WO1997019752A1 - Process for preparing a catalyst suitable for use in isomerising hydrocarbons, the catalyst thus obtained, and its use - Google Patents

Process for preparing a catalyst suitable for use in isomerising hydrocarbons, the catalyst thus obtained, and its use Download PDF

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Publication number
WO1997019752A1
WO1997019752A1 PCT/EP1996/005372 EP9605372W WO9719752A1 WO 1997019752 A1 WO1997019752 A1 WO 1997019752A1 EP 9605372 W EP9605372 W EP 9605372W WO 9719752 A1 WO9719752 A1 WO 9719752A1
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Prior art keywords
hydrocarbon
catalyst composition
catalyst
activated
process according
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PCT/EP1996/005372
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French (fr)
Inventor
Jacobus Johannes Leonardus Heinerman
Petrus Josephus Mangnus
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Akzo Nobel N.V.
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Publication date
Application filed by Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to EP96941653A priority Critical patent/EP0863800B1/en
Priority to BR9611792A priority patent/BR9611792A/en
Priority to AU10974/97A priority patent/AU718621B2/en
Priority to CA002238422A priority patent/CA2238422C/en
Priority to DE69614272T priority patent/DE69614272T2/en
Priority to JP52020097A priority patent/JP3998044B2/en
Publication of WO1997019752A1 publication Critical patent/WO1997019752A1/en

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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
    • 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
    • B01J23/42—Platinum
    • 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
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—Halides
    • 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
    • B01J37/08—Heat treatment
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • 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
    • B01J37/22—Halogenating
    • B01J37/24—Chlorinating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • C07C2/60—Catalytic processes with halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C07C2/68—Catalytic processes with halides
    • 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
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • 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
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2794—Catalytic processes with hydrides or organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
    • 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
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • 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
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
    • C07C2531/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of the platinum group metals, iron group metals or copper

