding additional cone.
  • NH 4 OH dropwise This slurry was then placed in the steambox for 72 hours.
  • the product formed was recovered by filtration, washed with excess H 2 O, and dried overnight at 85oC.
  • the material was then
  • This Example describes the preparation of a tungstate-modified zirconia containing 0.6 wt.% Pt (0.6 wt.%
  • This Example describes the preparation of 0.3 wt.% Pt/WO x /ZrO 2 . Twelve grams of WO x /ZrO 2 , prepared according to Example 1, were impregnated with a solution containing 0.096 grams of H 2 PtCl 6 • 6H 2 O dissolved in 20 ml of
  • This Example describes the preparation of 0.5 wt.% Pt/SiO 2 -WO x /ZrO 2 . Twelve grams of WO x /ZrO 2 , prepared according to Example 1, were mechanically mixed with 7 grams of a 0.5 wt.% Pt/SiO 2 catalyst. The 0.5 wt.% Pt/SiO 2 catalyst was prepared via ion exchange. Silica gel
  • This Example describes the preparation of Fe/WO x /Zr O2 .
  • Five hundred grams of ZrOCl 2 • 8H 2 O were dissolved with stirring in 6.5 liters of distilled H 2 O.
  • a solution containing 7.5 grams of FeSO 4 • 7H 2 O dissolved in 500 ml of distilled H 2 O was then added to the zirconyl-containing solution.
  • This Example describes the preparation of Pt-containing Fe/WO x /ZrO 2 .
  • the resulting catalyst was dried and then calcined at 300oC in dry air for 2 hours.
  • This Example describes the preparation of Mn/WO x /ZrO 2 .
  • Five hundred grams of ZrOCl 2 • 8H 2 O were dissolved with stirring in 6.5 liters of distilled H 2 O.
  • a solution containing 4.6 grams of MnSO 4 • 7H 2 O dissolved in 500 ml of distilled H 2 O was then added to the zirconyl-containing solution.
  • This Example describes the preparation of Pt-containing Mn/WO x /zrO 2 . Twelve grams of Mn/WO x /ZrO 2 , prepared according to Example 9, were impregnated with a solution containing 0.1926 grams of H 2 PtCl 6 • 6H 2 O dissolved in 20 ml of distilled deionized H 2 O by incipient wetness.
  • the resulting catalyst was dried and then calcined at 300°C in dry air for 2 hours.
  • Catalysts of Examples 7 and 8 were tested for n-hexane isomerization at 210oC, 450 psig, 2 mol H 2 /mol n-C 6 , and 2 LHSV (cc n-C 5 feed per cc catalyst per hour). The results are shown in Table 4. It is apparent that addition of Pt to the Fe/WO x /ZrO 2 improves both the n-hexane isomerization activity and the selectivity to the desirable high-octane dimethyl butanes.

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Abstract

L'invention se rapporte à un solide acide comprenant un oxyde métallique du Groupe IVB modifié par un oxyanion d'un métal du Groupe VIB. Un exemple de ce solide acide est la zircone, modifiée par le tungstate. Ce solide acide comprend également un oxyde de Mn ou Fe. Il peut être utilisé, par exemple, comme catalyseur, afin d'isomériser des paraffines en C4-C8. Il peut être préparé par coprécipitation de l'oxyde métallique du Groupe IVB et de l'oxyanion du métal du Groupe VIB.
PCT/US1995/014712 1994-10-31 1995-10-20 Oxydes solides acides WO1996013328A1 (fr)

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JP3034493B2 (ja) 1998-03-31 2000-04-17 財団法人石油産業活性化センター 固体酸触媒及びその製造方法並びにパラフィン類の異性化方法
WO2005066101A1 (fr) * 2003-12-23 2005-07-21 Exxonmobil Chemical Patents Inc. Decomposition selective d'ethers
WO2006135475A1 (fr) 2005-06-08 2006-12-21 Exxonmobil Chemical Patents Inc. Procédé pour la production d'un alcool par décomposition sélective d'un éther
WO2008018970A3 (fr) * 2006-08-03 2008-05-29 Abb Lummus Global Inc Composition de catalyseur d'acide solide dopé, procédé de conversion à l'aide de celle-ci et produits de conversion dudit procédé
WO2014018591A1 (fr) * 2012-07-25 2014-01-30 Clariant Corporation Catalyseur d'hydrodésoxygénation
EP1914216A4 (fr) * 2006-06-19 2017-11-01 Limited Liability Company "Scientific Industrial Enterprise Neftehim" Procédé d'isomérisation de fractions légères d'essence
WO2022081660A1 (fr) * 2020-10-13 2022-04-21 Phillips 66 Company Structure organométallique
US11745168B2 (en) 2021-06-17 2023-09-05 ExxonMobil Technology and Engineering Company Bifunctional metal oxides and paraffin isomerization therewith

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3034493B2 (ja) 1998-03-31 2000-04-17 財団法人石油産業活性化センター 固体酸触媒及びその製造方法並びにパラフィン類の異性化方法
WO2005066101A1 (fr) * 2003-12-23 2005-07-21 Exxonmobil Chemical Patents Inc. Decomposition selective d'ethers
US7102037B2 (en) 2003-12-23 2006-09-05 Exxonmobil Chemical Patents Inc. Selective decomposition of ethers
WO2006135475A1 (fr) 2005-06-08 2006-12-21 Exxonmobil Chemical Patents Inc. Procédé pour la production d'un alcool par décomposition sélective d'un éther
US7399891B2 (en) 2005-06-08 2008-07-15 Exxonmobil Chemical Patents Inc. Process for alcohol production by selective ether decomposition
EP1914216A4 (fr) * 2006-06-19 2017-11-01 Limited Liability Company "Scientific Industrial Enterprise Neftehim" Procédé d'isomérisation de fractions légères d'essence
WO2008018970A3 (fr) * 2006-08-03 2008-05-29 Abb Lummus Global Inc Composition de catalyseur d'acide solide dopé, procédé de conversion à l'aide de celle-ci et produits de conversion dudit procédé
JP2009545436A (ja) * 2006-08-03 2009-12-24 ラマス テクノロジ インコーポレイテッド ドープされた固体酸触媒組成物、そのドープされた固体酸触媒組成物を用いた変換プロセス、およびその変換生成物
WO2014018591A1 (fr) * 2012-07-25 2014-01-30 Clariant Corporation Catalyseur d'hydrodésoxygénation
US9278346B2 (en) 2012-07-25 2016-03-08 Clariant Corporation Hydrodeoxygenation catalyst
WO2022081660A1 (fr) * 2020-10-13 2022-04-21 Phillips 66 Company Structure organométallique
US11745168B2 (en) 2021-06-17 2023-09-05 ExxonMobil Technology and Engineering Company Bifunctional metal oxides and paraffin isomerization therewith

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