Definitions

  • the invention pertains to a process for preparing an activated catalyst composition suitable for use in isomerising hydrocarbons based on a catalyst composition comprising a Group VIII noble metal and a hydrocarbon-substituted aluminium compound on an alumina carrier containing up to 20 wt.% of other components, the catalyst thus obtained, and its use.
  • Isomerisation catalysts comprising a Group VIII noble metal and a hydrocarbon- substituted aluminium compound on an alumina carrier are known in the art, as are processes for the preparation thereof.
  • GB patent 1 432 639 describes a process for preparing an isomerisation catalyst of this description in which a composition comprising a Group VIII noble metal and alumina is contacted with a hydrocarbon-substituted aluminium halide, whereupon the resulting catalyst is used directly for isomerising paraffins.
  • GB patent 952 348 describes a process for preparing an isomerisation catalyst in which a composition comprising a Group VIII noble metal and alumina is contacted with a trialkyl aluminium compound, whereupon the whole is reacted with, e.g., a hydrogen halide at a temperature below 260°C. This treatment may be followed by a further activation with hydrogen at a temperature below 371 °C if so desired.
  • a catalyst composition comprising a Group VIII noble metal and a hydrocarbon-substituted aluminium compound on an alumina carrier containing up to 20 wt.% of other components
  • a high-temperature activation step in which the composition is contacted with a hydrogen-containing gas at a temperature of 500°C or higher
  • the hydrocarbon-substituted aluminium compound is not a hydrocarbon- substituted aluminium halide, it will be necessary to contact the catalyst composition to be activated with a halogen compound, either prior to or during the activating step
  • the Group VIII noble metal present in the catalyst may be selected from the group of ruthenium, rhenium, palladium, osmium, indium, and platinum, with preference being given to platinum, palladium, and mixtures thereof
  • the final catalyst preferably contains 0 01 -2 wt % of the Group VIII noble metal, calculated as metal, more particularly 0 05 to 1 wt %
  • Other metal components may also be present in the catalyst composition if so desired Examples of other metal components which may influence the activity, selectivity or stability of the catalyst are tin, lead, germanium, bismuth, cobalt, nickel, indium, gallium, zinc, uranium, thallium, zirconium, and mixtures thereof
  • the alumina carrier containing up to 20 wt % of other components preferably takes the form of particles, which are obtained by means of, e g , extrusion, pelletising, or by some other known method
  • the particles' shape may vary As suitable shapes may be mentioned spheres, cylinders, rings, and symmetric or asymmetric polylobes, such as t ⁇ lobes and quadrulobes Generally, the particles will have a diameter in the range of 1 to 10 mm, and a length which is also in the range of 1 to 10 mm
  • the alumina may contain up to 20 wt % of other constituents, such as silica, magnesia, titania, or zirconia It is preferred that more than 90 wt % of the carrier, more preferably over 95 wt %, and most preferably substantially all of the carrier consists of alumina
  • the term "substantially ad" means that the catalyst carrier consists essentially of alumina, with the only additional carrier components being
  • the compositing of the metals components with the earner may be in any manner known in the art
  • the carrier particles can then be impregnated with an impregnating solution comp ⁇ sing a soluble salt or complex of the metal or metals to be provided
  • an impregnating solution comp ⁇ sing a soluble salt or complex of the metal or metals to be provided
  • a strongly acid impregnation solution such as an impregnation solution containing chloroplatinic acid, HCl, and HN0 3
  • the Group VIII metal component present on the carrier may be reduced, e g , by passing hydrogen over the composition at a temperature in the range of 100 to 600°C
  • the hydrocarbon-substituted aluminium compound used in the process according to the invention may be a halide, in which case a hydrocarbon- substituted aluminium chloride is preferably used
  • the hydrocarbon-substituted aluminium halide may be, e g , a compound satisfying the formula AIX y R1 n R2 m , wherein X is a halogen atom, R1 and R2 may be the same or different and are selected from alkyl groups or aryl groups having 1-12 carbon atoms, y has the value 1 or 2, and n and m have the value 0 or 1 , with the sum of y, n, and m being 3
  • X may be selected from fluorine, chlo ⁇ ne, bromine, and iodine, and is preferably chlorine
  • hydrocarbon-substituted aluminium compound When the hydrocarbon-substituted aluminium compound is not a halide, it may satisfy the formula AIR1 R2R3, wherein R1 , R2, and R3 may be the same or different and are selected from alkyl groups or aryl groups having 1-12 carbon atoms, such as described above
  • R1 , R2, and R3 may be the same or different and are selected from alkyl groups or aryl groups having 1-12 carbon atoms, such as described above
  • Examples of hydrocarbon-substituted aluminium compounds include triethyl aluminium and isobutyl diethyl aluminium Mixtures of various non-halide hydrocarbon-substituted aluminium compounds may also be used
  • hydrocarbon-substituted aluminium compound can be incorporated into the catalyst composition in an amount of 0 05 to 0 20 mole of hydrocarbon- substituted aluminium compound per mole of carrier
  • the hydrocarbon- substituted aluminium compound is incorporated into the catalyst composition in a manner known in the art For example, it is possible to incorporate the hydrocarbon-substituted aluminium compound into the catalyst by contacting it with a composition comprising a Group VIII noble metal, optionally in the reduced form, on an alumina carrier containing up to 20 wt % of other components
  • a composition comprising a Group VIII noble metal, optionally in the reduced form, on an alumina carrier containing up to 20 wt % of other components
  • the incorporation of the hydrocarbon-substituted aluminium compound into the catalyst composition may take the form of the compound being dissolved in a solvent and impregnating the carrier, which optionally comprises the Group VIII noble metal component, with this solution, followed by removal of the solvent
  • the boiling point of the solvent will not be too high, since it is harder to remove high-boiling solvents from the composition
  • Suitable solvents include pentane, hexane, heptane, etc
  • a catalyst composition comprising a Group VIII noble metal and a hydrocarbon-substituted aluminium compound on a carrier is contacted with a hydrogen-containing gas at a temperature above 500°C, preferably in the range of 500 to 1000°C, more preferably in the range of 500 to 800°C, most preferably 600-750°C
  • the activation is carried out by contacting the catalyst with the hydrogen-containing gas over a period of 15 minutes to 5 hours, preferably of 30 minutes to 3 hours
  • a hydrogen-containing gas which may contain other constituents if so desired, such as diluents, e g , nitrogen, argon, or other inert gases
  • the hydrogen-containing gas used in the activation process according to the invention preferably holds less than 10 ppm of water and less than 10 ppm of oxygen or oxygen-containing components
  • the catalyst composition should be contacted with a halogen compound, particularly a chlorine compound, either before or during the activation treatment
  • a halogen compound particularly a chlorine compound
  • suitable halogen compounds to be used either before or in the activation step are hydrogen halides, such as hydrogen chloride, a halogen gas, a halogenated hydrocarbon, such as carbon tetrachloride chloroform, chloroethane, etc
  • Hydrogen halides, particularly HCl are generally preferred If the activation step is carried out in the presence of a halogen compound, the molar ratio of the activation step is carried out in the presence of a halogen compound, the molar ratio of the activation step is carried out in the presence of a halogen compound, the
  • the activated catalyst prepared by the process according to the invention is suitable for use in a variety of hydrocarbon conversion processes It can, for example, be used in the isomerisation of aromatic and aliphatic hydrocarbons, more particularly for isomerising n-paraffins having 4 to 12 carbon atoms It is also suitable for isomerising mixtures of different n-paraffins and mixtures of n- paraffins and aromatic hydrocarbons
  • the catalyst according to the invention produces particularly favourable results in the case of C 4 , C Cs, and C?
  • the feedstock to be isome ⁇ sed contains at least 50 wt % of paraffins to be isome ⁇ sed
  • the feedstock may contain olefins, but preferably less than 10%, because the presence of olefins leads to increased hydrogen consumption
  • the feed should be relatively free from sulphur components and water, because these materials act as catalyst poisons
  • the feed generally contains up to 1 ppm of sulphur, and up to 0 5 ppm of water
  • the isomerisation process may take the form of the feed to be isome ⁇ sed being contacted with the catalyst described hereinbefore in a fixed bed at a temperature in the range of 80 to 330°C, preferably of 100 to 200°C, in the presence of hydrogen
  • the pressure in the isomerisation reactor generally is in the range of 1 to 60 bar, preferably of 2 to 40 bar, with the LHSV ranging from 0 5 to 40 h "1 , preferably from 1 to 20 h '1 , and the molar ratio between the hydrogen and the feed being in the range of 0 005 to 10, preferably in the range of 0 01 to 5
  • a minute amount of a halogen-containing compound may be incorporated into the feed in order to extend the life of the catalyst
  • 0 001 to 1 wt % calculated as halogen, of a hydrogen halide, a halogen gas, or a halogenated hydrocarbon, such as carbon tetrachlor
  • INC 5 iC 5 x 100 iC 5 + nC ⁇
  • INC 4 ⁇ C 4 x 100 ⁇ C 4 + nC
  • the process for preparing the comparative catalyst according to GB 1432639 above was repeated, except that the product was subjected to an additional activation step After the removal of the remaining liquid by evaporation at a temperature of 130°C under a nitrogen flow of 1300 ml/min, the product in the round-bottom flask was heated to 640°C in a 5% hydrogen and 95% nitrogen flow (total flow 2000 ml/mm) After one hour of activating at 640°C using the same hydrogen/nitrogen flow the product was cooled to room temperature under 100% nitrogen to complete the preparation of the catalyst according to the invention
  • the catalyst according to the invention which differs from the catalyst according to GB 1432639 only in that it has been subjected to a high-temperature treatment in the presence of hydrogen, shows a highly improved isomerisation activity, as is evidenced by both a higher INC 5 and a higher INC 6
  • the catalyst according to the invention which differs from the catalyst according to GB 952.348 only in that it has been subjected to a high-temperature treatment in the presence of hydrogen, shows an improved isomerisation activity, as is evidenced by both a higher INCs and a higher INC 6 .

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Abstract

The invention pertains to a process for preparing an activated catalyst composition in which a catalyst composition comprising a Group VIII noble metal and a hydrocarbon-substituted aluminium compound on an alumina carrier containing up to 20 wt.% of other components is activated by being contacted with a hydrogen-containing gas at a temperature in excess of 500 °C, with the proviso that at least when the hydrocarbon-substituted aluminium compound present in the catalyst composition is not a hydrocarbon-substituted aluminium halide, the catalyst composition to be activated is contacted with a halogen compound either prior to or during the activating step. The catalyst obtainable by this process and the use thereof in hydrocarbon conversion processes, such as isomerisation and alkylation processes, are also part of the present invention. The effect of the high-temperature activation step is that the activity of the thus obtained catalyst is improved in comparison with a catalyst of the same composition which has not been subjected to said high temperature activation step.

Description

PROCESS FOR PREPARING A CATALYST SUITABLE FOR USE IN ISOMERISING HYDROCARBONS, THE CATALYST THUS OBTAINED, AND ITS USE
The invention pertains to a process for preparing an activated catalyst composition suitable for use in isomerising hydrocarbons based on a catalyst composition comprising a Group VIII noble metal and a hydrocarbon-substituted aluminium compound on an alumina carrier containing up to 20 wt.% of other components, the catalyst thus obtained, and its use.
Isomerisation catalysts comprising a Group VIII noble metal and a hydrocarbon- substituted aluminium compound on an alumina carrier are known in the art, as are processes for the preparation thereof.
GB patent 1 432 639 describes a process for preparing an isomerisation catalyst of this description in which a composition comprising a Group VIII noble metal and alumina is contacted with a hydrocarbon-substituted aluminium halide, whereupon the resulting catalyst is used directly for isomerising paraffins. GB patent 952 348 describes a process for preparing an isomerisation catalyst in which a composition comprising a Group VIII noble metal and alumina is contacted with a trialkyl aluminium compound, whereupon the whole is reacted with, e.g., a hydrogen halide at a temperature below 260°C. This treatment may be followed by a further activation with hydrogen at a temperature below 371 °C if so desired.
However, the catalysts described in these references fail to function in a satisfactory manner, and there is need for a catalyst of improved activity.
It has now been found that the activity of a catalyst composition comprising a Group VIII noble metal and a hydrocarbon-substituted aluminium compound on an alumina carrier containing up to 20 wt.% of other components can be enhanced by subjecting this composition to a high-temperature activation step in which the composition is contacted with a hydrogen-containing gas at a temperature of 500°C or higher In this respect it should be taken into account that if the hydrocarbon-substituted aluminium compound is not a hydrocarbon- substituted aluminium halide, it will be necessary to contact the catalyst composition to be activated with a halogen compound, either prior to or during the activating step
The Group VIII noble metal present in the catalyst may be selected from the group of ruthenium, rhenium, palladium, osmium, indium, and platinum, with preference being given to platinum, palladium, and mixtures thereof The final catalyst preferably contains 0 01 -2 wt % of the Group VIII noble metal, calculated as metal, more particularly 0 05 to 1 wt % Other metal components may also be present in the catalyst composition if so desired Examples of other metal components which may influence the activity, selectivity or stability of the catalyst are tin, lead, germanium, bismuth, cobalt, nickel, indium, gallium, zinc, uranium, thallium, zirconium, and mixtures thereof
The alumina carrier containing up to 20 wt % of other components preferably takes the form of particles, which are obtained by means of, e g , extrusion, pelletising, or by some other known method The particles' shape may vary As suitable shapes may be mentioned spheres, cylinders, rings, and symmetric or asymmetric polylobes, such as tπlobes and quadrulobes Generally, the particles will have a diameter in the range of 1 to 10 mm, and a length which is also in the range of 1 to 10 mm The alumina may contain up to 20 wt % of other constituents, such as silica, magnesia, titania, or zirconia It is preferred that more than 90 wt % of the carrier, more preferably over 95 wt %, and most preferably substantially all of the carrier consists of alumina Here, the term "substantially ad" means that the catalyst carrier consists essentially of alumina, with the only additional carrier components being impurities of which the presence is unavoidable Suitable aluminas include the active aluminas such as gamma-alumina, eta-alumina, theta-alumina, and mixtures thereof Gamma- alumina is particularly preferred The alumina carrier containing up to 20 wt % of other components preferably has a surface area of 100-500 m2/g, a total pore volume of 0 1 -1 ml/g, and an average pore diameter of 2-20 nm
The compositing of the metals components with the earner may be in any manner known in the art For example, one can start by preparing carrier particles by shaping a carrier precursor, for example by extrusion, and calcining the resulting shaped particles The carrier particles can then be impregnated with an impregnating solution compπsing a soluble salt or complex of the metal or metals to be provided For example, one may impregnate the earner with an impregnation solution containing chloroplatinic acid, platinum dichloride, platinum tetrachloride hydrate, etc It is well-known in the art to add additional components to the impregnation solution to stabilise the solution, or to influence the distribution of metal over the catalyst carrier For example, if a homogeneous platinum distribution is desired, a strongly acid impregnation solution, such as an impregnation solution containing chloroplatinic acid, HCl, and HN03, is commonly used The impregnated particles may optionally be calcined On the other hand, it is also possible to mix compounds of the metal or metals to be incorporated into the catalyst composition with the carrier precursor, and then shape the mixture, for example by extrusion, after which the extrudates are calcined
If so desired, the Group VIII metal component present on the carrier may be reduced, e g , by passing hydrogen over the composition at a temperature in the range of 100 to 600°C The hydrocarbon-substituted aluminium compound used in the process according to the invention may be a halide, in which case a hydrocarbon- substituted aluminium chloride is preferably used The hydrocarbon-substituted aluminium halide may be, e g , a compound satisfying the formula AIXyR1 nR2m, wherein X is a halogen atom, R1 and R2 may be the same or different and are selected from alkyl groups or aryl groups having 1-12 carbon atoms, y has the value 1 or 2, and n and m have the value 0 or 1 , with the sum of y, n, and m being 3 X may be selected from fluorine, chloπne, bromine, and iodine, and is preferably chlorine R1 and R2 may be selected from, e g , methyl, ethyl, isopropyl, butyl, phenyl, cyclohexyl, etc Suitable hydrocarbon-substituted aluminium halides include diethyl aluminium chloride, methyl aluminium dichloride, ethyl aluminium dichloride, and isobutyl aluminium dichloride It should be noted that the hydrocarbon-substituted aluminium halide also may be a mixture of vaπous hydrocarbon-substituted aluminium halides or a complex, for instance an alkyl aluminium sesquichloride
When the hydrocarbon-substituted aluminium compound is not a halide, it may satisfy the formula AIR1 R2R3, wherein R1 , R2, and R3 may be the same or different and are selected from alkyl groups or aryl groups having 1-12 carbon atoms, such as described above Examples of hydrocarbon-substituted aluminium compounds include triethyl aluminium and isobutyl diethyl aluminium Mixtures of various non-halide hydrocarbon-substituted aluminium compounds may also be used
If so desired one may also apply a combination of one or more hydrocarbon- substituted aluminium halides with one or more non-halide hydrocarbon- substituted aluminium compounds In that case, care should be taken that a sufficient amount of halide is added to the catalyst composition either with the hydrocarbon-substituted aluminium halide, or separately The hydrocarbon-substituted aluminium compound can be incorporated into the catalyst composition in an amount of 0 05 to 0 20 mole of hydrocarbon- substituted aluminium compound per mole of carrier The hydrocarbon- substituted aluminium compound is incorporated into the catalyst composition in a manner known in the art For example, it is possible to incorporate the hydrocarbon-substituted aluminium compound into the catalyst by contacting it with a composition comprising a Group VIII noble metal, optionally in the reduced form, on an alumina carrier containing up to 20 wt % of other components Although less preferred, it is also possible to first incorporate the hydrocarbon substituted aluminium compound into the catalyst composition, and only then incorporate the Group VIII noble metal
The incorporation of the hydrocarbon-substituted aluminium compound into the catalyst composition may take the form of the compound being dissolved in a solvent and impregnating the carrier, which optionally comprises the Group VIII noble metal component, with this solution, followed by removal of the solvent Preferably, the boiling point of the solvent will not be too high, since it is harder to remove high-boiling solvents from the composition Suitable solvents include pentane, hexane, heptane, etc It should be noted in this context that the removal of the solvent from the solution pπor to the activating step is not always required One possible alternative is to evaporate the solvent during the activating step Of course, the feasibility of this option is dependent upon the nature of the solvent and the other process conditions
In the process for the activation of a catalyst composition according to the invention, a catalyst composition comprising a Group VIII noble metal and a hydrocarbon-substituted aluminium compound on a carrier is contacted with a hydrogen-containing gas at a temperature above 500°C, preferably in the range of 500 to 1000°C, more preferably in the range of 500 to 800°C, most preferably 600-750°C The activation is carried out by contacting the catalyst with the hydrogen-containing gas over a period of 15 minutes to 5 hours, preferably of 30 minutes to 3 hours
In the activating process use is made of a hydrogen-containing gas which may contain other constituents if so desired, such as diluents, e g , nitrogen, argon, or other inert gases The hydrogen-containing gas used in the activation process according to the invention preferably holds less than 10 ppm of water and less than 10 ppm of oxygen or oxygen-containing components
As indicated before, when the hydrocarbon-substituted aluminium compound is not a hydrocarbon-substituted aluminium halide, the catalyst composition should be contacted with a halogen compound, particularly a chlorine compound, either before or during the activation treatment For instance, it is possible to first contact the catalyst composition with a halogen compound at a temperature in the range of 0 to 800°C, preferably in the range of 50 to 250°C, and then activate the catalyst with hydrogen at a temperature in excess of 500°C It is also possible to carry out the activation in the presence of a halogen compound Examples of suitable halogen compounds to be used either before or in the activation step are hydrogen halides, such as hydrogen chloride, a halogen gas, a halogenated hydrocarbon, such as carbon tetrachloride chloroform, chloroethane, etc Hydrogen halides, particularly HCl, are generally preferred If the activation step is carried out in the presence of a halogen compound, the molar ratio of the halogen compound to the hydrogen gas in the activation gas is preferably in the range of 0 1 to 10, more particularly in the range of 1 to 5 When the hydrocarbon-substituted aluminium compound is a hydrocarbon- substituted aluminium compound halide, it is possible to use either a hydrogen- containing gas which does not contain any halogen compounds or a hydrogen- containing gas which contains at least one halogen compound in the activating process Generally, the use of a hydrogen-containing gas which comprises a halogen compound will lead to a catalyst with a somewhat higher activity than the use of a hydrogen-containing gas which does not comprise a halogen compound It is also possible to contact the catalyst composition comprising a hydrocarbon- substituted aluminium halide and the Group VIII metal with a halogen compound before the activation is carried out in the manner described above, but generally little benefit is derived from this The final catalyst will generally contain 0 2-15 wt % of halogen, which is preferably chlorine
The activated catalyst prepared by the process according to the invention is suitable for use in a variety of hydrocarbon conversion processes It can, for example, be used in the isomerisation of aromatic and aliphatic hydrocarbons, more particularly for isomerising n-paraffins having 4 to 12 carbon atoms It is also suitable for isomerising mixtures of different n-paraffins and mixtures of n- paraffins and aromatic hydrocarbons The catalyst according to the invention produces particularly favourable results in the case of C4, C Cs, and C? isomeπsations Preferably, the feedstock to be isomeπsed contains at least 50 wt % of paraffins to be isomeπsed The feedstock may contain olefins, but preferably less than 10%, because the presence of olefins leads to increased hydrogen consumption As is known in the art, the feed should be relatively free from sulphur components and water, because these materials act as catalyst poisons The feed generally contains up to 1 ppm of sulphur, and up to 0 5 ppm of water
The isomerisation process may take the form of the feed to be isomeπsed being contacted with the catalyst described hereinbefore in a fixed bed at a temperature in the range of 80 to 330°C, preferably of 100 to 200°C, in the presence of hydrogen The pressure in the isomerisation reactor generally is in the range of 1 to 60 bar, preferably of 2 to 40 bar, with the LHSV ranging from 0 5 to 40 h"1, preferably from 1 to 20 h'1, and the molar ratio between the hydrogen and the feed being in the range of 0 005 to 10, preferably in the range of 0 01 to 5 As those skilled in the art will know, if so desired, a minute amount of a halogen-containing compound may be incorporated into the feed in order to extend the life of the catalyst Thus, 0 001 to 1 wt %, calculated as halogen, of a hydrogen halide, a halogen gas, or a halogenated hydrocarbon, such as carbon tetrachloride, chloroform, chloroethane, chloroisopropane, etc , may be added to the feed in addition, the catalyst prepared by the process according to the invention may be used for the alkylation of alkylatable aromatic or aliphatic hydrocarbons by contacting the compound to be alkylated with an alkylating agent at a suitable temperature and pressure in the presence of the catalyst obtained by the process according to the invention Alkylating reactions are known to those skilled in the art and require no further elucidation here
Other reactions in which the catalyst prepared by the process according to the invention may be used are the dimeπsation and o gomeπsation of olefins
Example 1
About 1000 g of gamma-alumina extrudates having a purity higher than 99 9% and an overall pore volume of 0 5 mi/g (determined by mercury porosimetry) were contacted for a peπod of 4 hours with about 2 kg of an aqueous solution containing 11 8 g of chloroplatinic acid (25% platinum), 26 7 g of 37%- hydrochloπc acid, and 39 7 g of 65%-nιtπc acid Next, the extrudates were dried at 120°C for 16 hours and calcined at 550°C for 1 5 hours The platinum content of the calcined product was 0 29 wt %, the chlorine content 0 9 wt % 306 g of the calcined product were transferred to a round-bottom flask, where 320 g of a 20 wt %-ethyl aluminium dichloride solution in heptane were added to it Duπng the addition, the temperature rose from 31 °C to 54°C, subsequently, it was increased to 80°C The reaction period at 80°C was one hour During the reaction a nitrogen flow was passed over the catalyst (100 ml/min) Next, the liquid was drained from the round-bottom flask; any remaining liquid was evaporated at a temperature of 130°C under a nitrogen flow of 1300 ml/mm The product in the round-bottom flask was then heated to 640°C in a 5% hydrogen and 95% nitrogen flow (total flow. 2000 ml/min). After one hour of activating at 640°C using the same hydrogen/nitrogen flow, the product was cooled to room temperature to complete the preparation of the catalyst. A small portion (10 g) of the catalyst was transferred to a test reactor with air being excluded. The temperature was then increased to 146°C and a mixture of oil feed and hydrogen was passed over the catalyst The hydrogen/oil feed molar ratio was 3, the pressure was 30 bar, and the space velocity was 4 g of oil per g of catalyst per hour To the oil feed, composed of 42 wt.% of normal pentane, 48 wt.% of normal hexane, and 10 wt.% of cyclohexane, was added 300 ppm of Cl, in the form of CCI4. After three hours of operating, the composition of the oil product was measured. This composition was used to calculate a INC5 and a INC6 number, in which the acronym IN stands for isomerisation number, by means of the following formulae:
INC5 = iC5 x 100 iC5 + nC<
ana
INC6 = 2.2 DMB x 100
2.2 DMB + 2.3 DMB + 2 MP + 3 MP + nC6
wherein the symbols iC5, nC5, 2 2 DMB, 2 3 DMB, 2 MP, 3 MP, and nC6 are concentrations in the oil product of iC5 = isopentaπe nC5 = normal pentane 2 2 DMB = 2 2 dimethyl butane 2 3 DMB = 2 3 dimethyl butane
2 MP = 2 methyl pentane
3 MP = 3 methyl pentane πC6 = normal hexane
In the experiment described above a INC5 value of 56 and a INC6 value of 19 were determined The amount of cracking products (butane and lighter) was less than 0 3 wt %
Example 2
300 g of high purity alumina extrudates containing 0 28 wt % of Pt and 1 1 wt % of chlorine and having a pore volume of 0 5 ml/g, which were prepared by a process analogous to that described in the first paragraph of Example 1 , were transferred to a round-bottom flask The extrudates in the flask were treated with 500 ml/mm of 100% hydrogen for two hours at 400°C, after which they were cooled down to room temperature with nitrogen 376 g of a solution of 20 wt % ethyl aluminium dichloride in heptane were added to the flask During the addition, the temperature rose to 42°C subsequently it was increased to 85°C The reaction mixture was kept at this temperature for a period of one hour During the reaction a nitrogen flow was passed over the catalyst (100 ml/min) Next, the liquid was drained from the round-bottom flask, any remaining liquid was evaporated at a temperature of 130°C under a nitrogen flow of 3000 ml/min After drying, the product in the round-bottom flask was heated to 675°C in a 5% hydrogen and 95% nitrogen flow (total flow 2000 ml/mm) After one hour of activating at 675°C using the same hydrogen/nitrogen flow, the product was cooled to room temperature under 100% nitrogen to complete the preparation of the catalyst according to the invention A small portion (10 g) of the thus-prepared catalyst was transferred to a test reactor with air being excluded The temperature was then increased to 155°C and a mixture of oil feed and hydrogen was passed over the catalyst The hydrogen/oil feed molar ratio was 0 1 , the pressure was 31 bar, and the space velocity was 5 g of oil per g of catalyst per hour To the feed, composed of n- butane, was added 100 ppm of CCl After approximately 1000 minutes of operation, the composition of the effluent was determined This composition was used to calculate a INC4 number using the following formula
INC4 = ιC4 x 100 ιC4 + nC
It appeared that the INC4 was 62 5
Example 3
300 g of high purity alumina extrudates containing 0 28 wt % of Pt and 1 1 wt % of chloπne and having a pore volume of 0 5 ml/g, which were prepared by a process analogous to that described in the first paragraph of Example 1 , were transferred to a round-bottom flask The extrudates in the flask were treated with 500 ml/min of 100% hydrogen for two hours at 400°C, after which they were cooled down to room temperature with nitrogen 380 g of a solution of 20 wt % ethyl aluminium dichloride in heptane were added to the flask During the addition, the temperature rose from 28°C to 50°C subsequently it was increased to 85°C The reaction mixture was kept at this temperature for a period of one hour During the reaction a nitrogen flow was passed over the catalyst (100 ml/min) Next, the liquid was drained from the round-bottom flask, any remaining liquid was evaporated at a temperature of 130°C under a nitrogen flow of 1300 ml/mm The product was then cooled down to room temperature In this way, a comparative catalyst according to the teaching of GB 1432639 was obtained, which contained 0 26 wt % of Pt, and about 8 wt % of Cl
To obtain a catalyst according to the invention, the process for preparing the comparative catalyst according to GB 1432639 above was repeated, except that the product was subjected to an additional activation step After the removal of the remaining liquid by evaporation at a temperature of 130°C under a nitrogen flow of 1300 ml/min, the product in the round-bottom flask was heated to 640°C in a 5% hydrogen and 95% nitrogen flow (total flow 2000 ml/mm) After one hour of activating at 640°C using the same hydrogen/nitrogen flow the product was cooled to room temperature under 100% nitrogen to complete the preparation of the catalyst according to the invention
Both the comparative catalyst according to GB 1432639 and the catalyst according to the invention were subjected to the test procedure described in Example 1 above After approximately 1000 minutes of operating, the composition of the oil product was measured This composition was used to calculate a INC and a INC6 number The test results are given in the following Table
Catalyst INC5 INC6
Catalyst according to GB 1432639 15 8 3 0
Catalyst according to the invention 61 9 21 8
From this table it appears that the catalyst according to the invention, which differs from the catalyst according to GB 1432639 only in that it has been subjected to a high-temperature treatment in the presence of hydrogen, shows a highly improved isomerisation activity, as is evidenced by both a higher INC5 and a higher INC6
Example 4
250 g of high punty alumina extrudates containing 0 28 wt % of Pt and 1 1 wt % of chlorine and having a pore volume of 0 5 ml/g, which were prepared by a process analogous to that described in the first paragraph of Example 1 , were transferred to a round-bottom flask 280 g of a solution of 20 wt % triethyl aluminium in heptane were added to the flask During the addition, the temperature rose from 28°C to 52°C, subsequently it was increased to 85°C The reaction mixture was kept at this temperature for a period of one hour During the reaction a nitrogen flow was passed over the catalyst (100 ml/min) Next, the liquid was drained from the round-bottom flask. A flow of hydrochloric acid, hydrogen, and nitrogen was introduced In 35 minutes the HCl flow was increased from 120 ml/mm to 720 ml/min Within the same time frame, the nitrogen flow was decreased from 1600 ml/min to 0 ml/mtn and the hydrogen flow from 200 ml/min to 72 ml/min At that point in time, the temperature was 108°C The catalyst then was heated to 250°C in 35 minutes under a flow of 720 ml/mm of HCl and 72 ml/min of hydrogen, and kept at that temperature for two hours Then, the HCl flow was shut off and the hydrogen flow increased to 500 ml/min The temperature was increased to 350°C These conditions were maintained for one hour, after which the catalyst was cooled down to room temperature under 100% nitrogen In this way, a comparative catalyst according to the teaching of GB 952 348 was obtained, which contained about 7 2 wt % of Cl
To obtain a catalyst according to the invention, 220 g of the catalyst according to GB 952 348 prepared above were heated in the round-bottom flask to 640°C in a 5% hydrogen and 95% nitrogen flow (total flow 2000 ml/miπ) After one hour of activating at 640°C using the same hydrogen/nitrogen flow, the product was cooled to room temperature under 100% nitrogen to complete the preparation of the catalyst according to the invention
Both the comparative catalyst according to GB 952 348 and the catalyst according to the invention were subjected to the test procedure described in Example 1 above After approximately 1000 minutes of operating, the composition of the oil product was measured This composition was used to calculate a INC5 and a INC6 number for both experiments The results thereof are given in the following Table
Catalyst INCs INCe
Catalyst according to GB 952.348 31.4 8.6
Catalyst according to the invention 49 0 14 3
From this table it appears that the catalyst according to the invention, which differs from the catalyst according to GB 952.348 only in that it has been subjected to a high-temperature treatment in the presence of hydrogen, shows an improved isomerisation activity, as is evidenced by both a higher INCs and a higher INC6.

Claims

1 A process for preparing an activated catalyst composition in which a catalyst composition comprising a Group VIII noble metal and a hydrocarbon-substituted aluminium compound on an alumina carrier containing up to 20 wt % of other components is activated by contacting it with a hydrogen-containing gas at a temperature above 500X, with the proviso that at least when the hydrocarbon-substituted aluminium compound present in the catalyst composition is not a hydrocarbon- substituted aluminium halide, the catalyst composition to be activated is contacted with a halogen compound either prior to or during the activating step
2 A process according to claim 1 , characterised in that the catalyst composition to be activated is prepared by a process in which the following successive steps are carried out"
(a) the preparation of a composition comprising a Group VIII noble metal and an alumina carrier containing up to 20 wt % of other components,
(b) the optional reduction of the noble metal, and (c) the contacting of the product of step (a) or (b) with a hydrocarbon- substituted aluminium compound.
3 A process according to claim 1 or 2, characteπsed in that the hydrocarbon- substituted aluminium compound present in the catalyst composition to be activated is a hydrocarbon-substituted aluminium halide
A process according to claim 3, characterised in that the hydrocarbon- substituted aluminium halide is a hydrocarbon-substituted aluminium chloride 5 A process according to claim 3 or 4, characterised in that the hydrocarbon- substituted aluminium halide is a compound of the formula AIXyR1 nR2m, wherein X is a halogen atom, R1 and R2 may be the same or different and are selected from alkyl groups and aryl groups having 1 to 12 carbon atoms, y has the value 1 or 2, and n and m have the value 0 or 1 , with the sum of y, n, and m being 3
6 A process according to claim 1 or 2, characterised in that the hydrocarbon- substituted aluminium compound present in the catalyst composition satisfies the formula AIR1 R2R3, wherein R1 , R2, and R3 may be the same or different and are selected from alkyl groups or aryl groups having 1 to 12 carbon atoms
7 A process according to claim 6, characteπsed in that the catalyst composition comprising the hydrocarbon-substituted aluminium compound which is not a hydrocarbon-substituted aluminium halide is contacted with a halogen compound prior to the activation step being effected
8 A process according to any one of claims 3, 4, 5, or 7, characterised in that the catalyst composition is activated using a hydrogen-containing gas which does not contain any halogen compounds
9 A process according to any one of claims 3 to 7, characterised in that the catalyst composition is activated using a gas which in addition to hydrogen contains a halogen compound
10 A process according to claim 9, characterised in that the halogen compound is hydrogen chloride A process according to any one of the preceding claims, characterised in that the catalyst composition contains platinum as Group VIII noble metal
An activated catalyst composition obtainable by the process according to any one of claims 1-11
A process for the conversion of a hydrocarbon feed, characterised in that the feed to be converted is contacted with the activated catalyst composition according to claim 12
A process according to claim 13, characterised in that in a process for isomerising n-paraffins a feed containing n-paraffins is contacted with the activated catalyst composition according to claim 12 in the presence of hydrogen
A process according to claim 14, characterised in that in a process for alkylating an alkylatable aromatic or aliphatic hydrocarbon a feed containing the compound to be alkylated is contacted with an alkylating agent in the presence of the activated catalyst composition according to claim 12
PCT/EP1996/005372 1995-11-30 1996-11-28 Process for preparing a catalyst suitable for use in isomerising hydrocarbons, the catalyst thus obtained, and its use WO1997019752A1 (en)

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EP96941653A EP0863800B1 (en) 1995-11-30 1996-11-28 Process for preparing a catalyst suitable for use in isomerising hydrocarbons, the catalyst thus obtained, and its use
BR9611792A BR9611792A (en) 1995-11-30 1996-11-28 Activated catalyst composition and process for preparing the same
AU10974/97A AU718621B2 (en) 1995-11-30 1996-11-28 Process for preparing a catalyst suitable for use in isomerising hydrocarbons, the catalyst thus obtained, and its use
CA002238422A CA2238422C (en) 1995-11-30 1996-11-28 Process for preparing a catalyst suitable for use in isomerising hydrocarbons, the catalyst thus obtained, and its use
DE69614272T DE69614272T2 (en) 1995-11-30 1996-11-28 METHOD FOR PRODUCING ISOMERIZATION CATALYSTS, CATALYSTS PRODUCED THEREOF AND THEIR USE
JP52020097A JP3998044B2 (en) 1995-11-30 1996-11-28 Method for preparing a catalyst suitable for use in hydrocarbon isomerization, catalyst obtained thereby, and method of use thereof

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WO2000021662A1 (en) * 1998-10-09 2000-04-20 Akzo Nobel N.V. Preparation of an activated catalyst using an inert gas in the absence of hydrogen
WO2003074173A1 (en) * 2002-03-06 2003-09-12 Akzo Nobel N.V. Isomerisation catalyst with a specific pore size distribution
US6673977B2 (en) * 1999-12-23 2004-01-06 Total Raffinage Distribution S.A. Procedure and device for the alkylation of isobutane by light olefins
FR3128132A1 (en) 2021-10-19 2023-04-21 IFP Energies Nouvelles Catalyst comprising doped sulfated zirconium oxide

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US7611680B2 (en) * 2004-10-28 2009-11-03 Nanostellar, Inc. Platinum-bismuth catalysts for treating engine exhaust
US7605109B1 (en) * 2004-10-28 2009-10-20 Nanostellar, Inc. Platinum-bismuth catalysts for treating engine exhaust
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WO2000021662A1 (en) * 1998-10-09 2000-04-20 Akzo Nobel N.V. Preparation of an activated catalyst using an inert gas in the absence of hydrogen
US6350715B1 (en) 1998-10-09 2002-02-26 Total Raffinage Distribution S.A. Preparation of an activated catalyst using an inert gas in the absence of hydrogen
US6673977B2 (en) * 1999-12-23 2004-01-06 Total Raffinage Distribution S.A. Procedure and device for the alkylation of isobutane by light olefins
WO2003074173A1 (en) * 2002-03-06 2003-09-12 Akzo Nobel N.V. Isomerisation catalyst with a specific pore size distribution
US6822130B2 (en) 2002-03-06 2004-11-23 Akzo Nobel N.V. Isomerization catalyst with a specific pore size distribution
FR3128132A1 (en) 2021-10-19 2023-04-21 IFP Energies Nouvelles Catalyst comprising doped sulfated zirconium oxide
WO2023066714A1 (en) 2021-10-19 2023-04-27 IFP Energies Nouvelles Catalyst comprising a doped sulphated zirconium oxide

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JP3998044B2 (en) 2007-10-24
BR9611792A (en) 1999-07-13
KR19990071831A (en) 1999-09-27
US6150296A (en) 2000-11-21
JP2000501023A (en) 2000-02-02
KR100437944B1 (en) 2004-07-16
DE69614272D1 (en) 2001-09-06
DE69614272T2 (en) 2002-03-14
RU2191627C2 (en) 2002-10-27
EP0863800A1 (en) 1998-09-16
AU718621B2 (en) 2000-04-20

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